RBFC Neet Chem 7

CHEMISTRY
MODULE - 7
INDEX
S.No. Chapter Name Page No.
4. Cheical Kinetics 1 - 42
5. Surface Chemistry 43 - 83
6. General Principles and Processes of Isolation of Elements 84 - 113
9. Coordination Compounds 114 - 160
Chemical Kinetics 1
CHEMICAL
KINETICS
Chapter 04
Percentage of Questions in Last 34 Years' in NEET / AIPMT from this Chapter
A. Order of Reaction 45%

C. 27%
B. 28%
A. 45%
C. Arrhenius Equations 27%
B. 28%
WHAT DO YOU WANT TO KNOW? 4.4 TEMPERATURE DEPENDENCE OF THE RATE OF

THE REACTION
4.1 RATE OF A CHEMICAL REACTION 4.4.1 Effect of Catalyst
4.2 FACTORS AFFECTING THE RATE OF 4.5 COLLISION THEORY OF REACTION RATE
REACTION
4.2.1 Rate Law (Dependence of Rate on 4.6 SYNOPSIS
Concentrartion)
4.7 MISCELLANEOUS Questions from NCERT
4.2.2 Rate Expression and Rate Constant
4.2.3 Order of a Reaction 4.8 NCERT Exemplar Questions
4.2.4 Molecularity of a Reaction 4.9 Assertion-Reason and Statement
Based Questions from NCERT
4.3 INTEGRATED RATE EQUATIONS
4.10 Matrix Based Questions
4.3.1 Zero Order Reactions
4.3.2 First Order Reactions 4.11 ARCHIVE QUESTIONS
4.3.3 Half-Life Period 4.12 ANSWER KEY
2 Chemical Kinetics
t1/2 = 0.693 / k; st
1 order :
th
n order : 1
independent of t1/2 
2.303 [A] 1 1 [A] 0–3
concentration of k log s0 0 3
  (n – 1)kt
reactants t [A]1 [A] c [A]00 2
for nth order:
–1 (+a) –1
(mol L ) s
Collision
frequency Can be –ve, not affected by
zero or concentration of affected by unit varies
Steric factor fractional reactants temperature with order
Explained by Order Integrated Rate constant

Collision theory
Arrhenius equation Rate Law Homogenous
Temperature Concentration Catalyst Heterogenous

Frequency factor
or Arrhenius factor Lowers ES and
Factors that affect it can alter
Energy of
mechanism
Activation Rate
k 2 E s T2  T1
n   KINETICS
k1 R T1T2 OF A REACTION
Mechanism
Single Complex - many Decides rate

elementary step elementary steps Slowest step, rds law and order
4.0 INTRODUCTION P.No.: 95
 Thermodynamics tells only about the feasibility of a reaction whereas chemical kinetics tells about the rate
of reaction.
 In a spontaneous chemical reaction following questions arises.
 How fast do the chemical reaction go?
 How can the speed of a reaction change?
 What is the mechanism of a reaction?
 To answer the above question we study chemical kinetics.
 So, chemical kinetics is the branch of physical chemistry which deals with study of rates of reactions, the
mechanism by which the reactions proceed and factors affecting rate of reaction.
On the basis of rate, chemical reaction are broadly divided into three categories :-
 Very fast or instantaneous reactions : Generally these reactions involve ionic species and known as ionic
reactions. These reactions take about 10–14 or 10–16 seconds for completion. So, it is almost impossible to
determine the rate of these reactions. For example,
AgNO3  NaCl 
 AgCl  NaNO 3 ; BaCl 2  H 2SO 4 
 BaSO 4  2HCl
(white ppt) (white ppt)
 Very slow reactions : These reactions proceed very slowly, may take days or months to show any measur-
able change at room temperature. For example,
Chemical Kinetics 3
 Rusting of iron.
 Reaction between H2 and O2 to form H2O at ordinary temperature in absence of catalyst.
at room temperature
 CO  2H 2   CH3OH
 Moderate or slow reactions : This type of reactions proceed with a measurable rates at normal temperatuer
and we can measure the rate of these reactions easily. Mostly these reactions are molecular in nature. For
example,
 Decomposition of H2O2 : 2H2O2  2H2O + O2
 Decomposition of N2O5 : 2N2O5  4NO2 + O2
4.1 RATE OF A CHEMICAL REACTION P.No.: 96
 The change in concentration of either reactant or product per unit time.

dc
Formula : v  
dt
dc = change in concentration in a small interval dt.
[–] sign is used when we refer to reactant concentration.
[+] sign is used when we refer to product concentration.
Example : N2 + 3H2  2NH3
d [NH3 ]
1. Rate of formation of ammonia  
dt
d [N 2 ]
2. Rate of disappearance of nitrogen  
dt
d [H 2 ]
3. Rate of disappearance of hydrogen  
dt
1 d [NH3 ] d [N 2 ] 1 d [H 2 ]
Rate of reaction    
2 dt dt 3 dt
d [N 2 ] 1 d [NH3 ]
Thus, Rate of reaction   
dt 2 dt
or rate of formation of ammonia = Twice the rate of disappearance of nitrogen
d [NH3 ] 2  d [H 2 ] 
i.e.  
dt 3 dt 
 Units of reaction rate : Units of reaction rate = mol L–1 time–1 i.e. (mol L–1 s–1 or mol L–1 min–1 or mol L–1 h–1)
AVERAGE RATE OF REACTION P.No.: 97
 Change in the concentration of reactants or products per unit time is called average reaction velocity. If c
is the change in the concentration of reactants and product in t time, then
c
Average velocity = ±
t
Concentration
(–) Change in the concentration of reactants Product

or Average velocity =
Time
Reactant
(+) Change in the concentration of products

Time
Time
4 Chemical Kinetics
Unit of concentration gram mole

–1 –1
Unit of average velocity = Unit of time = litre×Second = gram mole litre second
INSTANTANEOUS RATE OF THE REACTION P.No.: 98

 The rate of reaction determined at specified concentration or specified
time is called instantaneous rate.
The instantaneous rate of the reaction can be determined by measuring
Concentration

concentration of reactant or product at a instant of time and plotting
concentration versus time.
 The instantaneous rate at any time is determined by the slope of the B
tangent at a point on the time-concentration curve corresponding to
the specified time. The slope of the tangent at a point is the limiting
Time
c
value of .
t
c dc
lim 
t 0 t dt
dc
 In terms of the concentration of reactant, the rate of the reaction = – . The –sign indicates that the
dt
concentration of reactant decreases with time.
dc
 In terms of the concentration of product, the rate of the reaction = + . The +sign indicates that
dt
the concentration of product increases with time. In the reaction if at a time t the concentration of product
dx
is x and at time t + dt, the concentration becomes x + dx then the reaction rate = .
dt
 2NH 3
For example the rate of reaction : N 2  3H 2 
in terms of the concentrations of N2, H2 and NH3 can be expressed as :

d [N 2 ] 1 d [H 2 ] 1 d [NH3 ]
 , ,
dt 3 dt 2 dt
4.2 FACTORS AFFECTING THE RATE OF REACTION P.No.: 100
 Concentration : Law of mass action associates that greater is the conc. of the reactants, the more rapidly
the reaction proceeds.
 Pressure (Gaseous reaction) : On increasing the pressure, volume decreases and conc. increases and
hence the rate increases.
 Temperature : It is generally observed that rise in temperature increases the reaction rate.
 Nature of the reactants : The rate depends upon specific bonds involved and hence on the nature of
reactants.
g l s
 Surface area of the reactants : In heterogeneous reactions, more powdered is the form of reactants, more
is the velocity. [as more active centres are provided]
Chemical Kinetics 5
NCERT LIKE PROBLEM NCERT P.No.-98

From the concentrations of R at different times given below, calculate the average rate of the reaction :
R  Pduring different intervals of time.
t/s 0 5 10 20 30
3 –1
10 × [R] / mol L 180 80 40 10 2.5
We can determine the difference in concentration over different intervals of time and thus determine the
rate by dividing [R] by t.
[R]1 × 103 [R]2 × 103 t2 t1 rav 103  [ R2  R1 ]  103

mol L–1 mol L–1 s s mol L–1 s –1 [t 2  t 1 ]
160 80 5 0 16
80 40 10 5 8
40 10 20 10 3
10 2.5 30 20 0.75

What should be (a) the rate of disappearance of B and (b) the rate of formation of C, if the rate of disap-
pearance of A for the reaction A + B  2C is 10–2 mole / litre / second at a particular temperature ?
(a) Rate of disappearance of A = Rate of disappearance of B

= 10–2 mole / litre / second
1
(b) Rate of disappearance of A = × Rate of formation of C
2
Rate of formation of C = 2 × Rate of disappearance of A
= 2 × 10–2 mole / litre / second
2. In a catalytic conversion of N 2 to NH 3 by Haber’s

01 process, the rate of reaction was expressed as change
P.No.: 96-98 in the concentration of ammonia per time is 40 × 10 –3
mol L–1 s–1. If there are no side reaction, the rate of the
1. For the reaction,
reaction as expressed in terms of hydrogen is (in mol
2NO(g) + 2H2(g)  N2(g) + 2H2O(g)
L–1 s–1)
The rate expression can be written in the following (1) 60 × 10–3 (2) 20 × 10–3
ways: (3) 1.200 (4) 10.3 × 10–3
d [N 2 ] d [H 2O] 3. Which of the following is the fastest reaction
 k1[NO] [H 2 ];  k2[NO] [H 2 ]
dt dt 1 250º C
(1) C  O2  CO
d [NO] d [H 2 ] 2
  k3[NO] [H 2 ];   k4 [NO] [H 2 ]
dt dt 1 500º C
(2) C  O2  CO
The relationship between kl, k2, k3, k4 is 2
(1) k2 = kl = k3 = k4 1 750º C
(2) k2 = 2kl = k3 = k4 (3) C  O2  CO
2
(3) k2 = 2k3 = k1 = k4
1 1000º C
(4) k2 = kl = k3 = 2k4 (4) C  O2   CO
2
6 Chemical Kinetics
1 7. The rate constant of the reaction
4. For a reaction A 
 2 B , rate of disappearance of 2H2O2 (aq)  2H2O (l) + O2(g) is 3 × 10–3 min–1
2
‘A’ is related to the rate of appearance of ‘B’ by the At what concentration of H2O2, the rate of the reaction
expression: will be 2 × 10 –4 Ms–1?
d [ A] 1 d [ B] d [ A] 1 d [ B] (1) 6.67 × 10–3(M) (2) 2 (M)
(1)   (2)  
dt 2 dt dt 4 dt (3) 4 (M) (4) 0.08 (M)
d [ A] d [ B] d [ A] d[B] 8. In the formation of sulphur trioxide by the contact
(3)   (4)  4
dt dt dt dt 
process, 2SO2 + O2N  
 2SO3, the rate of reaction
5. 

For the reaction H2(g) + I2(g) 
 2HI(g), the rate of d [O2 ]
reaction is expressed as was measured as = 3.0 × 10 –4 mol L–1 s–1. The
dt
[I 2 ] [H 2 ] 1 [HI] rate of reaction expressed in terms of SO3 will be
(1)   
t t 2 t (1) 3.0 × 10–4 mol L–1s–1 (2) 6.0 × 10–4 mol L–1s–1
[I 2 ] [H 2 ] [HI] (3) 1.5 × 10–4 mol L–1s–1 (4) 4.5 × 10–4 mol L–1s–1
(2)   dB
t t 2t 9. If 3A  2B, then the rate of reaction of  is equal to
[H 2 ] 1 [I 2 ] [HI] dt
(3)   d [ A] 1 d [ A]
t 2 t t (1) 2 (2) 
(4) None of these dt 3 dt
6. Observe the following reaction: 2 d [ A] 3 d [ A]
(3)  (4) 
A(g) + 3B(g)  2C(g) 3 dt 2 dt
  d [ A]  10. The reduction of peroxydisulphate ion by I – ion is
The rate of this reaction   is 3 × 10–3 mol litre–1
expressed by S 2O82   3 I   2 SO42   I 3 . If rate of
 dt 
d [ B] disappearance of I – is 9/2 × 10 –3 mol L–1 S–1, what is the
min–1. What is the value of in mol litre–1 min–1? rate of formation of SO42  during same time?
dt
(1) 3 × 10–3 (2) 9 × 10–3 (1) 10 –3 mol/L–1 s–1 (2) 2 × 10 –3 mol L–1 s–1
(3) 10–3 (4) 1.5 × 10–3 –3
(3) 3 × 10 mol L s –1 –1
(4) 4 × 10 –3 mol L–1 s–1
4.2.1 P.No.: 100

 The experimental expression of rate of reaction in terms of concentration of reactions is known as rate law.
In this expression the rate of a reaction is proportional to the product of molar concentration of reactants
with each term raised to a power or exponent that has to be found experimentaly.
In a chemical reaction : aA + bB  Product
The rate law is : Rate  [A]x [B]y
 The values of exponents x and y are found experimentaly which may or may not be same as stoichiometric
coefficients.
Above relationship can be written as :
Rate = k [A]x [B]y
Where k is a proportionality constant known as rate constant.
4.2.2 P.No.: 100

 For a general reaction
aA + bB  cC + dD ;
According to law of mass action
Rate = k [A]a [B]b
But according to rate law (experimental concept)
Rate = k [A]x [B]y
Where x + y = n = order of reaction
If [A] = [B] = 1 mol/L then, Rate = K
Chemical Kinetics 7
Rate of reaction at unit concentration of reactants is called as rate constant or specific reaction rate.
Rate constant does not depands on concentration of reactant but it depands on temprature and catalyst.
Rate
k
[A]x [B] y
Concentration 1
   (concentration)(1 n ) time1
time (concentration) n
 Taking SI units of concentration, mol L–1 and time, s, the units of k for different reaction order can be
determined.
For gaseous reaction unit of k may be = (atm) 1 – n × tim–1
1. Zero order reaction : (n = 0)
mol L1 1
k   mol L1 s 1
s (mol L1 )
2. First order reaction : (n = 1)
mol L1 1
k   s 1
s (mol L1 )1
3. Second order reaction : (n = 2)
mol L1 1
k   mol1 L s 1
s (mol L1 )2
4. Third order reaction : (n = 3)
mol L1 1
k  1 3
 mol2 L2 s 1
s (mol L )
4.2.3 P.No.: 102

 The sum of powers of concentration of of reactants in rate law expression is known as order of reaction.
For the reaction : aA + bB  Product
Rate law is : rate = k [A]x [B]y
Here, x = order of reaction with respect to A, y = order of reaction with respect to B
x + y = n (overall order of reaction)
Order of reaction may be zero, positive, negative or fractional.
Order of reaction is an experimental quantity.
SOME COMMON EXAMPLE OF REACTIONS OF DIFFERENT ORDERS :
 Zero Order Reaction :
Pt
2NH3 (g)   N 2 (g)  3H 2 (g)
h
H 2 (g)  Cl2 (g)   2HCl ; Rate = k [H2]°[Cl2]°
 First Order :
1
H 2 O 2 
 H2O  O2 ; Rate = k [H2O2]
2
 Second Order :
CH3COOH + C2H5OH  CH3COOC2H5 + H2O ; Rate = k [CH3COOH] [C2H5OH]
 Fractional Order Reaction :
CH3CHO  CH4 + CO ; Rate = k [CH3CHO]3/2
ELEMENTARY REACTION P.No.: 102

 Those reactions which completes in single step and which have exponents in rate law equal to stoichiometric
coefficients of the reactions.
8 Chemical Kinetics
If A + B  Product ; is an elementary reaction
then rate law will be :
Rate = k [A][B]
 Zero order reactions can never be elementary reactions.
 For elementary reactions fractional order is not possible.
COMPLEX REACTIONS P.No.: 102

Those reactions which complete in multisteps. For these reactions a mechanism is proposed.
 For complex reactions the overall rate of reaction is controlled by the slowest step which is called as rate
determining step.
 In rate law expression rate of reaction depends on concentration of reactants of slowest step which must be
free from intermediate. For example,
2NO2Cl  2NO2 + Cl2
Experimentally, the rate law is Rate = k [NO2Cl]
The mechanism of the reaction is given as :
1. NO2Cl  NO2 + Cl (slow step)
2. NO2Cl + Cl  NO2 + Cl2 (fast step)
So the rate law from slowest step ; Rate = k [NO2Cl]
In this way the predicted rate law derived from two step mechanism agrees with experimental rate law.

d [A]
In the reaction, A + 2B  6C + 2D, if the initial rate – at t = 0 is 2.6 × 10–2 M sec–1, what will be
dt
d [B]
the value of – at t = 0 ?
dt
(A) 8.5 × 10–2 M sec–1 (B) 2.5 × 10–2 M sec–1 (C) 5.2 × 10–2 M sec–1 (D) 7.5 × 10–2 M sec–1
(C) From the reaction it is evident that when a mole of A is reacting, 2 moles of B must react. Hence the
decrease in the concentration of B must be twice that of A
d [B]  d [A] 
   2 
dt  dt 
= 2 × 2.6 × 10–2 = 5.2 × 10–2 M sec–1

The dimensions of rate constant of a second order reaction involves :
(A) time and concentration (B) neither time nor concentration
(C) time only (D) concentration only
Rate mol L–1s 1 s 1

(A) k  2
 –1 2
 –1
 (mol L–1 ) –1 s 1
[A] (mol L ) mol L

The rate constant of a reaction has same units as the rate of reaction. The reaction is of
(A) zero order (B) first order (C) second order (D) none of these
(A) For a zero order reaction, r = k [A]°. Thus the units of k are the same as that of rate of reaction.
Chemical Kinetics 9
4.2.4 P.No.: 102
 ‘‘Molecularity is defined as the number of molecules, atoms, or radicals that must collide simultaneously in
order for the reaction to take place.’’ It is always a whole number and cannot be negative.
In the elementary processes :
Participating species Molecularity
One species participates ..... unimolecular, 1
Two species participates ..... bimolecular, 2
Three species participates ..... trimolecular, 3
For example,
N2O4  2NO2 ...... unimolecular
H2 + I2  2HI ...... bimolecular
2FeCl3 + SnCl2  2FeCl2 + SnCl4 ...... trimolecular
Note : If the reaction takes place in two or more steps then the overall molecularity of the reaction is
monitored by the slow or rate determining step.
DIFFERENCE BETWEEN MOLECULARITY AND ORDER OF REACTION
S.No. Molecularity Order of Reaction
1 Molecularity can neither be zero nor fractional Order of a reaction can be zero, fractional
or integer
2 It is the number of molecules of reactants It is sum of power raised or the rate
concentration terms taking part in elementary expression.
step of a reaction.
3 It can not have negative value. Order of a reaction may have negative
value.
4 Molecularity is a theoretical property. Order is an experimental property.
5 Molecularity concerns with mechanism. Order concerns with kinetic (rate law).

For a chemical reaction, A  products, the rate of reaction doubles when the concentration of A is
increased by 4 times. The order of reaction is
(A) 4 (B) 0 (C) 1/2 (D) 1
(C) r = k [A]n ...(i) ; 2r = k [4A]n ...(ii)

n
2r k  4A 
Dividing (ii) by (i) 
r k  A 
or 2 = 22n or 2n = 1 or n = 1/2

For a hypothetical reaction
A + B  products, the rate law is, r = k [B] [A]°, the order of reaction is :
(A) 0 (B) 1 (C) 2 (D) 3
(B), 1 + 0 = 1
10 Chemical Kinetics

The slowest step of a particular reaction is found to be
1
X + Y2  XY2
2 2
The order of the reaction is
(A) 2 (B) 3 (C) 3.5 (D) 1.5
(D) r = k [X2]1/2 [Y2]1

 Order = 0.5 + 1 = 1.5

For a reaction ; 3A  Products, it is found that the rate of reaction doubles if concentration of A is
increased four times, calculate order of reaction.
Rate = k [Reactant]n = 4a ; rate = 2r1

r1 = k [a]n if [Reactant] = 4a ; rate = 2r1
n
1 1 1
2r1 = k [4a] ; n   n
2 4 2
02 14. For a reactions A + B  product, it was found that rate

of reaction increases four times if concentration of ‘A’
P.No.: 99-103 is doubled, but the rate of reaction remains unaffected.
If concentration of ‘B’ is doubled. Hence, the rate law
11. In a reaction 2A + B  A2B, the reactant A will disappear for the reaction is
at (1) rate = k[A][B]
(1) Half the rate that B will decrease (2) rate = k[A]2
(2) The same rate that B will decrease (3) rate = k[A]2[B]1
(3) Twice the rate that B will decrease (4) rate = k[A]2[B]2
(4) The same rate that A2B will form
15. Units of rate constant of first and zero order reactions
12. For a reaction 2A + B  Products, doubling the initial in terms of molarity M are respectively:
concentration of both the reactants increases the rate (1) s–1, M L–1 s–1
by a factor of 8, and doubling the concentration of B
(2) s–1, M
alone doubles the rate. The rate law for the reaction is
(3) Ms–1, s–1
(1)  = k[A][B]2
(4) M, s–1
(2)  = k[A]2[B]
(3)  = k[A][B] 16. For the irreversible process, A + B  products, the rate
is first-order w.r.t. A and seconds-order w.r.t. B. If 1.0
(4)  = k[A]2[B]2
mol each of A and B introduced into a 1.0 L vessel, and
13. The rate of a gaseous phase reaction becomes half if the initial rate was 1.0 × 10 –2 mol L–1s–1, rate when half
volume of container is doubled. Order of reaction is reactants have been turned into products is:
(1) 1 (1) 1.25 × 10–3 mol L–1 s–
(2) 1/2 (2) 1.0 × 10–2 mol L–1 s–
(3) 2 (3) 2.50 × 10–3 mol L–1 s–
(4) 1/3 (4) 2.0 × 10–2 mol L–1 s–
Chemical Kinetics 11
17. Trimolecular reactions are uncommon because 21. The rate of the first-order reaction X  products is
(1) The probability of three molecules colliding at an 7.5 × 10 –4 mol L–1 min–1. What will be the value of rate
instant is low constant when the concentration of X is 0.5 mol L–1?
(2) The probability of three molecules colliding at an (1) 3.75 × 10–4 s–1
instant is high (2) 2.5 × 10 –5 s–1
(3) The probability of three molecules colliding at an (3) 1.5 × 10 –3 s–1
instant is zero (4) 8.0 × 10 –4 s–1
(4) The probability of many molecules colliding at an 22. The rate of the reaction, 3A + 2B  Products is
instant is high given by the rate expression: Rate = k[A] [B] 2 .
18. For a reaction A  B, the rate of reaction quadrupled If A is taken in excess, the order of the reaction
when the concentration of A is doubled. The rate would be:
expression of the reaction is r = K[A] when the value (1) 3 (2) 2
of n is (3) 1 (4) 5
(1) 1 (2) 0 23. The rate law of a reaction A + B  Product is rate = K
(3) 3 (4) 2 [A] n [B] m. On doubling the concentration of A and
halving the concentration of B, the ratio of new rate to
19. For the reaction H2 + Br2  2HBr overall order is
the earlier rate of reaction will be:
found to be 3/2. The rate of reaction can be expressed
as: (1) n – m (2) 2 n – m
(1) [H2] [Br2]1/2 1
(3) m n (4) m+n
(2) [H2]1/2 [Br2] 2
(3) [H2]3/2 [Br2]0
24. The rate of reaction between A and B increases by a
(4) All of these
factor of 100, when the concentration of A is increased
20. The rate of the reaction 10 folds. The order of reaction with respect to A is
CCl3CHO + NO  CHCl3 + NO + CO is given by Rate = (1) 10 (2) 1
K[CCl 3CHO][NO]. If concentration is expressed in (3) 4 (4) 0
moles/litre, the units of K are
25. Fo r a reaction A + 2B  C, rate is given by
(1) litre2 mole–2 sec–1
R = K [A] [B] 2. The order of reaction is:
(2) mole litre–1 sec–1
(3) litre mole–1 sec–1 (1) 3 (2) 6
(4) sec –1 (3) 5 (4) 7
4.3 INTEGRATED RATE EQUATIONS P.No.: 105
4.3.1 P.No.: 105
 Reactions in which rate of reaction remains independent of initial concentration of the reactant are said to
be zero order reactions.
 Zero order reactions are relatively uncomon but they occur under special conditions. Some enzyme catalysed
reactions and reactions which occur on metal surfaces are a few examples of zero order reactions.
For example,
h
1. H 2 (g)  Cl2 (g)   2HCl(g)
Pt
2. 2NH3 (g) 

 N 2 (g)  3H 2 (g)
3. Reaction between Acetone and Bromine.
4. Dissociation of HI on gold surface.
5. Adsorption of gases on metal surface.
 Differential Rate Equation
A  Product
t 0 a 0
t  t sec (a  x) x
d [A]
  k[A]0
dt
dx
 k[A]0
dt
 Calculation of Rate Constant
Let us take the reaction
A 
 Product
d [A]
  k[A]0 = k
dt
  d [A]   kdt
– [A]t = kt + C
At t = 0 [A]f = [A]0
– [A]0 = k × 0 + C
C = – [A]0
On substituting the value of C [A]t Slope = – l
– [A]t = kt – [A]0
[A]t = [A]0 – kt [Intergrated rate equation]
y = c – mx t
[A]0 – [A]t = kt
[ A]0  [ A]t x x
k  Slope = k
t t
x = kt
t
x = Amount of reactant that will change in product.
 For zero order reaction, rate of reaction is equal to rate constant.
 Unit of rate constant
k = mol L–1 s–1 = unit of rate of reaction.
 Half-life period : The time in which half of the initial amount is consumed.
[A]0
At t = t1/2, [A]t 
2
[A]0 [A]0
 k t1/2  [A]0  or t1/ 2 
2 2k
 The half life period for a zero order reaction is directly proportional to the initial concentration of the
reactants.
 Time for completion of reaction
[A]t = [A]0 – kt
For completion [A]t = 0
[A]0 [A]0
k t100% 
t k
 Graphical representawtion
Zero Order
Rate t1/2
Concentration [A]0
4.3.2 P.No.: 106
 Reactions in which the rate of reaction is directly proportional to concentration of reactant.

For example,
1. 2N2O5  4NO2 + O2
2. NH4NO2  N2 + 2H2O
3. CH3COOC2H5 + H2O  CH3COOH + C2H5OH
4. 2H2O2  2H2O + O2
5. All radioactive decay
 Differential rate equation
A 
 Product
t 0 a 0
t  t sec (a  x) x
d [A] dx
  k[A]  k (a  x)
dt dt
 Calculation of rate constant
d [A]
  k  dt
[A]
– ln [A]t = kt + c ...(i)
At t = 0; [A]t = [A]0  C = – ln [A]0
Putting the value of C in equation (i)
– ln [A]t = kt – ln [A]0
ln [A]t = ln [A]0 – kt
y = c – mx
[A]0
ln  kt ...(ii)
[A]t
Slope = – k
 a 
kt  ln  
ax t
[A]0
2.303 log10  kt
[A]t
2.303 [A]0
k log
t [A]t
From equation (ii)
[A]0
 e kt [A]t
[A]t
[A]t
 e kt  [A]t = [A]0 e–kt Wihelmy equation t
[A]0
 Unit of rate constant : [k = time–1]
4.3.3 P.No.: 110
The time in which half of the initial amount of reactant is consumed.

At t = t1/2 ; x=a/2;a–x=a/2
1  a  ln 2 2.303 0.693
t1/ 2  ln   or t1/ 2 
 (log 2) or t1/ 2 
k a/ 2 k k k
Half-life period for first order reaction is independent of the initial concentration of reactant.
 Time for 3/4th of the Reaction (t3/4) : The time in which 3/4th of the initial amount of reactant is consumed.
At t = t3/4 ; x = 3a / 4 ; a – x = a / 4.
2.303 2.303
t3/ 4  (log 4)   2log 2  2  t1/2
k k
t3/4 for first order reaction is independent of the initial concentration of reactant.
 Interval Formula
2.303 a  x1
k log
t2  t1 a  x2
where x1 and x2 be the amounts consumed up to the time t1 and t2 respectively.
Time required for the completion of definite fraction fo the first ordr reaction is independent of the initial
concentration of the reactant.
 Graphical Representation
k
Slope =
log (a – x)
2.303
Rate
t1/2
  
Concentration a a

The t1/2 of first order reaction is 60 minutes. What percentage will be left after 240 minutes?
0.693 0.693
k 
t1/ 2 60
2.303 [A ]
t log 0
k [At ]
2.303 [A ]
240  log 0
 0.693  [A t ]
 
 60 
4  0.693 [A ]
 log 0
2.303 [A t ]
A0
At   0.0625[A 0 ]
16
[At] = 6.25% of [A0]

A first order reaction has a specific reaction rate of 10–3 s–1. How much time will it takes for 10 gm of the
reactant to reduce to 2.5 gm?
2.303 [A ]
k log 0
t [A t ]
2.303 10
t 3
log
10 2.5
t = 2303 × 0.301 × 2 = 1386 s.

A first order reaction is found to have a rate constant k = 7.39 × 10–5 s–1. Find the half life of this reaction.
For first order reaction

2.303 a
k log
t ax
a
For t = t1/2, x 
2
2.303 a
t1/ 2  log
k a
a
2
2.303
 log 2
k
2.303  0.3010
 = 9.38 × 103 s.
7.39  105
t0.75
Calculate t for a 1st order reaction :
0.50
2.303 C 2.303 C t log 4 2log 2

k log 0  log 0  3/4   2
t3/4 1 t1/2 C 0 t1/ 2 log 2 log 2
C0
4 2
SECOND ORDER REACTIONS (NOT IN NCERT)

1  1  1 1
 For second order : n = 2 kt   
(2  1)  (a  x)  (a  x) a
1 =k t1/2
pe
(a – x) Sl o 1
1 slope =
Half life t1/2  k
ak 1/a
t 1/a

90% of a first order reaction was completed in 10 hours. When will 99.9% of the reaction complete?
2.303 a
k1  log , a = 100, x = 90, t = 10
t ax
2.303 100
So, k1  log  2.303  101 hour 1
10 10
Now for 99.9% completion : a = 100 and x = 99.9
2.303 100 2.303
t log   3  30 hours
k1 0.1 2.303  101

20% of a first order reaction was completed in 5 min. When will 60% of the reaction complete?
t = 5 min, a = 100, x1 = 20
2.303  a  2.303 100 2.303 5 2.303
k log   log  log  [log 5  log 4]
t  a  x1  5 80 5 4 5
2.303 2.303
k [0.6989  0.6020]  [0.0969]  0.0446
5 5
Now x2 = 60
2.303  a 
k log  
t  a  x2 
2.303 100 2.303 2.303
t log  [log5  log 2]   0.3979  20.55 min.
0.0446 40 0.0446 0.0446

For the first order reaction, half life is 6 min. Calculate the rate constant of the reaction?
0.693 0.693 0.693

t1/ 2   k1    0.1155 min 1
k1 t1/2 6
HALF-LIFE METHOD P.No.: 110

1
 Relation between half-life period of a reaction and initial concentration is as follows : t1/ 2 
a n 1
For first order reaction (Half life  a0)
For second order reaction (Half life  1/a)
For third order reaction (Half life  1/a2)

For a first order reaction, t0.75 is 1386 seconds. Therefore, the specific rate constant is
(A) 10 –1 s –1 (B) 10 –3 s –1 (C) 10–2 s –1 (D) 10–4 s –1
1386 0.693
(B) t0.75 = 1386 s = 2 × t0.5 ; t0.5   693 s ; k  1 103 s 1
2 693 s
0.693
t1/2 of first order reactions is given by , t3/4 would be equal to
k
0.693 0.346 1.386 0.924
(A) (B) (C) (D)
k k k k
2  0.693 1.386
(C) t3/4  2(t1/ 2 )  
k k
PSEUDO UNIMOLECULAR REACTION P.No.: 112
 A chemical reaction in which value of order of reaction is one but molecularity is more than one are known
as pseudo unimolecular / pseudo first order reaction. For example,
 Hydrolysis of ester in acidic medium.

H
CH3COOC2H5 + H2O   CH3COOH + C2H5OH
Rate = k [CH3COOC2H5] [H2O]
Water is in excess then its concentration remain constant during the reaction and [H2O] is taken as
constant therefore,
Rate = k' [CH3COOC2H5] where k' = k [H2O]
 Inversion of cane sugar.

H
C12 H 22 O11  H 2 O   C6 H12 O 6  C6 H12 O 6
Cane sugar Glucose Fructose
Rate = k [C12H22O11] [H2O]

Water is in excess then its concentration remain constant during the reaction and [H2O] is taken as
constant therefore,
Rate = k' [C12H22O11] where k' = k [H2O]
03 31. A first-order reaction which is 30% complete in 30

minutes has a half-life period of
P.No.: 105-112 (1) 24.2 min (2) 58.2 min
(3) 102.2 min (4) 120.2 min
26. Which of the following is an example of pseudo
unimolecular reaction? 32. The half-life for the reaction,
H 
1
(1) CH3COOCH3 + H2O  

N 2O5 
 2 NO2  O2 in 24 hr at 30°C. Starting
CH3COOH + CH3OH 2

with 10 g of N2O5 how many grams of N2O5 will remain
H
(2) CH3COOCH3+H2O  after a period of 96 hours?
CH3COOH + CH3OH (1) 1.25 g (2) 0.63 g
(3) 2FeCl3 + SnCl2  SnCl4 + 2FeCl2 (3) 1.7 g (4) 0.5 g
(4) NaOH + HCl  NaCl + H2O 33. Half-life of a reaction is found to be inversely
27. In a first order reaction the concentration or reactant proportional to the cube of its initial concentration.
decreases from 800 mol/dm3 to 50 mol/dm3 in 2 × 10 2 The order of reaction is
sec. The rate constant of reaction in sec–1 is (1) 2 (2) 5
(1) 2 × 104 (3) 3 (4) 4
(2) 3.45 × 10–5
34. The rate for a first order reaction is 0.6932 × 10 –2 mol
(3) 1.386 × 10–2
L–1 min–1 and the initial concentration of the reactants
(4) 2 × 10–4
is 1 M, T 1/2 is equal to
28. The rate constant for a second order reaction is (1) 6.932 min
8 × 10–5 M–1 Min–1. How long will it take a 1 M solution (2) 100 min
to be reduced to 0.5 M
(1) 8 × 10–5 min (3) 0.6932 × 10–3 min
(2) 8.665 × 103 min (4) 0.6932 × 10–2 min
(3) 4 × 10–5 min 35. 99% at a first order reaction was completed in 32 min.
(4) 1.25 × 104 min When will 99.9% of the reaction complete?
29. A reaction that is of the first order with respect to (1) 48 min (2) 46 min
reactant A has a rate constant 6 min–1. If we start with (3) 50 min (4) 45 min
[A] = 0.05 mol l–1, when would [A] reach the value 0.05 36. Which graph rep resents zero -order reaction
mol l–1 [A (g)  B (g)]?
(1) 0.384 min
(2) 0.15 min
(3) 3 min d[A]
(4) 3.84 min [B]
(1) (2) dt
30. What is the order of a chemical reaction that obeys the t t
1
1 expression tip t1/ 2  ?
k.a
(1) first t1/2 t3/4
(2) second (3) (4)
(3) third
(4) fourth
[A]0 [A]0
37. For which order reaction a straight line is obtained 39. t1/4 can be taken as the time taken for concentration
along with x-axis by plotting a graph between half-life of reactant to drop to ¾ of its initial value. If the
(t1/2) and initial concentration 'a' rate constant for a first order reaction is K, then t1/4 can
be written as:
(1) 1 (2) 2
(1) 0.10/K (2) 0.29/K
(3) 3 (4) 0
(3) 0.69/K (4) 0.75/K
1 40. A reaction which is of first order with respect to reactant
38. For a given reaction t1/ 2  . The order of the ‘A’ has a rate constant of 6.0 min–1. If we start with
Ka
reaction is [A] = 0.5 mol L–1, when will [A] reach the value of
0.05 mol L–1?
(1) 1 (2) 0
(1) 0.384 min (2) 0.15 min
(3) 3 (4) 2 (3) 3 min (4) 3.84 min
4.4 TEMPERATURE DEPENDENCE OF THE RATE OF THE REACTION P.No.: 112
 On increasing temperature rate of reaction increases whether the reaction is exothermic or endothermic.
 When temperature increases KE of molecules increases, number of activated molecules increases thus rate
of reaction increases.
RELATION BETWEEN RATE CONSTANT AND TEMPERATURE :

 Generally it is found that for every 10°C rise in temperature Rate of reaction becomes 2 to 3 times.
 Temperature coefficient (µ) : It is defined as ratio of rate constant of a reaction at two different tempera-
ture which will be differ by 10°C.
KT 10 r2 K 2
  2 to 3 ;    T /10
KT r1 K1
If temperature of reaction is not specified then consider 25°C.
(If µ is not given consider it as minimum 2)
MAXWELL AND BOLTZMANN ENERGY DISTRIBUTION CURVE P.No.: 114
most probable KE
at T
Fraction of molecules
(N E / N T )
at (T + 10)
threshold
energy
KT of reactant
ARRHENIUS EQUATION P.No.: 115
K  Ae Ea / RT ...(1)
A = Arrhenius constant / pre-expoential factor / Frequency factor
Ea = Activation energy
R = gas constant
T = Temperature (Kelvin)
 K increases with increase in temperature
If T   ; K  A
K
  e  Ea / RT = fraction of molecules having energy
A
e  Ea / RT  Boltzman factor
On taking logrithm for equation (1) on both sides.
ln K  ln A  ln e Ea / RT
Ea
2.303 log10 K  2.303 log10 A  Ea
RT –
log10 K 2.303 R
Ea
log10 K  log10 A 
2.303RT 1/T ...(2)
y  c  mx
 Ea of reaction can be determined by measuring rate cosntant at two different temperature
At temperature T1 :
Ea
log10 K1  log10 A  ...(3)
2.303RT1
At temperature T2 :
Ea
log10 K 2  log10 A  ...(4)
2.303RT2
Equation (4) – Equation (3) gives :
Ea  1 1 
log K 2  log K1    
2.303R  T1 T2 
K2 Ea  T2  T1 
log10   
K1 2.303R  T1T2 
4.4.1 P.No.: 116
 If k and kcat be the rate constant of a reaction at a given temperature T, and Ea and E 'a are the activation
energies of the reaction in absence and presence of catalyst, respectively, the
kcat Ae  E 'a / RT
  Ae( Ea  E 'a ) RT
k Ae  Ea / RT
kcat
Since Ea  E 'a is positive so kcat > k. the ratio gives the number of times the rate of reaction will
k
increase by the use of catalyst at a given temperature
 The rate of reaction in the presence of catalyst at any temperature T1 may be made equal to the rate of
reaction in absence of catalyst but for this sake we will have to raise the temperature. Let this temperature
be
E 'a Ea
T2  e E 'a / RT1  e  Ea / RT2 or 
T1 T2
Catalyzed pathway Uncatalyzed pathway
Potential energy
Potential energy
Ea Ea
Reactants Reactants
Products Products
Reaction progress Reaction progress

(a) (b)
RDS(RATE DETERMINE STEP) IS HAVING INTERMEDIATE ON REACTANT SIDE (NOT IN NCERT)

 To calculate order, we have to specify [ intermediate] in expression of rate law in terms of conc. of [R], [P]
or catalyst with the help of same equilibrium step given in mechanism.

2O3  3O2

k1
O3  
 O2  O
k 2
(Intermediate)
(fast eq. step)
k3
O  O3   2O 2 (slow)
From R.D.S., rate = k3 [O3] [ O]
According to equilibrium step.

k1 [O2 ][O]
K eq  
k2 [O3 ]
 k [O ] 
[O]   1 3 
 k 2 [O 2 ] 
 k1[O3 ] 
Rate = k3 [O3] [O]  k 3 [O3 ]  k [O ]  .
 2 2 
k1k 3 [O3 ]2
Rate 
k 2 [O 2 ]
4.5 COLLISION THEORY OF REACTION RATE P.No.: 116
 This theory was given by Max Trautz and William Lewis. According to it, for a reaction to occur there must
be collision in between reacting molecules.
 Total number of collisions per second in unit volume is called collision frequency(z). Generally its value is
very high for gaseous reactions (10 25 to 10 28 collisions / sec-cm3. But only a small fraction of these
collisions are capable to convert reactant into product. These collisions are called as effective collisions.
 For effective collision following two conditions must be satisfied at a time :
1. Reacting molecules must posses a minimum amount of energy.
2. Proper oreintation of collision
 Threshold energy : The minimum energy which must be possesedd by reacting molecules for a
chemical reaction to occur.
 Activation energy : The minimum extra amount of energy required by reactant molecules for con-
verting into products.
Endothermic reaction
1. Ea (f) = Activation energy for forward reaction
2. Ea (b) = Activation enerlgy for backward reaction
If not specified in questions then consider Ea for forward reaction.
H = Ea(f) – Ea(b) ; H = HP – HR
ACTIVATION ENERGY MAINLY DEPENDS UPON :

 Nature of reactant : For different reactants, number of bonds and bond energies are different, therefore
activation energy will also be different. Reactions which have less Ea, take place at faster rate.
 Presence of reactant : Catalyst provide an alternative path of reaction mechanism for the reaction.
 In presence of positive catalyst threshod energy decreases, activation energy decreases and rate of
reaction increases.
 In presence of negative catalyst threshold energy increases, activation energy increases, rate of reac-
tion decreases.
 Orientation :
A A A A A A
Case-I : Proper orientation
B B B B B B
Activated Products
complex
Reactant (transition state)
A
A
A A
A A
Case-II : Improper orientation B B B
B B B
Reactant No Product
Limitations :
1. This theory is mainly applicable for gaseous reactions and also for solutions in which reacting species
are molecules.
2. This theory is mainly applicable for simple bimolecular reactions but fails for complex reactions.
3. It considers molecules to be hard sphere and ignors structural aspect of molecules.

The Ea of exothermic reaction A  B is 80 kJ/mol. Heat of reaction is 20 kJ/mol. Ea for the reaction B
 A will be?
H  Ea ( f )  Ea (b )   20  80  Ea (b )
Ea(b) = 100 kJ/mol

For the reaction A + B  C + D the activation energy is 32 kJ/mol. For the reverse reaction the Ea is 58
kJ/mol. Determine (i) Nature of reaction (ii) H
H = Ea(f) – Ea(b)
H = 32 – 58
H = – 26 kJ/mol (exothermic)

An exothermic chemical reaction is occuring in two steps as follows
(i) A + B  X (slow) 2. X  AB (fast)
E E
(A) A+B AB (B) A+B AB

t t
E E
(C) (D) AB
A+B x A+B x
AB
t t

Ethylene oxide is decomposed into CH4 and CO. Rate constant for this reaction may be described by the
1.25×104
equation l og k (s–1) = 14.34 –
T
(i) What will be the energy of activation of this reaction ?
(ii) What will be the value of k at 670 K ?
(iii) At what temperature will its half-life period be 25.6 minutes ?
Ea
(i) We know, log10 k  log10 A  ...(i)
2.303RT
1 1.25  104
Given, log k ( s )  14.34  ...(ii)
T
Comparing Eqs. (i) and (ii), we get
Ea
 1.25  104
2.303R
(ii) Ea = 1.25 × 104 × 2.303 × 8.314 × 10–3
 Ea = 239.339 kJ/mol
Substituting the value of T (670 K) in Eq. (ii),
1.25  104
log k ( s 1 )  14.34   4.3167
670
 k = 4.82 × 10–5 s–1
0.693 0.693
(iii) k  t   0.000451sec1
1/2 256  60
 log 0.000451 sec–1
1.25  104
= 14.34 –  T = 706.79 K
T

Explain on the basis of temprature coeff. of rate const. that equilibrium of endothermic reaction shifts in
forward direction on increasing temprature while equilibriums of exothermic shift back.
 keq.1  H 1 1 
ln     
 keq.2  R  T1 T2 
 
H = Eaf – Eab > 0 (for endothermic)

Eaf > Eab
On increasing temp. kf  more than kb
Equilibrium will shift in forward direction.

Value of rate constant for a first order reaction at 500 K is 1.60 × 10–5 second–1, whereas at 600 K, it is 6.36
× 10–3 second–1. Find out the activation energy of the reaction.
k   Ea  1 1 
log  1     
 k2  2.303R  T1 T2 
– Ea  1 1 
log 1.60 × 10–5 – log 6.36 × 10–3 = –
2.303  8.314  500 600 

Ea 1
5.241  3.8035   Ea  2.5999  19.15  3000
19.15 3000
Ea = 1.49 × 105
04 43. Which of the following statements is not true according

to collision theory of reaction rates?
P.No.: 113-117 (1) Collision of molecules is a precondition for any
reaction to occur
1 (2) All collisions result in the formation of the
41. Figure shows a graph in log10 K vs where K is rate
T products
constant and T is temperature. The straight line BC (3) Only activated collisions result in the formation
of the products
1 (4) Molecules which have acquired the energy of
has 1 slope, | tan  | and an intercept of 5 on
2.303 activation can collide effectively
y-axis. Thus EA, the energy of activation is:
44. The activation energies of two reactions are Ea1 and
B Ea2 with Ea1 > Ea2. If the temperature of the reacting
systems is increased from T to T’, which of the following
is correct?
log10K
C
K1' K 2' K1' K'
(1)  (2) 2 2
A 1/T K1 K 2 K1 K2
(1) 2.303 × 2 cal K1' K 2' K1' K 2'
(2) 2/2.303 cal (3)  (4) 
(3) 2 cal K1 K 2 K1 K 2
(4) None of these
45. Which one is correct for K  Ae Ea / RT ?
42. Rate of which reactions increases with temperature:
(1) Ea is energy of activation
(1) of any
(2) of exothermic reactions (2) R is Rydberg constant
(3) of endothermic (3) K is equilibrium constant
(4) of none (4) A is adsorption factor
52. The rate constant, the activation energy and the
1
46. The slope of the line for the graph of log k versus Arrhenius parameter of a chemical reaction at 25°C are
T 3.0 × 10–4 s–1, 104.4 kJ mol–1 and 6.0 × 1014 s–1 respectively.
1 The value of the rate constant as T  is
for the reaction, N 2O 5  2NO 2 + O is – 5000. (1) 2.0 × 10 18 s–1
2 2
(2) 6.0 × 10 14 s–1
Calculate the energy of activation of the reaction
(kJ K–1 mol–1) (3) Infinity
(1) 95.7 (2) 9.57 (4) 3.6 × 10 30 s–1
(3) 957 (4) None 53. Which is incorrect from the theory of Arrhenius’s
47. For a zero order reaction, which of the following equation?
statement is false? (1) The number of effective collisions is proportional
(1) the rate is independent of the temperature of the to the number of molecules above a certain
reaction. threshold energy
(2) the rate is independent of the concentration of (2) As the temperature increases, the number of
the reactants. molecules with energies exceeding the threshold
(3) the half life depends upon the concentration of energy increases
the reactants. (3) The rate constant is a function of temperature
(4) the rate constant has the unit mole L–1 sec–1. (4) activation energy and pre-exponential factors are
temperature-dependent
48. A large increase in the rate of a reaction for a rise in
temperature is due to 54. Rate of a reaction can be expressed by Arrhenius
(1) increase in the number of collisions equation as:
(2) the increase in the number of activated molecules
(3) The shortening of mean free path k  Ae Ea / RT
(4) the lowering of activation energy In this equation, Ea represents:
(1) The fraction of molecules with energy greater than
49. The rate constant (K’) of one reaction is double of the
rate constant (K”) of another reaction. Then the the activation energy of the reaction
relationship between the corresponding activation (2) The energy abo ve which all the collid ing
energies of the two reactions (Ea' and Ea") will be molecules will react
(1) Ea' > Ea" (2) Ea' = Ea" (3) The energy below which colliding molecules will
(3) Ea' < Ea" (4) Ea' = 4Ea" not react
(4) The total energy of the reacting molecules at a
50. The energy of activations for forward and backward temperature, T
change for an endothermic reaction; X  Y are Ef and
Eb, respectively. Which of the following is correct? 

55. The H value of the reaction H2 + Cl 
 2HCl is –
(1) Eb < Ef
(2) Eb > Ef 44.12 kcal. If E1 is the activation energy of the products,
(3) Eb = Ef then for the above reaction
(4) No relation between them (1) E1 > E2
(2) E1 < E2
51. The maximum value of activation energy is equal to: (3) E1 = E2
(1) zero (2) heat of the reaction
(4) H is not related to E1 and E2
(3) threshold energy (4) none of these
4.6 Synopsis
A. Rate of Reaction : Change in concentration of reactants or products as function of time.
(Unit : mol L–1 s–1 or M s–1)
1. Differential Rate Equation
aA  bB 
 c C  dD
1 d [A] 1 d [B] 1 d [C] 1 d [D]
Rate     
a dt b dt c dt d dt
d [R] d [P]
2. Instantaneous Rate : rins   
dt dt
R P
Average Rate : rav   
t t
3. Rate Law / Rate Equation :
 The expression of rate in terms of molar concentration of reactants.
For eaction, aA  bB   c C  dD
Rate = k [A]x [B]y
Where, k = rate constant or specific reaction rate.
 Depends only upon temperature.
1 n
 mol 
 Unit of k    s 1 , where n = order of reaction.
 L 
4. Order of Reaction
 Sum of powers of concentration terms in the rate law expression.
e.g. Rate = k [A] [B]2
 Order = 1 + 2 = 3
1
 For nth order, t1/ 2 
a n 1
 Experimental concept and can be zero or fractional.
 Depends upon pressure and temperature.
5. Molecularity of Reaction
 The number of molecules of reactants taking part in a elementary step of a reaction.
 Theoretical concept of can never be zero or fractional.
 Independent of pressure and temperature.
B. INTEGRATED RATE EQUATION

1. Zero Order Reaction [R]0
 Rate = k or kt = [R]0 – [R]
Rate
[R]
 Unit of k = mol L–1 s–1 k = – slope
[ R]0
 t1/2 (half-life) 
2k t [R]
2. First Order Reaction
2.303 [ R ]0
 Rate = k [R] or k  log
t [ R]
Unit of k = s–1 ln [R]0
ln [R]

Rate
k = – slope
 t1/2 = 0.693 / k
2.303 pi
 In terms of pressure, k  log
t 2 pi  pt t [R]
3. Useful Relations for First Order Reaction :
t75% = 2t1/2, t87.5% = 3t1/2, t93.75% = 4t1/2, t96.87% = 5t1/2, t99.9% = 10t1/2
4. Second Order Reaction
1 1
 Rate  k[ R]2 or  kt 
[ R]t [ R]0 1
Rate
Slope = k
 Unit of k = L mol s –1 –1
II order [R ]
1 Intercept = 1/[R]0
 t1/ 2  2
k[ R]0 (conc.) Time 't'
5. nth Order Reaction

1 1
 Rate = k [R]n or (n  1)kt  n 1

[ R] [ R]0n 1
 Unit of k = (mol L–1)1 – n s–1
1
 t1/2  2n 1 
k (n  1)[ R]0n 1
C. DEPENDENCY OF RATE ON TEMPERATURE

1. Arrhenius Equation
 k  Ae  Ea / RT
Here, A = pre-exponential factor, R = Gas constant, Ea = Activation energy
k2 Ea  T2  T1 
 log   
k1 2.303R  T1T2 
2. Activation Energy (Ea)
 Energy required by the reactant molecules for effective
collisions to form products. Reaction path
with out catalyst
1 Ea
 The slope of ln k vs has the value  and is used to
T R
calculate value of Ea.
Potential energy
3. Effect of Catalyst on Activation Energy Ea

 A catalyst increases the rate of reaction by providing a Ea Reaction
path of lower activation energy. path with
4. Temperature Coefficient catalyst
 It is the ratio of k298 to k308.
Reactants Energy of
 For every 10° rise in temperature the rate becomes double. reaction
5. Collision Theory Production
 Rate = P  Z AB e Ea / RT Reaction coordinate
1. The rate of a reaction is expressed in different ways as 5. In the reaction ; A + 2B  3C + D, which of the
follows ; following expression does not describe changes in the
1 d [C ] 1 d [ D] 1 d [ A] d [ B] concentration of various species as a function of time:
    . d [C] 3d [A] 3d [D] d [C]
2 dt 3 dt 4 dt dt (1)  (2) 
The reaction can be : dt dt dt dt
(1) 4 A + B  2C + 3D 3d [B] 2d [C] 2d [B] d [A]
(2) B + 3D  4A + 2C (3)  (4) 
dt dt dt dt
(3) 4A + 2B  2C + 3D
(4) B + (1/2) D  4A + 3C 6. In the following reaction : xA  yB
 d [A]   d [B] 
2. Consider the chemical reaction : log     log  dt   log 2
 dt   
N2 (g) + 3H2 (g)  2NH3(g)
where –ve sign indicates rate of disappearance of the
The rate of this reaction can be expressed ; in terms of
reactant. Thus, x : y is :
time and of concentration of N2(g), H2(g) or NH3(g).
Identify the correct relationship amongest the rate ex- (1) 1 : 2 (2) 2 : 1
pressions. (3) 3 : 1 (4) 3 : 10
d [N 2 ] 1 d [H 2 ] 1 d [NH3 ] 7. aA + bB  Product, dx/dt = k [A] a [B] b. If conc of A

(1) Rate =    is doubled, rate is four times. If conc. of B is made four
dt 3 dt 2 dt times, rate is doubled. What is relation between rate of
d [N 2 ] 3d [H 2 ] 2d [NH3 ] disappearance of A and that of B ?
(2) Rate =   
dt dt dt d [A] d [B] d [A] d [B]
(1)   (2)  4
d [N 2 ]  d [H 2 ] d [NH3 ] dt dt dt dt
(3) Rate =   
dt 3 dt dt 4d [A] d [B]
(3)   (4) None of these
d [N 2 ] d [H 2 ] d [NH3 ] dt dt
(4) Rate =   
dt dt dt 8. For a reaction pA + qB  products, the rate law
3. In a reaction N2(g) + 3H2(g)  2NH3(g) the rate expression is r = k [A] 1 [B] m, then :
of appearance of NH3 is 2.5 × 10 –4 mol L–1 sec–1. The (1) (p + 1) < (1+ m)
rate of reaction and rate of disappearance of H2 will be (2) (p + q) > (1 + m)
(in mol L–1 sec–1) (3) (p + q) may or may not be equal to (1 + m)
(1) 3.75 × 10–4, 1.25 × 10–4 (4) (p + q) = (1 + m)
(2) 1.25 × 10–4, 2.5 × 10–4 9. For the reaction H2 + Br 2  2HBr overall order is
(3) 1.25 × 10–4, 3.75 × 10–4 found to be 3/2. The rate of reaction can be expressed
(4) 5.0 × 10–4, 3.75 × 10–4 as:
(1) [H2][Br2]1/2 (2) [H2]1/2 [Br2]
 d [B] 3/2
(3) [H2] [Br2] 0
(4) All of these
4. 3A  2B, rate of reaction is equal to :
dt d [A] d [B] d [C]
3 d [A] 10. xA  yB  ZC . If    1.5 
(1)  dt dt dt
2 dt then x, y and z can be :
2 d [A] (1) 1, 1, 1 (2) 3, 2, 3
(2)  (3) 3, 3, 2 (4) 2, 2, 3
3 dt
1 d [A] 11. If concentration of reactants is increased by a factor
(3)  x then the rate constant k becomes :
3 dt
k k
d [A] (1) ln (2)
(4) 2 x x
dt (3) k+x (4) k
12. The rate of certain hypothetical reaction A + B + C 19. The rate law for the single step reaction 2A + B 
 products is given by 2C, is given by
d [A] (1) Rate = K [A][B] (2) Rate = K [A]2[B]
r  K[A]1/ 2[B]1/ 3 [C]1/4. (3) Rate = K [2A][B] (4) Rate = K[A]2[B]0
dt
The order of the reaction : 20. For the reaction A + B  Products, it is found that
(1) 1 (2) 1/2 the order of A is 2 and of B is 3 in the rate expression.
(3) 2 (4) 13/12 When concentration of both is doubled the rate will
increase by a factor of :
13. 2A  B + C it would be a zero order reaction when :
(1) 10 (2) 6
(1) The rate of reaction is proportional to square of
conc. of A (3) 32 (4) 16
(2) The rate of reaction remains same at any conc. of A 21. For a reaction A + B  products, the rate of the
(3) The rate remains unchanged at any conc. of B reaction was doubled when the concentration of. A
and C was doubled, the rate was again doubled when the
(4) The rate of reaction doubles if conc. of B is in- conc. of A and B were doubled the order of the reac-
creased to double tion with respect to A & B are :
14. The rate equation for the reaction 2A + B  C is (1) 1, 1 (2) 2, 0
found to be : rate k [A][B]. The correct statement in (3) 1, 0 (4) 0, 1
relation to this reaction is that the
(1) Rate of formation of C is twice the rate of disap- THE INTEGRATED RATE LAWS
pearance of A. 22. The rate constant of reaction 2 A + B  C is 2.57 ×
(2) Half life is a constant 10 –5. It mole –1 sec –1 after 10 sec. 2.65 × 10 –5. It. mole–1
(3) Unit of k must be s–1 sec–1 after 20 sec. and 2.55 × 10 –5 It. mole –1 sec –1 after
(4) Value of k is independent of the initial concen- 30 sec. The order of the reaction is:
tration of A and C. (1) 0 (2) 1
(3) 2 (4) 3
15. The rate constant for a reaction is 10.8 × 10 –5 mol L–1
S–1 The reaction obeys : 23. For a first order reaction, the plot of ‘t’ against log C
(1) First order (2) Zero order gives a straight line with slope equal to :
(3) Second order (4) All are wrong (1) (k / 2.303) (2) (– k / 2.303)
(3) (ln k / 2.303) (4) – k.
16. The energies of activation for forward and reverse
reaction for A2 + B2  2AB are 180 kJ mol–1 and 200 kJ 24. In a first order reaction the amount of reactant decayed
mol–1 respectively. The presence of catalyst lowers the in three half lives (let a be is initial amount) would be :
activation energy of both (forward and reverse) (1) 7 a / 8 (2) a / 8
reactions by 100 kJ mol–1. The enthalpy change of the (3) a / 6 (4) 5 a / 6
reaction (A2 + B2  2AB) in the presence of catalyst
will be in kJ mol–1): 25. A graph plotted between log t50% vs. log concentration
d (1) 300 (2) 120 is a straight line. What conclusion can you draw from
(3) 280 (4) –20 this graph.
17. If a reaction gets completed in finite time then its order log t50%
can be :
(1) 3 (2) 2 log a
(3) 1 (4) Zero 1
(1) n  1; t1/ 2  a (2) n  2 ; t1/ 2 
18. For the irreversible process, A + B  products, the a
rate is first–order w.r.t. A and second–order w.r.t. B. If 0.693
1.0 mol each of A and B introduced into a 1.0 L vessel, (3) n  1; t1/ 2  (4) None of these
k
and the initial rate was 1.0 × 10 –2 mol L–1 s–1, rate when
half reactants have been turned into products is : 26. In a first order reaction the concentration of the reac-
(1) 1.25 × 10–3 mol L–1 s–1 tant is decreased from 1.0 M to 0.25 M in 20 min. The
(2) 1.0 × 10–2 mol L–1 s–1 rate constant of the reaction would be –
(3) 2.50 × 10–3 mol L–1 s–1 (1) 10 min–1 (2) 6.931 min–1
–1
(4) 2.0 × 10–2 mol L–1 s–1 (3) 0.6931 min (4) 0.06931 min–1
27. In a certain reaction, 10% of the reactant decomposes d [ A]
in one hour, 20 % in two hours, 30% in three hours and 34. For the reaction A  Products, – = k and at
dt
so on the dimensions of the rate constant is : different time interval, [A] values are :
(1) hour –1
(2) mole litre–1 sec–1 Time 0 5 min 10 min 15 min
(3) litre mole–1 sec–1 [A] 20 mol 18 mol 16 mol 14 mol
(4) mole sec–1 At 20 minute, rate will be :
(1) 12 mol /min (2) 10 mol/min
28. If a first order reaction is completed to the extent of
75% and 50% in time intervals, t1 and t2, what is the (3) 8 mol/min (4) 0.4 mol/min
ratio, t1 : t2 ? 35. The rate law for a reaction A + B  product is rate =
ln (3/ 4) K [A]1 [B] 2. Then which one of the following statement
(1) ln 2 (2) is false :
ln 2
(3) 2 (4) 1/2 (1) If [B] is held constant while [A] is doubled, the
reaction will proceed twice as fast
ln 2 (2) If [A] is held constant while [B] is reduced to one
29. The rate constant for a reaction is min–1. What quater, the rate will be halved
10
will be the order of reaction and time taken to change (3) If [A] and [B] are both doubled, the reaction will
concentration from 1 M to 0.25 M. proceed 8 times as fast
(1) one, 10 min (2) zero, 10 min (4) This is a third order reaction
(3) one, 20 min (4) two, 20 min
36. The reaction A(s)  2 B(g) + C(g) is first order.
30. In the first order reaction 75% of the reactant disap- The pressure after 20 min. and after very long time are
peared in 1.388 hrs. Calculate the rate constant of the 150 mm Hg and 225 mm Hg. The value of rate constant
reaction : and pressure after 40 min. are :
(1) 1 s–1 (1) 0.05 ln 1.5 min–1, 200 mm
(2) 2.8 × 10–4 s–1 (2) 0.5 ln 2 min–1, 300 mm
(3) 17.2 × 10–3 s–1 (3) 0.05 ln 3 min–1, 300 mm
(4) 1.8 × 10–3 s–1 (4) 0.05 ln 3 min–1, 200 mm
31. In the case of zero order reaction, the ratio of time re- METHODS TO MONITOR THE PROGRESS OF THE RE-
quired for 75% completion to 50% completion is : ACTION
(1) ln 2 (2) 2 37. Consider the reaction 2A(g)  3B(g) + C(g). Start-
(3) 1.5 (4) None ing with pure A initially, the total pressure doubled in 3
32. The data for the reaction : A + B  C is hrs. The order of the reaction might possibly be
(1) zero
Exp. [A]0 [B]0 Initial rate (2) first
1 0.012 0.035 0.10 (3) second
2 0.024 0.035 0.80 (4) unpredictable from this data
3 0.012 0.070 0.10
4 0.024 0.070 0.80 38. Let there be as first-order reaction of the type, A 
B + C. Let us assume that only A is geseous. We are
(1) r = k [B]3 required to calculate the value of rate constant based
(2) r = k [A]3 on the following data :
(3) r = k [A] [B]4
Time 0 0 
(4) r = k [A]2 [B]2.
Partial pressure of A P0 Pt –
dx
33. A + B  Product, = k [A]a [B]b 1 P  1 P 
dt (1) k  ln  0  (2) k  ln  t 
t  Pt  t  P0 
 dx 
If   = k, then order is :
 dt  1  2P  1  P 
(1) 4 (2) 2 (3) k  ln  0  (4) k  ln  t 
t  Pt  t  2 P0 
(3) 1 (4) 0
39. Let there be a first order reaction, A  B + C. Let us 45. The activation energy for the forward reaction X  Y
assume all there are gases. We are required to calculate is 60 KJ mol–1 and H is – 20 KJ mol–1. The activation
the value of rate constant based on the following data energy for the backard reaction Y  X is :
 (1) 80 KJ mol–1
Time 0 t
– (2) 40 KJ mol–1
Total pressure P0 Pt
(3) 60 KJ mol–1
Calculate the expression of rate constant. (4) 20 KJ mol–1
1  2P  P  1  P0  46. For producing the effective collisions, the colloiding
(1) k  ln  0 t  (2) k  ln  
t  P0  t  2 P0  Pt  molecules must posses :
(1) A certain minimum amount of energy
t  P0  1  Pt  (2) Energy equal to or greater than threshold en-
(3) k  ln   (4) k  ln   ergy
1  2 P0  Pt  t  2 P0  Pt 
(3) Proper orientation
40. Rate of which reactions increases with temperature : (4) Threshold energy as well as proper orientation of
(1) of any collision.
(2) of exothermic reactions 1
(3) of endothermic 47. In a gaseous state reaction, A2(g)  B(g) + C (g),
2
(4) of none. The increase in pressure from 100 mm to 120 mm is
41. For a zero order reaction. Which of the following state- notices in 5 minutes. The average rate of disapearance
ment is false : of A2 in mm min–1 is :
(1) the rate is independent of the temperature of the (1) 4
reaction. (2) 8
(2) the rate is independent of the concentration of (3) 16
the reactants. (4) 2
(3) the half life depends as the concentration of the 48. The first order rate constant k is related to temp. as log
reactants. k = 15.0 – (10 6 /T) Which of the following pair of value
(4) the rate constant has the unit mole lt–1 sec–1. is correct ?
42. A large increase in the rate of a reaction for a rise in (1) A = 10 15 and E = 1.9 × 10 4 KJ
temperature is due to (2) A = 10 –15 and E = 40 KJ
(A) increase in the number of collisions (3) A = 10 15 and E = 40 KJ
(2) the increase in the number of activated mol- (4) A = 10 –15 and E = 1.9 × 10 4 KJ.
ecules 49. For a given reaction, energy of activation for forward
(3) The shortening of mean free path reaction (Eaf) is 80kJ.mol–1. H = – 40 kJ .mol–1 for the
(4) the lowering of activation energy reaction. A catalyst lowers Eaf to 20 kJ.mol –1. The ratio
43. According to collision theory of reaction rates : of energy of activation for reverse reaction before
and after addition of catalyst is :
(1) Every collision between reactant leads to chemi-
cal reaction (1) 1.0
(2) Rate of reaction is proportional to velocity of (2) 0.5
molecules (3) 1.2
(3) All reactions which occur in gaseous phase are (4) 2.0
zero order reaction 50. Following mechanism has been proposed for a
(4) Rate of reaction is directly proportional to colli- reaction.
sion frequency. 2A + B  D + E
44. Activation energy of a reaction is : Step -1 A + B  C + D – (slow)
(1) The energy released during the reaction Step -2 A + C  E – (fast)
(2) The energy evolved when activated complex is The rate law expression for the reaction is :
formed (1) r = K [A]2 [B]
(3) Minimum amount of energy needed to overcome (2) r = K [A] [B]
the potential barrier of reaction (3) r = K [A] 2
(4) The energy needed to form one mole of the product. (4) r = K [A][C]
(Concept Builder)
1. The role of a catalyst is to change : 5. Consider the following figure & mark the correct option.
(1) Gibbs energy of reaction
(2) enthalpy of reaction E1
(3) activation energy of reaction
Energy
Products
(4) equilibrium constant E2
2. In the presence of a catalyst, heat evolved or absorbed Reactants
during reaction :
Reaction Coordinate
(1) increases
(1) Activation energy of forward reaction is E1 + E2
(2) decreases and product is less stable than reactant.
(3) remains unchanged (2) Activation energy of forward reaction is E1 + E2
(4) may increase or decrease and product is more stable than reactant.
(3) Activation energy of both forward and backward
3. Activation energy of a chemical reaction can be
reactions is E 1 + E 2 and reactant is more stable
determined by : than product.
(1) determining the rate constant at standard (4) Activation energy of backward reaction is E, and
temperature product is more stable than reactant.
(2) determining the rate constants at two temperatures 6. According to Arrhenius equation rate constant k is
(3) determining probability of collision equal to Ae  Ea / RT . Which of the following options
(4) using catalyst represents the graph of In k versus (1/T)?
4. Consider a first order gas phase decomposition reaction

given below: In k In k
A(g)  B(g) + C(g) (1) (2)
The initial pressure of the sys tem before 1/T 1/T

decomposition of A was Pi. After lapse of time ‘t’, total
pressure of the system increased by x units and In k In k
(3) (4)
became ‘P t’. The rate constant k for the reaction is
given as : 1/T 1/T
7. Consider the Arrhenius equation given below and mark
2.303 P the correct option. k  Ae  Ea / RT
(1) k log i
t Pi  x (1) Rate constant increases exponen tially with
increasing activation energy and decreasing
2.303 Pi temperature.
(2) k log (2) Rate constant decreases exponen tially with
t 2 Pi  Pt
increasing activation energy and decreasing
temperature.
2.303 Pi (3) Rate constant increases exponen tially with
(3) k log
t 2 Pi  Pt decreasing activation energy and decreasing
temperature.
2.303 P (4) Rate constant increases exponen tially with
(4) k log i decreasing activation energy and increasing
t Pi  x
temperature.
8. A graph of volume of hydrogen released vs time for 11. Which of the following statement is correct?
the reaction between zinc and dil. HCl is shown below. (1) The rate of a reaction decreases with passage of
On the basis of this, mark the correct option. time as the concentration of reactants decreases.
(2) The rate of a reaction is same at any time during
V5 the reaction.
V4 (3) The rate o f a reaction is independent of
V3 temperature change.
(4) The rate of a reaction decreases with increase in
V2 concentration of reactant(s).
V1 12. Which of the following expressions is correct for the
rate of reaction given below?
5 Br(aq )  BrO3(
 
aq )  6 H ( aq ) 
 3 Br2( aq )  3 H 2O(l )
0 2030 40 50 [ Br  ] [ H  ] [ Br  ] 6 [ H  ]
(1) 5 (2) 
V3  V2 t t t 5 t
(1) Average rate upto 40 second is
40 [ Br  ] 5 [ H  ] [ Br  ] [ H  ]
(3)  (4) 6
V3  V2 t 6 t t t
(2) Average rate upto 40 seconds is
40  30 13. Which of the following graph represents exothermic
V3 reaction?
40 Activated Complex
V3  V1
40  20
Energy
9. Which of the following statement is not correct about

order of a reaction? (i)
(1) The order of a reaction can be a fractional number. Reactants
(2) Order of a reaction is experimentally determined Products
quantity. Reactants coordinate
(3) The order of a reaction is always equal to the sum
Activated Complex
of the stoichiometric coefficients of reactants in
the balanced chemical equation for a reaction.
(4) The order of a reaction is the sum of the powers
Energy
of molar concentration of the reactants in the rate

law expression.
(ii) Products
10. Consider the graph given in Q. 8. Which of the following
option does not show instantaneous rate of reaction
Reactants
at 40th second? Reactants coordinate
V5  V2 Activated Complex
(1)
50  30
V4  V2
Energy
(2)
50  30
(iii) Reactants Products
V3  V2
(3)
40  30
Reactants coordinate
V3  V1
(4) (1) (i) only (2) (ii) only
40  20 (3) (iii) only (4) both (i) and (ii)
14. Rate law for the reaction ‘B’ is doubled, keeping the 19. The value of rate constant of a pseudo first order
concentration of ‘A’ con stant, the value of rate reaction :
constant will be : (1) depends on the concentration of reactants present
(1) the same (2) doubled in small amount
(3) quadrupled (4) halved
(2) depends on the concentration of reactants present
15. Which of the following statement is incorrect about in excess
the collision theory of chemical reaction? (3) is independent of the concentration of reactants
(1) It considers reacting molecules or atoms to be
(4) depends only on temperature
hard spheres and ignores their structural features.
(2) Number of effective collisions determines the rate 20. Consider the reaction A  B. The concentration of
of a reaction. both the reactants and the prod ucts varies
(3) Collision of atoms or molecules possessing exponentially with time. Which of the following figures
sufficient threshold energy resul ts into the correctly describes the change in concentration of
product formation. reactants and products with time?
(4) Molecules should collide with sufficient
threshold energy and proper orientation for the
collision to be effective. [B]
Concentration
16. A first order reaction is 50% completed in 1.26×1014 s.
How much time would it take for 100% completion?
(1)
(1) 1 26 × 1015 s (2) 2.52×1014 s
[A]
(3) 2.52 × 10 28 s (4) infinite
Time
17. Compounds ‘A’ and ‘B’ react according to the following
chemical equation. [B]
A(g) + 2B(g)  2C(g)
Concentration of either ‘A’ or ‘B’ were changed keeping
Concentration
the concentrations of one of the reactants constant

and rates were measured as a function of initial
(2)
concentration. The following results were obtained.
Choose the correct option for the rate equations for [A]
this reaction. Time
Experiment 1 2 3
Initial concentration of [A]/mol L–1 0.30 0.30 0.60 [B]
Initial concentration of [B]/mol L–1 0.30 0.630 0.30
Concentration
–1 –1
Initial rate of formation of [C]/mole L s 0.10 0.40 0.20
(1) k[A]2 [B]y
(2) k[A] [B]2 (3)
(3) k[A] [B]y [A]
(4) k[A]2 [B]
Time
18. Which of the following statement is not correct for the
catalyst?
[A]
(1) It catalyses the forward and backward reactions
Concentration
to the same extent.

(2) It alters G of the reaction.
(3) It is a sub stance that does not change the (4)
equilibrium constant of a reaction. [B]
(4) It provides an alternate mechanism by reducing
activation energy between reactants and products. Time
• Instructions for Questions 1 to 10 8. Assertion : Vision is not a photochemical reaction.

Reason : Halogenation of alkenes is a photochemical
Given below are two statements: One is labelled as Assertion
reaction.
(A) and the other is labelled as Reason (R).
In the light of the above statements, choose the most 9. Assertion : Glow worm shows chemiluminescence.
appropriate answer from the options given below : Reason : Glow worm emits light due to oxidation of pro-
(1) Both (A) and (R) are correct and (R) is the correct tein, luciferin present in it.
explanation of (A) 10. Assertion : The pre-exponential factor A has the same
(2) Both (A) and (R) are correct but (R) is not the correct units for all reactions.
explanation of (A)
Reason : e  Ea / RT has no unit.
(3) (A) is correct the (R) is not correct
(4) (A) is not correct but (R) is correct • Instructions for Questions 11 to 15
1. Assertion : Instantaneous rate of reaction is equal to Given below are two statements :
dx/dt. In the light of the above s tatements, choose the most
Reason : It is the rate of reaction at any particular inappropriate answer from the options given below :
stant of time. (1) Both Statement I and Statement II are correct
2. Assertion : Molecularity has no meaning for a com- (2) Both Statement I and Statement II are incorrect
plex reaction. (3) Statement I is correct but Statement II is incorrect
Reason : The overall molecularity of a complex reac- (4) Statement I is incorrect but Statement II is correct
tion is equal to the molecularity of the slowest step. 11. Statement I : The kinetic of the reaction
3. Assertion : If in a zero order reaction, the concentra- mA  nB  pC  m 'X  n 'Y  p 'Z
tion of the reactant is doubled, the half-life period is
also doubled. dx
obeys the rate expression as  k [A]m [B]n .
Reason : For a zero order reaction, the rate of reaction dt
is independent of initial concentration. Statement II : The rate of the reaction does not depend
upon the concentration of C.
4. Assertion : If the activation energy of a reaction is
12. Statement I : If the activation energy of reaction is
zero, temperature will have no effect on the rate con-
zero temperature will have no effect on the rate con-
stant.
stant.
Reason : Lower the activation energy, faster is the re-
action. Statement II : Lower the activation energy faster is the
reaction
5. Assertion : According to steady state hypothesis, in a
k k
multistep reaction, the change in concentration with 13. Statement I : In A  1
 B  2
 C
time for reactive intermediates is zero. If half life of A is very less as compared to B, so the net
Reason : The intermediates are so reactive that after a reaction is A 
 C with rate constant.
brief initial period their concentrations rise from zero ( k1  k 2 )
to a small value and remains constant for most of the Statement II : Slowest step is the rate determining step
duration of the reaction. so B  C is rate determining step.
6. Assertion : Half-life period of a reaction of first order 14. Statement I : For A + 2B  C (rate = K[A] 1 [B] 0), the
is independent of initial concentration. half life time of reaction is only defined when conc. of
Reason : Half-life period for a first order reaction A and B are in stoichiometric ratio.
2.303 Statement II : For above given order half life of
t1/ 2  log 2.
K reaction is directly proportional to conc. of A and not
7. Assertion : Half life of a certain radioactive element to conc. of B due to its zero order.
is 100 days. After 200 days, fraction left undecaye will 15. Statement I : Many reactions occurring on solid sur-
be 25%. face are zero order reactions.
Ct  1 
n
Au 1
Reason :   Statement II : N 2O(g)  N 2 (g)  O2 ;
C0  2  2
where symbols have standard meaning. rate = k [N 2O] 0 = k = constant is a zero order reaction
(Direct from
NCERT)
Match the List – I and List – II and choose the correct (c) Rate = k [A] 3/2 [B] 1/2 (iii) First order
combination from the options given. when A is in excess
1. Match the following: (d) Rate = k [A] 2 [B] 1 (iv) Second order
List – I List – II when B is in excess
(a) 2N2O5(g)  Ist order (i)

All the gaseous products Choose the correct answer from the options given below :
(1) (a) – (iii, iv); (b) – (ii); (c) – (iv); (d) – (i)
4NO2(g) + O2(g) are paramagnetic in nature
Ist order
(2) (a) – (ii); (b) – (i); (c) – (i); (d) – (iii, iv)
(b) 2H2O2(aq)  (ii) Hybridisation of reactant
(3) (a) – (i); (b) – (ii, i); (c) – (iii, iv); (d) – (iv)
2H2O(aq) + O2 involves only s p orbital (4) (a) – (iii, (iv); (b) – (iii); (c) – (i); (d) – (ii, iv)
Zero order
(c) 2NH3(g)  (iii) As the reaction proceeds

N2(g) + 3H2(g) half life of reactant 4. Match the following:
changes with time
List – I List – II
Zero order
(d) 2Cl2O7(g)  (iv) Rate of production of gases

(a) Zero order reaction (i)
Acid hydrolysis of an
4ClO2(g) + 3O2 decreases with increases in
ester
concentration of product
(b) First order reaction (ii) Saponification of an
Choose the correct answer from the options given below : ester
(1) (a) – (i, iii); (b) – (ii, iii); (c) – (iv); (d) – (i, ii, iv) (c) Second order reaction (iii) 2NO + Cl2  2NOCl
(2) (a) – (i, ii, iv; (b) – (ii, iii, iv); (c) – (iii, iv); (d) – (i, ii, iv) (d) Third order reaction (iv) Substrate in an
(3) (a) – (iii, iv); (b) – (i, ii); (c) – (i, ii, iv); (d) – (ii, iv) enzyme reaction
(4) (a) – (i, ii, iv); (b) – (i, ii, iv); (c) – (ii, iii); (d) – (i,ii,iii) (v) Hydrolysis of cane
2. Match the statements given in List – I and List – II. sugar
List – I List – II Choose the correct answer from the options given below :
(1) (a) – (iv); (b) – (i, v); (c) – (ii); (d) – (iii)
(a) Catalyst alters are (i) Cannot be fraction
(2) (a) – (i); (b) – (ii); (c) – (iv, v); (d) – (iii)
rate of reaction or zero
(b) Molecularity (ii) Proper orientation (3) (a) – (iv, i); (b) – (ii); (c) – (iii); (d) – (i, v)
is not there (4) (a) – (i, ii); (b) – (iii); (c) – (i, v); (d) – (iv)
(c) Second half-life of (iii) By lowering the
first order reaction activation energy 5. Match List – I with List – II
1
(d) e  E a / RT (iv) Is same as the first List – I List – II
(e) Energetically (v) Total probability is one
favourable reactions (a) C v/s t (abscissa) (i) unity
are sometimes slow for zero order
(f) Area under the (vi) Refers to the fraction (b) log C v/s t (abscissa) (ii) zero
maxwell, Boltzmann of molecules with energy for first order
curve is constant equal to or greater than  dC 
activation energy. (c)    v/s C for (iii)  k
 dt 
Choose the correct answer from the options given below : zero order
(1) (a) – (iii); (b) – (ii); (c) – (i); (d) – (iv); (e) – (v); (f) – (vi)  dC  k
(2) (a) – (i); (b) – (ii); (c) – (v); (d) – (iii); (e) – (iv); (f) – (vi) (d) In   dt  v/s In C (iv) 
  2.303
(3) (a) – (iii); (b) – (i); (c) – (iv); (d) – (vi); (e) – (ii); (f) – (v) for zero order
(4) (a) – (ii); (b) – (iii); (c) – (i); (d) – (iv); (e) – (v); (f) – (vi) (v) In k
3. Match the following: Choose the correct answer from the options given below :
List – I (Rate law) List – II (Order) (1) (a) – (iii); (b) – (ii); (c) – (iv); (d) – (i)
(a) Rate = k × Intensity (i) Second order (2) (a) – (i); (b) – (ii); (c) – (iv); (d) – (iii)
of light (3) (a) – (ii); (b) – (i); (c) – (iv); (d) – (iii)
(b) Rate = k [A] 1 [B] 1 (ii) Zero order (4) (a) – (ii); (b) – (iii); (c) – (i); (d) – (iv)
(Previous Year Questions)
1. The reaction, A B follows first order kinetics. The 8. For the reaction, [AIPMT-2006]
time taken for 0.8 mole of A to produce 0.6 mole of B is 2A + B  3C + D
1h. what is the time taken for the conversion of 0.9 which of th e following does not express the
mole of A to 0.675 mole of B? [AIPMT-2003] reactionrate ?
(1) 0.25h (2) 2h
d [C ] d [ B]
(3) 1h (4) 0.5 h (1)  (2) 
3dt 3dt
2. The temperature dependence of rate constant (k) of a d[ D] d [ A]
chemical reaction is written in terms of Arrhenius (3) (4) 
equation, k = Ae –E*/RT , Activation energy (E*) of the dt 2dt
reaction can be calculated by plotting [AIPMT-2003] 9. Consider the reaction :
N2(g) +3 H2(g)  2NH3(g)
1 1
(1) log k vs (2) log k vs The equality relationship between
T log T
d [NH3 ] d [H 2 ]
1 and is [AIPMT-2006]
(3) k vs T (4) k vs dt dt
log T d [NH3 ] 1 d [H 2 ]
3. If the rate of a reaction is equal to the rate constant, (1) 
dt 3 dt
the order of the reaction is [AIPMT-2003]
d [NH3 ] 2 d [H 2 ]
(1) 2 (2) 3 (2)  
dt 3 dt
(3) 0 (4) 1
d [NH3 ] 2 d [H 2 ]
4. The activation energy for a simple chemical reaction, (3)  
AB is Ea in forward direction. The activation energy dt 3 dt
for reverse reaction [AIPMT-2003] d [NH3 ] d [H 2 ]
(4) 
(1) can be less than or more than Ea dt dt
(2) is always double of Ea 10. In a first order rection, A B, if k is rate constant and
(3) is negative of Ea initial concentration of the reactant A is 0.5 M, then
the half-life is [AIPMT-2007]
(4) is always less than E a
5. The rate of first order reaction is 1.5 × 10 –2 mol L–1
0.693 log 2
(1) (2)
min –1 at 0.5 M concentration of the reactant. The half- 0.5 k k
life on the reaction is [AIPMT-2004]
log 2 ln 2
(1) 0.383 min (3) (4)
k 0.5 5
(2) 23.1min
(3) 8.73 min 12. The reaction of hydrogen and iodine mono-chloride is
(4) 7.53 min given as [AIPMT-2007]
6. For a fistt order reaction, A  B, the reaction rate at H2(g) + 2ICl(g)  2HCl(g) + I2(g)
reactant concentration of 0.01 M is found to be 2.0 × This reaction is of first order with respect to H2(g) and
10 –5 mol L –1 s –1. The half-life period of the reaction is ICl(g), following mechanisms wee proposed
(1) 220 s (2) 30 s [AIPMT-2005] Mechanism A : H2(g)2 + ICl(g)  2HCl(g) + I2(g)
(3) 300 s (4) 347 s Mechanism B : H2(g) + ICl(g)  HCl(g) + HI(g), slow
7. The rate of reaction between two reactants A and B HI(g) + ICl (g)  HCl (g) + I2 (g) fast
decreases by a factor of 4, if the concentration of
Which of the above mechanism (s) can be consistent with
reactant B is doubled. The order of this reaction with
respect to reactant B is [AIPMT-2005] the given information about the reaction?
(1) –1 (2) –2 (1) Only 1 (2) Both 1 and 2
(3) 1 (4) 2 (3) Neither 1 nor 2 (4) Only 2

12. If 60% of a first order reactionwas completed in 60 min, 18. In the reaction,
50% of the same reaction would be completed in BrO3– (aq) + 5Br– (aq) + 6H+  3Br2 (l) + 3 H2O(l)
approximately (log 4 = 0.60, log 5 = 0.69) [AIPMT-2007] the rate of appearance of bromine (Br 2) is related to
(A) 50 min (2) 45 min rate of disappearance of bromide ions as following :
(3) 60 min (4) 40 min
d [Br2 ] 3 d [Br  ]
13. The bromination of acetone that occurs in acid solution (1)  [AIPMT-2009]
dt 5 dt
is represented by this equation
CH3COCH3(aq) + Br2(aq)  d [Br2 ] 5 d [Br  ]
(2) 
CH3COCH2Br (aq) + H+ (aq) + Br– (aq) dt 3 dt
These kinetic data ware obtained for given reaction d [Br2 ] 5 d [Br  ]
concentrations. (3) 
dt 3 dt
Initial concentrations,M
d [Br2 ] 3 d [Br  ]
[CH3COCH3] [Br 2] [H+] (4) 
dt 5 dt
0.30 0.05 0.05
19. During the kinetic study of the reaction, 2A + B  C
0.30 0.10 0.10 + D, following results were obtained
0.40 0.05 0.20
Initial rate, disappearance of Br2, Ms–1
Run A/mol L–1 B/Mol L–1 Initial rate of formation of
D/mol L–1 min–1
5.7 × 10 -5 5.7 × 10 –5 1.2 × 10–4 3.1 × 10–4 –3
I 0.1 0.1 6.0 × 10
Based on these data, the rate equation is –2
II 0.3 0.2 7.2 × 10
(1) rate = k [CH3 COCH3][H+] [AIPMT-2008] –1
III 0.3 0.4 2.88 × 10
(2) rate = k [CH2 = COCH3] [BR2] IV 0.4 0.1 2.40 × 10
–2
(3) rate = k [CH3COCH3][Br2][H+]2

Based on the above data which one of the folloiwng is
(4) rate = k [CH3COCH3][Br2] [H+]
correct ? [AIPMT-2010]
14. The rate constants k1 and k2 for two different reactions
(1) Rate = k[A] 2[B] (2) Rate = k[A][B]
are 10 16 .e –2000T and 10 15 .e –1000T , respectively. The
(3) Rate = k[A] 2[B] 2 (4) Rate = k[A] [B] 2
temperature at which k1 = k2 is [AIPMT-2008]
20. For an endothermic reaction, energy of activation is
2000
(1) 1000 K (2) K E and enthalphy of reaction is H (both of these in
2.303
kj/mol.) Minimum value of E will be [AIPMT-2010]
1000
(3) 2000 K (4) K (1) less than H (2) equal to H
2.303
(3) more than H (4) equal to zero
15. Half-life period of a first order reaction is 1386s. The
specific rate constant of the reaction is [AIPMT 2009] 21. For the reaction, [AIPMT-2010]
(1) 5.0 × 10 –3 s–1 (2) 5.0 × 10–2 s–1 1
N 2O5 ( g ) 
 2 NO2 ( g )  O2 ( g )
(3) 0.5 × 10 s –3 –1
(4) 5.0 × 10–3 s–2 2
The value of rate of disappearance of N2O5 is given as
16. For the reaction, A+B  products, it is observed that
6.25 × 10–3 mol L–1 s–1. The rate of formation of NO2 and
[AIPMT-2009]
O2 is given respectively as
I. On doubling the initial concentration of A only,
(1) 6.25 × 10–3 mol L–1 s–1 and 6.25 × 10–3 mol L–1 s–1
the rate of reaction is alos doubled and
(2) 1.25 × 10–2 mol L–1 s–1 and 3.125 × 10–3 mol L–1 s–1
II. On doubling the initial concentrations of both A
(3) 6.25 × 10–3 mol L–1 s–1 and 3.125 × 10–3 mol L–1 s–1
and B, there is a change b a factor of 8 inthe rate
(4) 1.25 × 10–2 mol L–1 s–1 and 6.25 × 10–3 mol L–1 s–1
of the reaction
22. Which one of the following statements for the order of
The rate of this reaction is,given by
a reaction is incorrect? [AIPMT-2011]
(1) rate = k[A] 2[B] (2) rate = k[A] [B] 2
2
(1) Order is no t influenced by stoi chiometric
(3) rate = k[A] [B] (4) rate = K[A][B]
coefficient of the reactants
d [ NH3 ]
17. For the reaction, N2 + 3H2  2NH3. If = 2 × 10-4 (2) Order of reactionis sum of po wer to the
dt concentration terms of reactanst to express the
d [ H 2 ]
mol L–1 , the value of would be [AIPMT-2009] rate of reaction
dt
–4
(1) 3 × 10 mol L s –1 –1
(2) 4 × 10–4 mol L–1s–1 (3) Order of reaction is always whole number
(3) 6 × 10 –4 mol L–1s–1 (4) 1 × 10–4 mol L–1 s–1 (4) Order can be determined only experimentally
23. In a zero orde reaction for veery 10 0 C rise of 30. The rae of a first-order reaction is 0.04 mol L–1 s –1 at 10
temperature, the rate is doubled. If the temperature is sec and 0.03 mol L–1 s–1 at 20 sec after initiation of the
incresed from 10 0C ot 100 0C, the rate of the reaction reaction. The half-life period of the reactions is
will become [AIPMT-2012] (1) 34.1 s (2) 44.1 s [NEET-2016]
(1) 256 times (2) 512 times (3) 54.1 s (4) 24.1 s
(3) 64 times (4) 128 times 31. Mechanism of a hypothetical reaction
24. In a reaction, A + B  Product, rate is doubled when X2 + Y2  2XY is given below [Neet-2017]
the concentration of B is doubled and rate increases 
(i) X  
 X + X (fast)
by a factor of 8 when the concentrations of both the
(ii) X + Y2  XY+Y (slow)
reactants (A and B) are doubled. Rate law for the
(iii) X + Y  XY (fast)
reaction can be written as [AIPMT-2012]
The overall order of the reaction will be
(1) rate = k[A] [B] 2
(1) 1 (2) 2
(2) rate = k [A] 2[B] 2
(3) 0 (4) 1.5
(3) rate = k[A] [B]
32. A first order reaction has a specific reaction rate of 10–2
(4) rate = k [A] 2[B]
s–1. How much time will it take for 20g of the reactant
25. What is the activation energy for a reaction if its rate to reduce to 5 g? [NEET-2017]
doubles when the temperature is raised from 20 0C ot (1) 238.6 s (2) 138.6
35 0C? (R = 8.314 j mol–1 K–1) [AIPMT-2013]
(3) 346.5 s (4) 693.0 s
–1
(1) 342 kJ mol (2) 269 kJ mol–1
33. Which one of the following statements is not correct?
(3) 34.7 kJ mol–1 (4) 15.1 kJ mol–1 [NEET-2017]
26. The rate constant of the reaction A  B is 0.6 × 10–3 (1) Catalyst does not initiate any reaction
mole per second. If the concentration of A is 5 M then
(2) The value of equilibrium constant is changed in the
con-centration of B after 20 min is [AIPMT-2000]
presence of a catalyst in the reaction equilibrium
(1) 1.08 M (2) 3.60 M (3) Enzymes catalyse mainly biochemical reaction
(3) 0.36 M (4) 0.72 M (4) co-enzymes increase the catalytic activity of enzme
27. The activation energy of a reaction can be determined 34. When initial concentration of the reactant is doubled,
from the slope of which of the following grapsh? the half-life period of a zero order reaction
[AIPMT-2015] [NEET-2018]
ln K (1) is tripled (2) is doubled
(1) ln K vs T (2) vs T (3) is halved (4) remains unchanged
T
35. The correct difference between first-and second-
I T I order reactions is that [NEET-2018]
(3) ln K vs (4) vs (1) a first-order reaction can be catalyzed ; a second-
T ln K T
order reaction cannot be catalyzed
28. When initial concentration of a reactant is doubled in (2) the half-life of a first - order reaction does not
a reaction, its half-life period is not affected. The order depend on [A] 0 ; the half - life of a second- order
of the reactions is [AIPMT-2015] reaction does depend on [A] 0
(1) zero (3) the rate of a first-order reaction does not depend
(2) first on reactant concentrations ; the rate of a second
(3) second - order reaction does depend on reactant concen-
(4) more than zero but less than first trations
29. The decomposition of phosphine (PH3) on tungsten at (4) the rate of a first-order reaction does depend on
low pressure is a first-order reaction. It is because the reactant concentrations ; the rate of a second-
[NEET-2016] order react ion does not depend on reactant
(1) rate is proportional to the surface coverage concentrations
(2) rate is inversely proportional to the surface 36. If the rate constant for a first order reaction is k, the
time required for the completion of 90% of the reaction
covergage
is given by [NEET-2019]
(3) rate is independent of the surgface coverage
(1) t = 0.693/k (2) t = 6.909/k
(4) rate of decomposition is very slow (3) t = 4.606/k (4) t = 2.303/k
37. 

For the chemical : N2 + 3H2 
 2NH3 [NEET-2019] 45. The half life of a first order reaction is 2000 years. If the
concentration after 8000 years is 0.02 M, then the initial
1 d [H 2 ] 1 d [NH3 ] d [N 2 ] d [NH3 ] concentration was: [NEET-2022]
(1)   (2)  2
3 dt 2 dt dt dt (1) 0.16 M (2) 0.32 M
(3) 0.08 M (4) 0.04 M
d [N 2 ] 1 d [NH3 ] d [H 2 ] d [NH3 ]
(3)   (4) 3 2 46. For a chemical reaction [NEET-2022]
dt 2 dt dt dt
4 A  3 B  6C  9 D
38. The rate constant for a first order reaction is 4.606 ×
10 –3 s –1. The time required to reduce 2.0 g of the reactant rate of formation of C is 6×10–2 mol L–1 s–1 and rate of
to 0.2 g is : [NEET-2020] disappearance of A is 4 × 10–2 mol L–1 s–1. The rate of
reaction and amount of B consumed in interval of 10
(1) 1000 s (2) 100 s
seconds, respectively will be
(3) 200 s (4) 500 s (1) 1× 10–2 mol L–1 s–1 and 30 × 10–2 mol L–1
39. An increase in the concentration of the reactants of a (2) 10× 10–2 mol L–1 s–1 and 10 × 10–2 mol L–1
reaction leads to change in : [NEET-2020]
(3) 1× 10–2 mol L–1 s–1 and 10 × 10–2 mol L–1
(1) collision frequency (2) activation energy (4) 10× 10–2 mol L–1 s–1 and 30 × 10–2 mol L–1
(3) heat of reaction (4) threshold energy 47. The given graph is a representation of kinetics of a
40. The half-life for a zero order reaction having 0.02 M
reaction. [NEET-2022]
initial concentration of reactant is 100 s. The rate
constant (in mol L–1 s–1) for the reaction is [NEET-2020]
(1) 1.0 × 10 –4 (2) 2.0 × 10–4
Constant tem. T
y
(3) 2.0 × 10 –3 (4) 1.0 × 10–2
41. In collision theory of chemical reaction, ZAB represents
[NEET-2020]
(1) the fraction of molecules with energies greater x
than E a The y and x axes for zero and first order reactions,
(2) the collision frequency of reactants, A and B respectively are
(3) steric factor (1) zero order (y = rate and x = concentration), first
(4) the fraction of molecules with energies equal to Ea order (y = t½ and x = concentration)
42. Match List - I with List - II [NEET-2021] (2) zero order (y = rate and x = concentration), first
List - I List - II order (y = rate and x = t½)
(a) PCl5 (i) Square pyramidal (3) zero order (y = concentration and x = time), first
order (y = t½ and x = concentration)
(b) SF 6 (ii) Trigonal planar
(4) zero order (y = concentration and x = time), first
(c) BrF5 (iii) Octahedral
order (y = rate constant and x = concentration)
(d) BF3 (iv) Trigonal bipyramidal 48. For a fi rst order reaction A  Products, initial
Choose the correct answer from the options given concentration of A is 0.1 M, which becomes 0.001 M
below: after 5 minutes. Rate constant for the reaction in min–1
(1) (a)-(iv), (b)-(iii), (c)-(i), (d)-(ii) is [NEET-2022]
(2) (a)-(ii), (b)-(iii), (c)-(iv), (d)-(i) (1) 0.4606 (2) 0.2303
(3) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii) (3) 1.3818 (4) 0.9212
(4) (a)-(iv), (b)-(iii), (c)-(ii), (d)-(i) 49. The half life of a first order reaction is 2000 years. If the
concentration after 8000 years is 0.02M, then the initial
 1
The slope of Arrhenius Plot  ln k v/s concentration was : [NEET-2022]
T 
43. of first order
 (1) 0.16 M (2) 0.32 M
reaction is –5 × 103 K. The value of Ea of the reaction is. (3) 0.08 M (4) 0.04 M
Choose the correct option for your answer. [Given R = 50. For a chemical reaction : 4A + 3B  6C + 9D
8.314 JK–1 mol–1] [NEET-2021]
rate of formation of C is 6 × 10–2 mol L–1 s–1 and rate of
(1) 41.5 kJ mol–1 (2) 83.0 kJ mol–1 disappearance of A is 4 × 10–2 mol L–1 s–1. The rate of
(3) 166 kJ mol–1 (4) – 83 kJ mol–1 reaction and amount of B consumed in interval of 10
44. For a chemical reaction [NEET-2021] seconds, respectively will be : [NEET-2022]
4A + 3B  6C + 9D (1) 1 × 10–2 mol L–1 s–1 and 30 × 10–2 mol L–1
rate of formation (2) 10 × 10–2 mol L–1 s–1 and 10 × 10–2 mol L–1
(1) 41.5 kJ mol–1 (2) 83.0 kJ mol–1 (3) 1 × 10–2 mol L–1 s–1 and 10 × 10–2 mol L–1
–1
(3) 166 kJ mol (4) – 83 kJ mol–1 (4) 10 × 10–2 mol L–1 s–1 and 30 × 10–2 mol L–1
DAILY PRACTICE PROBLEM (DPP) – 01 41. (1) 42. (2) 43. (2) 44. (3) 45. (1)
46. (2) 47. (2) 48. (1) 49. (2) 50. (2)
1. (2) 2. (1) 3. (2) 4. (2) 5. (1)
6. (2) 7. (3) 8. (2) 9. (3) 10. (3)
NCERT EXEMPLAR OBJECTIVE TYPE QUESTIONS
6. (1) 7. (2) 8. (3) 9. (3) 10. (2)
11. (3) 12. (2) 13. (1) 14. (2) 15. (1)
11. (1) 12. (3) 13. (1) 14. (1) 15. (3)
16. (1) 17. (1) 18. (2) 19. (2) 20. (3)
21. (2) 22. (2) 23. (2) 24. (2) 25. (1) 16. (2) 17. (2) 18. (2) 19. (2) 20. (2)
DAILY PRACTICE PROBLEM (DPP) – 03 ASSERTION–REASON & STATEMENT QUESTIONS

1. (2) 2. (2) 3. (2) 4. (2) 5. (1)
26. (1) 27. (3) 28. (2) 29. (1) 30. (2)
31. (2) 32. (2) 33. (2) 34. (2) 35. (1) 6. (1) 7. (1) 8. (4) 9. (1) 10. (1)
36. (2) 37. (2) 38. (2) 39. (2) 40. (1) 11. (1) 12. (2) 13. (4) 14. (3) 15. (2)
DAILY PRACTICE PROBLEM (DPP) – 04 MATRIX TYPE QUESTIONS
41. (3) 42. (1) 43. (2) 44. (3) 45. (1) 1. (4) 2. (3) 3. (2) 4. (1) 5. (3)
46. (1) 47. (1) 48. (2) 49. (3) 50. (1)
51. (2) 52. (2) 53. (2) 54. (3) 55. (1) ARCHIVE QUESTIONS
1. (3) 2. (1) 3. (3) 4. (1) 5. (2)
MISCELLANEOUS QUESTIONS FROM NCERT
6. (2) 7. (2) 8. (1) 9. (2) 10. (2)
1. (2) 2. (1) 3. (3) 4. (2) 5. (2) 11. (1) 12. (2) 13. (1) 14. (2) 15. (3)
6. (2) 7. (2) 8. (3) 9. (2) 10. (3) 16. (2) 17. (1) 18. (1) 19. (2) 20. (3)
11. (2) 12. (2) 13. (2) 14. (2) 15. (2) 21. (2) 22. (3) 23. (2) 24. (2) 25. (3)
16. (2) 17. (2) 18. (1) 19. (2) 20. (3) 26. (2) 27. (3) 28. (2) 29. (1) 30. (2)
21. (3) 22. (3) 23. (2) 24. (1) 25. (3) 31. (2) 32. (2) 33. (2) 34. (2) 35. (2)
26. (2) 27. (2) 28. (3) 29. (3) 30. (2) 36. (3) 37. (3) 38. (2) 39. (1) 40. (1)
31. (3) 32. (2) 33. (2) 34. (2) 35. (2) 41. (2) 42. (1) 43. (1) 44. (*) 45. (2)
36. (2) 37. (1) 38. (1) 39. (2) 40. (1) 46. (1) 47. (1) 48. (4) 49. (2) 50. (1)
Surface Chemistry 43
SURFACE
CHEMISTRY
Chapter 05
C . 9%
A. Colloidal Solution 54%
B. Adsorption 37%
A. 54% B. 37%
C. Catalysis 9%
WHAT DO YOU WANT TO KNOW?

5.4 CLASSIFICATION OF COLLOIDS
5.4.1 On the Basis of Physical State of D.P. and D.M.
5.0 INTRODUCTION 5.4.2 On the Basis of Interaction of D.P. for D.M.
5.1 ABSORPTION 5.4.3 Multimolecular, Macromolecular & Associated
5.1.1 Distinction between Adsorption and Colloids
Absorption 5.4.4 Preparation of Colloids
5.1.2 Mechanism of Absorption 5.4.5 Purification of Colloidal Solutions
5.1.3 Types of Absorption 5.4.6 Properties of Colloidal Solutions
5.1.4 Absorption Isotherm (by Freundlich)
5.5 EMULSIONS
5.1.5 Absorption from solution phase
5.6 COLLOIDS AROUND US
5.1.6 Application of Absorption
5.7 SYNOPSIS
5.2 CATALYSIS
5.2.1 Homogenous Catalysis
5.9 NCERT Exemplar Questions
5.2.2 Absorption Theory of Heterogenous Catalysit
5.10 Assertion-Reason and Statement
5.2.3 Zeolites (Shape Selective Catalyst) Based Questions from NCERT
5.2.4 Enzyme Catalysis 5.11 Matrix Based Questions
5.2.5 Catalysit in Industry 5.12 ARCHIVE QUESTIONS
5.3 COLLOIDS 5.13 ANSWER KEY
44 Surface Chemistry
Absorption Adsorption
Sorption
Physisorption Adsorbent
ADSORPTION
Chemisorption Adsorbate
Factors influencing Applications

Temperatures Laboratory
Pressure Isotherms Industrial
Adsorbate Daily life

Frendlich’s Langmuir’s
Isotherm Isotherm
Adsorbent
x ap
Gases on Solutions 
Solids Phase m 1  bp
x 1 x 1
 kP n  kc n
m m
Ultracentrifugation
Dialysis Purification Ultrafiltration
Oxidation
Mechanical Reduction
Physical methods
Preparation
Peptisation Hydrolysis
Bredig’s arc Double decomposition
Associated (e.g., soaps & detergents) COLLOIDS Disperse phase

Multimolecular (e.g., sulphur sol) Disperse medium
Macromolecular (e.g., starch sol, proteins) Solid-in-liquid type Sols (e.g., Gold sol)
SOLS Lyophobic
Gels (e.g., Al(OH)3, ppt
Lyophilic
Properties Emulsion (e.g., milk oil)
of Sols Protective Gold
action Number
Optical Electrical Kinetic
Tyndal effect Charge on particles Brownian motion
Professional adsorption +ve sols (e.g., Fe(OH)3, sol

Ionisation –ve sols (e.g., As2S3 sol
Stability of sols
Coagulation
Addition of electrolytes Mutual Heating/Cooling Centrifugation

Hardy-Shculze rule

 The properties of substances are different at the surfaces and in the bulk, because the molecules present in
the bulk are equally attracted in all direction having net force zero but the molecules present at surface
experience attraction unequally.
 Due to unbalanced forces these molecules present at surface tends to take up molecules of a gas or any
other substance in order to release the surface tension which they are experiencing.
 This tendency is more prominent in transition metals. The surface is more activated in case of finely
divided state or rough surface. In this unit we will study phenomenon related to surface.
 Surface chemistry is the branch of chemistry which deals with the study of nature of surface and the
species present on it.
 This phenomenon is studied with the help of adsorption and colloidal state which are quite useful to understant
the physical and chemical characteristics of the substance.
5.1 ABSORPTION P.No.: 124
 The phenomenon of attracting and retaining the molecules of a substance on the surface of a liquid or a solid
resulting into a higher concentration of the molecules on the surface is called adsorption. As a result of
adsorption, there is a decrease of surface energy.
 The process of removal of an adsorbed substance from the surface on which it is adsorbed is called desorp-
tion. It is the reverse of adsorption and can be brought about by heating or by reducing the pressure.
5.1.1 P.No.: 124

 The terms adsorption and absorption are different.
 Adsorption is a phenomenon in which there is higher concentration of another substance on the surface than
in the bulk.
 On the other hand, absorption is a phenomenon in which the molecules of a substance are uniformly distrib-
uted throughout the body of other substance. For example, when silica gel is placed in the environment of
water, it adsorbs the water vapour.
 The water vapour are present in high concentration at the surface of silica gel. On the other hand, when
calcium chloride is placed in the environment of water, it absorbs water.
 The water vapour uniformly get distributed throughout the body of calcium chloride. Thus, silica gel adsorbs
water vapour while anhydrous calcium chloride absorbs water.
ABSORPTION ADSORPTION
It is the phenomenon in which the particles of gas It is the phenomenon of higher concentration of
or liquid get uniformly distributed throughout the gas or liquid on the surface than in the bulk of
body of the solid. the solid.
The concentration is the same throughout the The concentration on the surface of the adsorbent
material. Therefore, it is a bulk phenomenon. is different (has higher concentration) from that in
the bulk. Therefore, it is a surface phenomenon.
Absorption occurs at uniform rate. Adsorption is rapid in the beginning and its rate
slowly decreases.
ADSORBENT AND ADSORBATE P.No.: 124

 The substance on the surface of which adsorption occurs is known as adsorbent.
 The substances that get adsorbed on the solid surface due to intermolecular attractions are called adsorbate.
Charcoal, silica, gel, alumina gel are good adsorbents because they have highly porous structures and have
large surface area.
 Colloids on account of their extremely small dimensions possess enoromous surface area per unit mass and
are, therefore, also good adsorbents.
EXAMPLES OF ADSORPTION P.No.: 124

 Adsorption of a gas by charcoal : Finely divided activated charcoal has a tendency to adsorb a number of
gases like ammonia, sulphur dioxide, chlorine, phosgene, etc. In this case, charcoal acts as an adsorbent
while gas molecules act as adsorbate.
 Adsorption of a dye by charcoal : Animal charcoal is used for decolourising a number of organic sub-
stances in the form of their solutions. The discharge of the colour is due to the fact that the coloured
component (generally an organic dye) gets adsorbed on the surface of the adsorbent (animal charcoal).
 Sorption : When both adsorption and absorption take place simultaneously. For example, Dyes get adsorbed
as well as absorbed in the cotton fibre i.e. adsorption takes place.
5.1.2 P.No.: 124

 Adsorption is an exothermic process. Therefore H of adsorption is always negative. When a gas is adsorbed
the entropy of the gas decreases i.e. S is negative.
 Adsorption is thus accompanied by decrease in enthalpy as well as entropy of the system, for a process to
be spontaneous requirement is that G must be negative.
 On the basis of equation, G = H – TS, G can be negative if H has sufficiently high negative value as
– TS is positive. Thus, in an adsorption process, which is spontaneous, S is negative, and H is also
sufficiently negative and as a combination of these two factors, G is negative.
 H becomes less and less negative as adsorption proceeds further and further. Ultimately H becomes
equal to TS and G becomes zero. This is the state at which equilibrium is attained.
 Enthalpy of adsorption Hadsorption : It is the amount of the heat released when 1 mole of an adsorbate
gets adsorbed on a particular adsorbent at adsorption equilibrium. It depends upon the nature of both the
adsorbate as well as adsorbent.
5.1.3 P.No.: 125

The adsorption is classified into two types :
 Physical adsorption (i.e. physisorption) : When the particles of the adsorbate are held to the surface of
the adsorbent by the physical forces such as van der Waal’s forces, the adsorption is called physical adsorp-
tion or vanderwaals adsorption.
 Chemical adsorption (i.e. chemisorption) : When the molecules of the adsorbate are held to the surface
of the adsorbent by the chemical forces, the adsorption is called chemical adsorption.
DIFFERENCE BETWEEN PHYSICAL ADSORPTION AND CHEMICAL ADSORPTION
PHYSICAL ABSORPTION CHEMICAL ADSORPTION
The forces between the adsorbate molecules The forces between the adsorbate molecules and
and the adsorbent are weak van der Waal’s the adsorbent are strong chemical forces.
forces.
Low heat of adsorption of the order of 20-40 kJ High heat of adsorption of the order 80-240 kJ
mol–1. mol–1
Usually occurs at low temperature and decreases It occurs at high temperature
with increasing temperature.
It is reversible. It is irreversible.
The extent of adsorption depends upon the ease There is no correlation between extent of
of liquefication of the gas. adsorption and the ease of liquefication of gas.
It is less specific in nature, all gases are adsorbed It is highly specific in nature and occurs only
on the surface of a solid to some extent. when there is bond formation between adsorbent
and adsorbate molecules.
It forms multimolecular layers. It forms mono-molecular layer.
ADSORPTION OF GASES ON SOLIDS P.No.: 126
The extent of adsorption of a gas on a solid surface is affected by the following factors:
 The nature of the gas (i.e. nature of the adsorbate). The easily liquefiable gases such as HCl, NH3, Cl2
etc. are adsorbed more than the permanent gases such as H2, N2 and O2. The ease with which a gas can be
liquefied is primarily determined by its critical temperature. Higher the critical temperature (Tc) of a gas, the
more easily it will be liquefied and, therefore, more readily it will be adsorbed on the solid.
Gas SO2 CH4 H2
TC 330 K 190 K 33 K
 Nature of adsorbent : The extent of adsorption of a gas depends upon the nature of adsorbent. Activated
charcoal (i.e. activated carbon), metal oxides (silica gel and aluminium oxide) and clay can adsorb gases
which are easily liquified. Gases such as H2, N2 and O2 are generally adsorbed on finely divided transition
metals Ni and Co.
 Activation of adsorbent :
 Metallic adsorbents are activated by mechanical rubbing or by subjecting it to some chemical
reactions.
 To increase the adsorbing power of adsorbents, they are sub-divided into smaller pieces. As a results,
the surface area is increased and therefore, the adsorbing power increases.
 Effect of temperature : Mostly the process of adsorption is exothermic and the reverse process or
desorption is endothermic. If the above equilibrium is subjected to increase in temperature, then accord-
ing to Le-Chaterlier’s principle, with increase in temperature, the desorption will be favoured. Physical
adsorption decreases continuously with increase in temperature whereas chemisorption increases initially,
shows a maximum in the curve and then it decreases continuously.
x x
m m
Temperature Temperature
The initial increase in chemisorption with increase in temperature is because of activation energy required.
This is why the chemical adsorption is also known as “Activated adsorption”.
A graph between degree of adsorption (x/m) and temperature ‘t’ at a constant pressure of adsorbate gas is
known as adsorption isobar.
 Effect of pressure :
 The extent of adsorption of a gas per unit mass of adsorbent x/m
depends upon the pressure of the gas. The variation of extent of
adsorption expressed as x/m (where x is the mole of adsorbate
and m is the mass of the adsorbent) and the pressure is given as
below. A graph between the amount of adsorption and gas pres-
sure keeping the temperature constant is called an adsorption O P Ps
isotherm. Figure-1
 It is clear from the figure-1 that extent of adsorption (x/m) increases with pressure and becomes
maximum corresponding to pressure Ps called equilibrium pressure. Since adsorption is a reversible
process, the desorption also takes place simultaneously. At this pressure (Ps) the amount of gas adsorbed
becomes equal to the amount of gas desorbed.
5.1.4 P.No.: 127
The variation of extent of adsorption (x/m) with pressure (P) was given mathematically by Freundlich.
 At low pressure the graph is almost straight line which indicates that x/m is directly proportional to the
pressure. This may be expressed as :
(x / m)  p or (x / m) = kp where k is constant.
 At high pressure the graph becomes almost constant which means that x / m becomes independent of
pressure. This may be expressed as :
(x / m) = constant or (x / m)  p° (since p° = 1) or (x / m) = kp°.
 Thus, in the intermediate range of pressure, x / m will depend upon the power of pressure which lies
between 0 to 1, fractional power of pressure. This may be expressed as :
(x / m)  p1/n or (x / m) = kp1/n
 Where n can take any whole number value which depends upon the nature of adsorbate and adsorbent. The
above relationship is also called Freundlich’s adsorption isotherm.
 The constant k and n can be determined as explained below :
Taking logarithms on both sides of
Eq. (x / m) = kp1/n we get
log (x / m) = log k + (1/n) log p.
 One of the drawbacks of Freundlich isotherm is that it fails at high pressure of the gas.
 This equation applicable only when adsorbate substance form unimolecular layer on adsorbent
surface. i.e. chemical adsorption.
5.1.5 P.No.: 128

 The process of adsorption can take place from solutions also. It is observed that solid adsorbents adsorb
certain solutes from solution in preference to other solutes and solvents. For example, animal charcoal
decolouries impure sugar solution by adsorbing colouring dye in preference to sugar molecules.
 The extent of adsorption from solution depends upon the concentration of solute in the solution as given by
Freundlich isotherm : (x / m) = k (c)1/n (n  1)
where c is the equilibrium concentration of the solute in solution.
 Temperature dependence here also is similar to that for adsorption of gases and in place of equilibrium
pressure, we use equilibrium concentrations of the adsorbates in the solution.
5.1.6 P.No.: 128

 In gas masks : Activated charcoal is generally used in gas masks to adsorb poisonous and toxic gases from
air. These masks are commonly used by the miners because there are poisonous gases like CO, CH4 etc. in
the atmosphere in coal mines.
 In dyeing of cloths : Mordants such as alums are used in dyeing of cloths. They adsorb the dye particles
which, otherwise, do not stick to the cloths.
 In dehumidizers : Silica gel is commonly used to adsorb humidity or moisture from air.
 Removal of colouring matter : Many substances such as sugar, juice and vegetable oils are coloured due
to the presence of impurities. They can be decolourised by placing them in contact with adsorbents like
activated charcoal or fuller’s earth.
 Heterogeneous catalysis : The phenomenon of adsorption is useful in the heterogeneous catalysis. The
metals such as Fe, Ni, Pt, Pd, etc, are used in the manufacturing processes such as Contact process, Haber
process and the hydrogenation of oils. Their use is based upon the phenomenon of adsorption.
 Refining Petroleum : Silica gel is used as adsorbent in petroleum refining.
 Chromatography : It is a method for separation of component and is based on preferential adsorption
column is very common device used.
 Creating vacuum : High vacuum can be created by removing gas by adsorption.
 Adsorption Indicators : In volumetric analysis, adsorption indicator is used Surface of certain precipitates
such as silver halide have the property of adsorbing some dye like eosin, fluorescein, etc In the case of
precipitation titration (AgNO3 vs NaCI) of the indicator is adsorbed at the end point producing a character-
istic colour on the precipitate.
 In froth floatation process : (in metallurgy).
 Softening of hard water : Ion exchange resins used for softening of hard water is based upon selective and
competive adsorption of ions on resins.
Na2Z + Ca+2  CaZ + 2 Na+
The organic polymers containing groups like – COOH, – SO3H and – NH2 etc. possess the property of
selective adsorption of ions from solution. These are quite useful in the softening of water.
4. Which is correct in case of van der Waals adsorption?

01 (1) High temperature, low pressure
(2) Low temperature, high pressure
P.No.: 123-128 (3) Low temperature, low pressure
1. If x is the amount of adsorbate and m is the amount of (4) High temperature, high pressure
adsorbent, which of the following relations is not
related to adsorption process? 5. According to Langmuir adsorption isotherm, the
amount of gas adsorbed at very high pressures
x (1) Reaches a constant limiting value
(1)  pxT
m (2) Goes on increasing with pressure
x (3) Goes on decreasing with pressure
(2)  f ( p ) at constant T (4) Increases first and decreases later with pressure
m
x 6. Bone charcoal is used to decolourise sugar. In this
(3)  f (T ) at constant p case, bone and colour on sugar respectively are
m (1) adsorbate, adsorbent
x (2) Both are adsorbent
(4) p  f (T ) at constant (3) Both are adsorbate
m
(4) adsorbent, adsorbate
2. When the temperature is raised, the viscosity of liquid
decreases, this is because 7. What will be the effect of increase in temperature on
(1) Decreased volume of the solution physical adsorption?
(2) Increase in temperature increases the average (1) It will decrease
kinetic energy of molecules, which overcome the (2) It will increase
attractive force between them (3) First increase then decrease
(3) Decreased covalent and hydrogen bond forces (4) None of these
(4) Increased attraction between molecules
8. Gas masks containing activated charcoal to remove
3. Which one of the following is an incorrect statement poisonous gases from atmosphere acts on principle
for physisorption of:
(1) It is a reversible process (1) Adsorption
(2) It requires less heat of adsorption (2) Absorption
(3) It requires activation energy (3) sorption
(4) It takes place at low temperature (4) All of these
9. Which one is not the characteristic of chemisorption: 13. Following is the variation of physical adsorption with
(1) Multilayer adsorption temperature:
(2) Exothermic nature
(3) Strong adsorption by adsorption sites
Adsorption
Adsorption
(4) Irreversible
10. Which of t he following statements about (1) (2)

chemisorption is not applicable?
(1) It involves chemical forces between adsorbent T T
and adsorbate
(2) It is irreversible in nature
(3) It involves high heat of adsorption
Adsorption
Adsorption
(4) It does not require activation energy
11. The equation for Freundlich adsorption isotherm is (3) (4)
x T T
(1)  kp1/n
m 14. Adsorption is the phenomenon in which a substance:
(2) x = mkp 1/n (1) accumulates on the surface of the other substance
(3) x/m = kp –n (2) goes into the body of the other substances
(4) All of these (3) remains close to the other substance
(4) none of these
12. Adsorption due to strong chemical forces is called
15. Which is not a purely surface phenomena?
(1) Chemisorption
(1) surface tension
(2) Physiosorption
(2) adsorption
(3) Reversible adsorption
(3) absorption
(4) Both (2) and (3)
(4) none of these
5.2 CATALYSIS P.No.: 129
 Berzillus in 1835 used the word catalyst first time for some substance which alter rate of chemical reaction
and themselves remain chemically and quantitatively unchanged after the reaction and the phenomenon is
known as catalysis.
 For example, potassium chlorate when heated at 653K to 873K, it gives O2. When MnO2 is used in this
reaction the O2 is quickly at the low temperature hence MnO2 is a catalyst
2KClO3  2KCl + 3O2
5.2.1 P.No.: 130
 When catalysts and reactants are in same phase then the process is said to be homogeneous catalysis and
For example,
NO(g)
1. 2SO2 (g)  O2 (g)   2SO3 (g)
HCl( l )
2. CH3COOCH3 (l )   CH3COOH(aq)
H 2SO4 ( l )
3. C12 H 22 O11 (aq)  H 2 O(l )   C6 H12 O6 (aq)  C6 H12 O 6 (aq)
Glucose Fructose
HETEROGENEOUS CATALYSIS P.No.: 130
 When catalysts and reactants are in different phases, then process a know as heterogenous catalysis and
catalyst is called heterogeneous catalyst. For example,
Pt(s)
1. 2SO3 (g)  O2 (g)   2SO3 (g)
Fe(s)
2. N 2 (g)  3H 2 (g)   2NH3 (g)
Pt(s)
3. 4NH3 (g)  5O2 (g)   4NO(g)  6H 2 O(g)
Ni(s)
4. Vegetable oils (l )  H 2 (g)   Vegetable ghee (s).
TYPES OF CATALYSIS
 Positive Catalysis : A substance which increase the rate of chemical reaction is called positive catalyst
and this process called positive catalysis.
Pt (s) Fe(s)
1. 2SO 2 (g)  O 2 (g) 
positive catalyst
 2SO3 (g) 2. N 2 (g)  3H 2 (g) 
Positive catalyst
 2NH 3 (g)
 Negative Catalysis : A substance which decrease the rate of chemical reaction is called negative catalyst
and this process called negative catalysis. For example,
H3 PO4 or glycerol
1. 2H 2 O2 
negative catalyst
 2H 2 O  O2
2. Decomposition of chloroform reduces in the presence of 1% ethyl alcohol.
1 1% ethyl alcohol
CHCl3  O 2 
negative catalyst
 COCl2  HCl
2
 Auto Catalysis : When one of the reaction product behave as catalyst for that reaction and increase the
rate of reaction then the phenomenon is called autocatalysis. “Auto catalytic reactions are slow in the
beginning but become increasingly rapid as the reaction proceeds.” For example,
1. CH3COOC2 H5  HOH 
 CH3COOH (Auto catalyst) + C2 H5OH
2. 2KMnO 4  5COOH  3H 2 SO 4 
 K 2 SO 4  MnSO 4 (Auto catalyst)  8H 2 O  10CO 2
COOH
 Induced Catalyst : When one reaction catalyse an other reaction than the phenomenon is called induced
catalysis and that reaction is called induced catalyst. For example,
1. Sodium sulphite (Na2SO3) is oxidised to Na2SO4 in atmosphere but sodium arsenite (Na3AsO3) does
not oxidises to Na3AsO4 in air. When both are kept together both are oxidised in air. Here oxidation of
Na2SO3 catalyse the oxidation of Na3AsO3. Hence oxidation reaction of Na2SO3 act as an induced
catalyst for oxidation reaction of Na3AsO3.
2. Similarly reduction of HgCl2 to Hg2Cl2 by oxalic acid is very slow while that of KMnO4 is fast but
mixture of HgCl2 and KMnO4 is reduced rapidly by oxalic acid.
 Promoters / Activators : Substance which themselves are not catalyst but its presence can increase the
catalytic activity of catalyst. A promoters increase the number of active sites on the surface. For example,
Fe(catalyst)
1. N 2  3H 2 
Mo(Promoter)
 2NH 3
Ni (catalyst)
2. Vegetable Oil + H2 
Cu (promoter)
 Vegetable ghee.
ZnO
3. CO  2H 2  
Cr2 O3 (promoter)
 CH3OH
 Catalytic Poisons / Anti catalysts / Catalyst Inhibitor : Substance which themselves are not catalyst
but whose presence decrease the activity of the catalyst. Poisoning is due to preferential adsorption of
poison on the surface of the catalyst. For example,
Fe (catalyst)
1. N 2  3H 2 
CO / H 2S (Catalystic poisons)
 2NH3
Platinised asbestos (catalyst)
2. 2SO2  O2 
As 2S3 (Catalytic poisons)
 2SO3
Pd (catalyst)
3. Rosunmund Reactions : RCOCl  H 2 
BaSO4 (poisons catalyst )
 RCHO  HCl
CHARACTERISTICS OF CATALYSIS
 A Catalyst remains unchanged in mass and chemical compositions at the end of reactions. However
its physical state can be change. For example, granular MnO2 during decomposition of KClO3 is left as
powder at the end of the reaction.
 Finely devided state of catalyst is more efficient for the reactions because surface area increases and more
adsorption take place.
 A small amount of catalyst is generally sufficient to catalyse almost unlimited reaction but in some cases the
rate of reaction depends on amount of catalyst.
Exception :
1. In Friedal Craft reaction more amount of catalyst is required.
2. Hydrolysis of ester in acidic and alkaline medium its rate of reaction is proportional to concentration of
H+ or OH– ions.
 A catalyst cannot initiate reaction. But some times the activation energy is so large that practically a reac-
tion may not start until a catalyst lowers the activation energy significantly. For example, mixture of hydro-
gen and oxygen do not react at room temperature but the reaction occurs very rapid in presence of Pt black.
room temperature
H 2  O2    No reaction
Pt black
H 2  O2  H2O
 Catalyst are generally specific in nature. A substance which act as a catalyst in a particular reaction, fails to
catalyse other reaction.
 Catalyst cannot change equilibrium state but it help to attain equilibrium quickly.
 A catalyst does not change the enthalpy, entropy and free energy of a reaction.
 Optimum temperature : There is a particular temperature at which the efficiency of a catalyst a maxi-
mum this temperature is known as optimum temperature. On either side the optimum temperature, the
activity of catalyst decreases.
5.2.2 P.No.: 131
 This theory explain the mechanism of heterogeneous catalyst. This theory is combination of two theory,
intermediate compound formation theory and the old adsorption theory, the catalytic activity is localised on
the surface on the catalyst. The mechanism involve 5 steps.
1. Diffusion of reactant to the surface of the catalyst.
2. Adsorption of reactant molecules on the surface of the catalyst.
3. Formation of activated intermediate.
4. Formation of reactions product on the catalyst surface.
5. Diffusion of reactions product from the catalyst surface or desorption.
Examples, Let us consider addition of H2 gas to ethelene in presence of Ni catalyst, the reaction take
places as follows.
HH
HH
diffusion of H2 Physical adsorption
Ni Ni + H H Ni Ni Ni Ni
catalyst chemical adsorption
H H
C C CH2=CH2 strain
H H
H H H H H H
chemical adsorption diffusion of C2H4
Ni Ni Ni Ni Ni Ni
activated intermediate
formation
CH3 – CH3
diffusion of product
Ni Ni Ni Ni + CH3 – CH3
or desorption product
catalyst
5.2.4 P.No.: 133
 Enzymes are complex nitrogenous organic compounds which are produced from living plants and animals.
 They are actually protein molecules of high molecular mass and form colloidal solutions in water.
 They catalyse biochemical reactions.
REACTIONS CATALYZED BY ENZYMES P.No.: 133

Enzyme Source Reaction
1. Invertase Yeast Sucrose  Glucose and Fructose
2. Zymase Yeast Glucose  Ethyl alcohol and carbon dioxide
3. Diastase Malt Starch  Maltose
4. Maltase Yeast Maltose  Glucose
5. Urease Soyabean Urea  Ammonia and CO2
6. Pepsin Stomach Proteins  Amino acid
CHARACTERISTICS OF ENZYME CATALYSIS P.No.: 133
 Highly efficient : One molecule of an enzyme may transform one million molecules of the reactant per
minute.
 Highly specific nature : One catalyst cannot catalyse more than one reaction.
 Highly active under optimum temperature (298 K to 310 K)
 Highly active under optimum pH (5 to 7)
 Increasing activity in presence of cofactor (Na+, Mn2+, Co2+, Cu2+ etc.) and co-enzymes
MECHANISM OF ENZYME CATALYSIS (KEY LOCK THEORY) P.No.: 133
 These are number of active centres of definite shape present on the surface of colloidal particles of
enzymes. The molecules of the reactant (substrate), which have complementary shape fit into these cavities
just like a key fits into a lock. On account of the presence of active groups an activated complex is formed
which then decomposes to yield the product.
Enzyme Substrate Activated complex Enzyme Products
E + S 
 [E – S]  E + P
5.2.5 P.No.: 135

S.N. PROCESS Catalyst
1. Haber's Process for the manufacture of ammonia Finely divided iron, Molybdenum as promoter.
N2 + 3H2 2NH3 Conditions : 200 atmospheric pressure and
450-500ºC temperature.
2. Ostwald's process for the manufacture of nitric acid. Platinised asbestos
4NH3 + 5O2  4NO + 6H2O ; 2NO + O2  2NO2
4NO + 2H2O + O2  4HNO3 . Temperature 300ºC
3. Lead chamber process for the manufacture of sulphuric Nitric oxide.

acid 2SO2 + O2 2SO3 ; SO3 + H2O  H2SO4.
4. Contact process for the manufacture of sulphuric acid. Platinised asbestos or vanadium pentoxide(V2O5).
2SO2 + O2 2SO3 ; SO3 + H2SO4  H2S2O7 Temperature 400–450ºC.
5. Deacon's process for the manufacture of hydrogen. Cupric chloride (CuCl2). Temperature 500ºC.
4HCl + O2  Cl2 + 2H2O.
6. Bosch's process for the manufacture of hydrogen. Ferric oxide(Fe2O3)+chromic oxide as a promoter.
CO + H2 + H2O  CO2 + 2H2 . Temperature 400–600ºC.
Water gas
7. Synthesis of methanol. Zinc oxide(ZnO) + chromic oxide as a promoter.
CO + 2H2  CH3OH. Pressure 200 atmospheres and temperature
250ºC.
8. Hydrogenation of vegatble oils. Nickel (finely divided).
Oil + H2  vanaspati ghee. Temperature 150ºC – 200ºC. High pressure.
9. Manufacture of ethyl alcohol by fermentation of molasses Invertase enzyme and zymase(yeast) enzyme.
(sugar solution). Invertase Temperature 25–30ºC.
C12H22O11 + H2O C6H12O6 + C6H12O6 Conversion occures in 2 or 3 days.
Zymase
C6H12O6 2C2H5OH + 2CO2 .
10. Manufacture of ethyl alcohol from starch. Germinated barley (diastase enzyme)
Diastase
Temperature 50º-60ºC.
(a) Starch Maltose. Yeast(maltase and zymas enzymes).
Maltase Zymase
Temperature 25º–30ºC.
(b) Maltose Glucose Alcohol.
11. Manufacture of acetic acid from ethyl alcohol. Mycoderma aceti.
C2H5OH + O2  CH3COOH + H2O. Temperature 25º–30ºC.
12. Bergius process for the synthesis of petrol form coal Ferric oxide (Fe2O3).Temperature 475ºC.
Coal + H2  Mixture of hydrocarbons. Pressure 200 atmoshpere.
5.2.3 P.No.: 132
 The calatytic reaction that depends upon the the pore structure of the catalyst & the size of the reactant is
called shape selective catalyst. The pore size is generally in range 260-740 pm. For example,
1. Zeolite (honey comb – like structure).
2. Formula of Zeolite is Nax/n [(AlO2)x (SiO2)y]z H2O
 Zeolite is also called sodium alumino silicate, water softner & cationic exchanger (Exchange only cation
from hard water).
 Zeolite is 3D silicate.
 Zeolite, before using as catalyst are heated in vacuum so that the water of hydration is lost and as a result
Zeolite becomes porous.
02 22. A catalyst increases rate of reaction by:

(1) Decreasing enthalpy
(2) Decreasing internal energy
P.No.: 129-132
(3) Decreasing activation energy
16. The decomposition of hydrogen peroxide can be (4) Increasing activation energy
slowed by the addition of a small amount of acetamide.
23. Which of the following types of metals form the most
The latter acts as a
efficient catalysts?
(1) Detainer
(1) Alkali metals
(2) Stopper (2) Alkaline earth metals
(3) Promoter (3) Transition metals
(4) Inhibitor (4) All of these
17. When KClO3 is heated, it decomposes into KCl+O2. If 24. Formation of ammonia from H 2 and N 2 by Haber’s
some MnO 2 is added, the reaction goes much faster process using Fe is an example of
because (1) Heterogeneous catalysis
(1) MnO2 decomposes to give O 2 (2) Homogeneous catalysis
(2) MnO 2 provides heat by reacting (3) Enzyme catalysis
(3) Better contact is provided by MnO2 (4) Non-catalytic process
(4) MnO2 acts as a catalyst
25. What is the role of a catalyst in a catalysed reaction
18. Which is universally correct for catalyst? (1) Lowers the activation energy
(1) A catalyst remain unchanged chemically at the (2) Increases the activation energy
end of chemical reaction. (3) Affects the free energy change
(2) A catalyst takes part in a chemical reaction (4) Affects the enthalpy change
(3) All kinds of catalysts undergo catalyst poisoning 26. The catalys t used in the contact process for
(4) A catalyst physically changes at the end of the manufacturing of sulphuric acid is
reaction (1) Copper
(2) Iron/aluminium oxide
(3) Vanadium pentoxide
19. In the redox reaction 2MnO 4  5C2 O 42   16H 
(4) Platinized asbestos
 2Mn 2   10CO 2  8H 2 O , the ion acting as 27.
 The role of a catalyst in a reversible reaction is to
autocatalyst is (1) Increase the rate of forward reaction
(2) Decrease the rate of backward reaction
(1) MnO 4 (3) Alter the equilibrium constant of the reaction
(4) Allow the equilibrium to be achieved quickly
(2) C2 O42
28. Which of the following catalyses the conversion of
(3) H+ glucose into ethanol?
(4) Mn 2+ (1) Zymase
Pt (2) Invertase
20. In the reaction 2SO 2  O 2 
As 2 O3
 2SO3 , As2O3 acts (3) Maltase
as a (4) Diastase
(1) Autocatalyst
(2) Poison 29. Hydrolysis of ethyl acetate is catalysed by aqueous
(3) Promotor (1) Na 2SO 4
(2) K2SO 4
(4) Positive catalyst
(3) H2SO 4
21. Which one is false in the following statement? (4) BaSO4
(1) A catalyst is specific in its action
30. A catalyst
(2) A very small amount of the catalyst alters the rate (1) Increases the free energy change in the reaction
of a reaction (2) Decreases the free energy change in the reaction
(3) The number of free vacancies on the surface of (3) Does not increase or decrease the free energy
the catalyst increases on sub-division change in the reaction
(4) Ni is used as a catalyst in the manufacture of (4) Can either increase or decrease the free energy
ammonia change depending on what catalyst we use
31. Which of the following is used as a catalyst in the 34. The components of Ziegler–Natta catalyst, used in the
manufacture of toluene from benzene with CH3Cl? polymerisation of propylene, are
(1) Ni (1) TiCl3 + Al(C2H5)3
(2) Anhydrous AlCl 3
(2) TiCl4 + Al(C2H5)3
(3) Pd
(4) Pt (3) Ti(C2H5)3 + A1Cl3
(4) Ti(C2H5)4 + AlCl3
32. Hydrolysis of ethyl acetate is catalysed by
aqueous 35. In the reversible reaction a catalyst is the substance
(1) Na 2SO 4 (2) K2SO 4 which
(3) H2SO 4 (4) BaSO4 (1) Increases the rate of the forward reaction
(2) Decreases the value of enthalpy change in the
33. The transition metal used as a catalyst is
reaction
(1) Nickel
(2) Platinum (3) Reduces the time required for reaching the
(3) Cobalt equilibrium state in the reaction
(4) All of these (4) Decreases the rate of the reverse reaction
5.3 COLLOIDS P.No.: 136
 Colloid State : A substance is said to be in colloidal state when the size of the particle of disperse phase is
greater than particle of true solution and less than that of suspension solution particle, their range of diam-
eters between 1 and 1000 nm (10–9 to 10–6 m).
 Colloid solution : It is a heterogeneous system consisting of 2 phase :
1. Disperse Phase (D.P) : The phase which is dispersed through the medium is called dispersed phase
or discontinuous phase or internal phase.
2. Dispersion Medium (D.M) : A medium in which colloidal particles are dispersed is called dispersion
medium. It is also known as continuous phase or outer phase or external phase.
Colloidal solution = D.P. + D.M.
For example, in n Gold sol, Gold is D.P and water is D.M.
 DIFFRENCIATING POINT OF COLLOIDS :

 A colloid is a heterogeneous system in which one substance is dispersed (dispersed phase) as very fine
particles in another substance called dispersion medium.
 The solution and colloid essentially differ from one another by particle size.
1. In a solution, the particles are ions or small molecules.
2. In a colloid, the dispersed phase may consist of particles of a single macromolecule (such as
protein or synthetic polymer) or an aggregate of many atoms, ions or molecules.
3. Colloidal particles are larger than simple molecules but small enough to remain suspended. They
have a range of diameters between 1 and 1000 nm (10–9 to 10–6 m).
5.4 CLASSIFICATION OF COLLOIDS P.No.: 136
5.4.1 ON THE BASIS OF PHYSICAL STATE OF D.P. AND D.M.

On the bases of physical state of D.P. and D.M. colloidal solution may be divided into eight system.
Dispersion Dispersion Name of Examples

medium Phase System
Solid Liquid Gel Cheese, butter, iellies
Solid Solid Solid sol Ruby glass, gold in glass
Solid Gas Solid form Pumice stone, sponge, rubber
Liquid Liquid Emulsion Milk
Liquid Solid Sol Au, As2S3, S in water, paints, milk
of magnesia
Liquid Gas Foam Whipped cream, shaving cream,
foam on beer
Gas Liquid Aerosol Fog, mist, clouds
Gas Solid Aerosol Smoke
* Solution of gas in gas is not a colloidal system because it form homogeneous mixture.
ON THE BASIS OF DISPERSION MEDIUM
Colloidal solution are classified as

D.M. Name of colloidal system
Water Hydro sol or aqua sol
Alcohol Alco sols
Benzene Benzo sols
Air Aero sols
 Aquadag & oildag are colloidal solution of graphite in water & oil respectively.
 Colloidal solution are often termed as sol.
5.4.2 ON THE BASIS OF INTERACTION OF D.P. FOR D.M. P.No.: 137

There are two types :
 Lyophilic colloids / liquid loving sols / intrinsic colloid. :
 The colloidal solution in which the particles of the dispersed phase have a great affinity (or love) for the
dispersion medium, are called lyophilic colloids.
 These solutions are easily formed and the lyophilic colloids are reversible in nature. In case water acts
as the dispersion medium, the lyophilic colloid is called hydrophilic colloid.
 The common examples of lyophilic colloids are glue, gelatin, starch, proteins, egg albumin, rubber, etc.
 Lyophobic colloids / solvent hating colloid / extrinsic colloid.
 The colloidal solutions in which there is no affinity between particles of the dispersed phase and the
dispersion medium are called lyophobic colloids.
 Such solutions are formed with difficulty only by special methods.
 These sols are readily precipitated (or coagulated) on the addition of small amounts of electrolytes, by
heating or by shaking and hence are not stable. Further, once precipitated, they do not give back the
colloidal sol by simple addition of the dispersion medium. Hence these sols are also called irreversible
sols.
 They need stabilising agents for their preservation. In case the dispersion medium is water, the lyopho-
bic sol is called hydrophobic colloid. For example, the solution of metals like Ag and Au, hydroxides
like Al (OH)3, Fe(OH)3, metal sulphides like As2S3 etc.
* Lyophilic sols are more stable than lyophobic sols, the additional stability is due presence of an
envelope of the solvent layer (say water) around the colloidal particle, the process is known as hydra-
tion, To coagulate a hydrophilic sols we have to add a dehydrating agent in addition to electrolyte.
DISTINCTION BETWEEN LYOPHILIC AND LYOPHOBIC COLLOIDS
S.No. Property Lyophilic colloids Lyophobic colloids
1 Ease of preparation There are easily formed by direct mixing. These are formed only by special methods
2 Reversible or
These are reversible in nature These are irreversible in nature.
irreversible nature
3 Particles nature The particles of colloids are true The particles are aggregates of many
molecules but are big in size molecules
4 Stability These are very stable These are unstable and require traces of
stabilizers
5 Action of electrolytes No effect The addition of small amount of
electrolytes causes precipitation
(called coagulation) of colloidal solution.
6 Charge on particles The particles do not carry any charge.
7 Hydration The particles of colloids are heavily

hydrated due to the attraction for the
solvent.
8 Viscosity The viscosity and surface tension of the
sols are less than that of the dispersion
medium
9 Tyndall effect They do no show tyndall effect
5.4.3 MULTIMOLECULAR, MACROMOLECULAR AND ASSOCIATED COLLOIDS P.No.: 137
 Multimolecular colloids : In this type, the particles consist of an aggregate of atoms or small molecules
size less than 1 nm. For example, sols of gold atoms and sulphur (S8) molecules. In these colloids, the
particles are held together by van der Waal’s forces.
 Macromolecular colloids : In this types, the particles of the dispersed phase are sufficiently big in size
(macro) to be of colloidal dimensions. These macromolecules forming the dispersed phase are generally
polymers having very high molecular masses. These colloids are quite stable and resemble true solutions in
many respects. Naturally occuring macromolecules are starch, cellulose, proteins, enzymes, gelatin, etc.
 Associated colloids (Micelles) : These are the substances which behave as normal strong electrolytes at
low concentration but behave as colloidal particles at higher concentration. These associated particles are
also called micelles. Ex. Soap.
MICELLES : P.No.: 138

 There are some substances which at low concentrations behave as normal strong electrolytes but at higher
concentrations exhibit colloidal behaviour due to the formation of aggregated particles.
 The aggregated particles thus formed are called micelles. These are also known as associated colloids.
 The formation of micelles takes place only above a particular temperature called Kraft Temperature (Tk)
and above a particular concentration called Critical Micelle Concentration (CMC).
 On dilution, these colloids revert back to individual ions. Surface active agents such as soaps and synthetic
detergents belong to this class. For soaps, the CMC is ~ 10–4 to 10–3 mol L–1. These colloids have both
lyophobic and lyophilic parts. Micelles may contain as many as 100 molecules or more.
MECHANISM OF MICELLE FORMATION : P.No.: 138

 Let us take the example of soap solutions. Soap is sodium salt of a higher fatty acid and may be represented
as RCOO–Na+ e.g., sodium stearate viz.CH3(CH2)16COO– Na+ which is a major component of many bar
soaps. When dissolved in water, it dissociates into RCOO– and Na+ ions. The RCOO– ions, however, consist
of two parts i.e., long hydrocarbon chain R (also called non-polar 'tail') which is hydrophobic (water repel-
ling) and the polar group COO– (also called polar-ionic 'head') which is hydrophilic (water loving). The
RCOO– lons are, therefore, present on the surface with their COO– groups in water and the hydrocarbon
chains R staying away from it, and remain at the surface, but at higher concentration these are pulled into
the bulk of the solution and aggregate in a spherical form with their hydrocarbon chains pointing towards the
centre with COO– part remaining outward on the surface. An aggregate thus formed is known as ‘Ionic
micelle'. These micelles may contain as many as upto 100 such ions.
 Aggregation of RCOO– ions to form an ionic micelle.
Water Na+
+ COO¯ +
Na Na
COO¯ COO¯
Micelle
COO¯ Na+
+ COO¯
Na
COO¯ COO¯ +
Na+ COO¯ Na
+
Na
Similarly, in case of detergents, e.g., sodium lauryl sulphate viz. CH3(CH2)11SO4– Na+, the polar group is –
SO4– along with the long hydrocarbon chain. Hence, the mechanism of micelle formation is same as that of
soaps.
CRITICAL MICELLE CONCENTRATION [CMC] :
 The minimum concentration required for micelle formation is called critical micelle concentration. Its value
depends upon the nature of D.P. and D.M. For example, surface active agent (surfactants, which de-
crease the surface tension) like soaps and detergents form micelle beyond CMC (~10–3 mol/litre for soaps).
 Usually longer the hydrophobic chain, smaller is its CMC.
 Also CMC increase with decreasing polarity of the D.M.
 The micelles ‘formation takes place only above a particular temperature called as Kraft Temperature (Tk).
 At CMC, the micelles are spherical in shape, but that start flattening with increase in concentration and
ultimately form sheet or film like structures which have a thickness of two molecules. These are called
lamelar micelles or McBain Micelles.
Example of micelles :
1. Sodium stearate C17H35COO–Na+(Soap).
2. Sodium lauryl sulphate CH3 [CH2]11 SO4– Na+ (Detergent).
3. Cetyl trimethyl ammonium bromide (Detergent). CH3(CH2)15N+(CH3)3Br–.
4. Sodium p-dodecylbenzenesulphonate (Detergent) : C12H 25 SO 3–Na+
5. Acidic (negative colloids) and basic (positive colloids) dyes.
THE CLEANSING ACTION OF SOAPS : P.No.: 139

 It has been mentioned earlier that a micelle consists of a hydrophobic hydrocarbon like central core. The
cleansing action of soap is due to these micelles, because oil and grease can be solubilised in their hydrocar-
bon, like centres which are not otherwise soluble in water. This is shown diagrammatically in Figure The dirt
goes out along with the soap micelles.
CH2 CH2 CH2 CH 2 CH 2 CH 2 CH2 CH2 C

CH2 CH 2 CH 2 CH2 CH2 CH2 CH2 CH2 CH2 O¯Na+
(a) Sodium stearate (C17H35COO– Na+)
Hydrophilic head
 –
(b) Hydrophobic tail
Grease
(c) (d) (e)

Fig.: The cleansing action of soap.
 A sodium stearate molecule
 The simplified representation of the molecule that shows a hydrophilic head and a hydrophobic tail
 Grease (oily substance) is not soluble in water
 When soap is added to water, the non-polar tails of soap molecules dissolve in grease
 Finally, the grease is removed in the form of micelles containing grease.
 Surfactants : They can be ionic as well as non-ionic. The ionic are soaps and detergent. The surfactant gets
adsorbed at the interface between the dispersed droplets and dispersion medium in a form of mono molecular
layer and lowers the interfacial tension between oil and water so as to facilitate the mixing of two liquids.
5.4.4 P.No.: 139
 In these methods particles of atomic or molecular size are induced to combine to form aggregates having
colloidal dimensions. For this purpose chemical as well as physical methods can be applied.
CHEMICAL METHODS P.No.: 139

Colloidal solutions can be prepared by chemical reactions leading to formation of molecules by double
decomposition, oxidation, reduction or hydrolysis. These molecules then aggregate leading to formation of sols.
 Double decomposition : When a hot aqueous dilute solution of arsenous oxide (As2O3) is mixed with a
saturated solution of H2S in water, a colloidal sol of arsenous sulphide (As2S3) is obtained.
double decomposition
As2O3(in hot water) + 3H2S (saturated solution in H2O)   As 2S3 (sol)  3H 2 O
CH(OH)COOK CH(OH)COOK
+ 3H2S   + Sb2S3 (orange sol) + 2H2O
CH(OH)COO(SbO) CH(OH)COOH
 Oxidation : A colloidal sol of sulphur is obtained by passing H2S into a solution of sulphur dioxide.
SO2 + 2H2S (saturated solution in H2O) 
Oxidation
 3S(sol) + 2H2O
Sulphur sol can also be obtained when H2S is bubbled through Br2 water or nitric acid (oxidizing agent).
2H2S (aq.) + Br2 (aq.)  2HBr (aq.) + S (sol).
or by bubbling O2 (g) through a solution of H2S :
2H2S (aq.) + O2 (g)  2H2O (l) + 2S (sol).
 Reduction : Colloidal sol of metals like gold, silver solution are obtained by following method.
2AuCl3  3HCHO  3H 2 O 
 2Au(Sol)  3HCOOH  6HCl
(Purple of cassius)
reduction
2AuCl3  3SnCl2 
 3SnCl4  2Au(sol)
Reduction
AgNO3  tannic acid   silver sol.
NH2NH2 can also be used as reducing agent.
*Sol of gold is also known as purple of cassius.
 Hydrolysis : A colloidal sol of metal hydroxides like Al(OH)3 or Cr(OH)3 is obtained by boiling a dilute
solution of FeCl3, AlCl3 or CrCl3.
FeCl3 + 3H2O  Fe(OH)3 (sol) + 3HCl ; AlCl3 + 3H2O  Al(OH)3 (sol) + 3HCl
The colloidal sol of sillicic acid is also obtained by hydrolysis of dilute solution of sodium silicate with hydro-
chloric acid.
Na4SiO4 + 4HCl  Si(OH)4 (sol) + 4NaCl.
DISPERSION METHODS P.No.: 139

In these methods large particles of the substance are broken into particles of colloidal dimensions in the
presence of dispersion medium. These are stabilized by adding some suitable stabilizer. Some of the methods
employed are given below :
 Mechanical dispersion (By colloidal mill) : P.No.: 139
 Here the substance is first finely pow- Suspension
dered. It is shaken with the D.M. to form Hollow shaft
a suspension.
 This suspension is passed through a Driving belt
colloidal mill. The simplest type of colloi-
dal mill is disc mill which consists of two
metal discs nearly touching each other &
Discharge
rotating in opposite. Direction at a Discharge
high speed (7,000 revolutions per min.).
The suspended particles are broken to
produce colloidal size particle. Metal disc
 This method is used to prepare printing
ink. Fig. : A colloid mill
 Electrical disintegration or Bredig's Arc method : P.No.: 139

 This process involves dispersion as well as condensa- + Electrodes –
tion. Colloidal sols of less reactive metals such as gold,
silver, platinum, copper, lead etc., can be prepared by
this method.
 In this method, electric arc is struck between electrodes
of the metal immersed in the dispersion medium as Dispersion
shown in fig. The intense heat produced vaporises the medium
metal, which then condenses to form particles of colloi-
dal size by surrounding cooling mixture (ice). Ice-Bath
 A slight trace of KOH is added in water to stabilized
colloidal solutions. Fig. : Bredig's Arc method
 Peptization : P.No.: 140
 The term has originated from the digestion of proteins by the enzyme pepsin. Peptization may be de-
fined as (the process of converting a precipitate into colloidal sol by shaking it with dispersion medium
in the presence of a small amount of electrolyte).
 The electrolyte used for this purpose is called peptizing agent. This method is applied, generally, to
convert a freshly prepared precipitate into a colloidal sol. During peptization, the precipitate adsorbs
one of the ions of the electrolyte on its surface.
 The ion adsorbed on the surface is common either with the anion or cation of the electrolyte. This
causes the development of positive or negative charge on precipitates which ultimately break up into
smaller particles having the dimensions of colloids.
peptizing agent
ppt. Colloidal particle

For example :
1. When freshly precipitated Fe(OH)3 is shaken with aqueous solution of FeCl3 (peptizing agent) it
adsorbs Fe3+ ions and thereby breaks up into small-sized particles.
FeCl3  Fe3+ + 3Cl– ; Fe(OH)3 + Fe3+  Fe(OH)3 | Fe3+
+3 +3
+3
+3 +3 +3 +3
+3 +3
+3 +3 +3
+ Fe 3+ +3
+3 +3
Peptizing agent +3 +3 +3
+3
ppt of Fe (OH)3 +3 +3 +3 +3 +3 +3
+3 +3 +3
+3 +3
+3 +3 +3 +3
+3 +3
Charge Colloidal particals of Fe (OH)3
2. Freshly prepared stannic oxide on treatment with a small amount of dilute hydrochloric acid forms
a stable colloidal sol of stannic oxide, SnO2 ; Sn4+.
SnO2 + 4HCl  Sn4+ + 2H2O + 4Cl– ; SnO2 + Sn4+  SnO2 / Sn4+.
3. Freshly precipitated silver chloride can be converted into a colloidal sol by adding a small amount
of hydrochloric acid, AgCl : Cl–.
4. Cadmium sulphide can be peptised with the help of hydrogen sulphide, CdS : S2– .
5.4.5 P.No.: 140
 The colloidal sols obtained by various methods are impure and contain impurities of electrolytes and other
soluble substances. These impurities may destabilise the sol. Hence, they have to be removed. A very
important method of removal of soluble impurities from sols by a semipermeable membrane is known as
dialysis.
DIALYSIS P.No.: 140
 It is a process of removing a dissolved substance from a

colloidal solution by means diffusion through suitable mem-
brane. Since particles in true solution (ions or smaller mol-
ecules) can pass through animal membrane or parchment Distilled
paper or cellophane sheet but colloidal particle do not, the water
appratus used for this purpose is called Dialyser.
 A bag of suitable membrane containing the colloidal solu-
tions is suspended in a vessel through which fresh water Cellophane bag
continously flow. The molecules and ions (crystalloids) dif- Fig. : An apparatus for electrodialysis.
fuse through membrane into the outer water & pure colloidal
solution is left behind.
 Movement of ions across the membrane can be expedited by applying electric potential through two
electrodes as shown in figure.
 This method is faster than simple dialysis and is known as Electrodialysis.
 The most important applications of dialysis is in the purification of blood in the artificial kidney machine.
In case of kidney failure, blood cannot be purified. under such condition, the blood is separated from
dissolved toxic impurities by dialysis and re-introduced in the bloods stream.
*Dialysis is not applicable for non-electrolytes like glucose, sugar, etc.
ULTRA FILTRATION P.No.: 140

 In this method, colloidal sols are purified by carrying out filtration through special type of graded filters
called ultra-filters. These filter papers allow only the electrolytes to pass through.
 These filter papers are made of particular pore size by impregnating with colloidal solution and subse-
quently hardened by soaking in formaldehyde collodion. In order to accelerate the filtration through such
filter papers, increased pressure or section is employed.
03 39. Some of the properties given below are for colloidal

sols.
P.No.: 136-140 (I) Viscosity is same as that of the medium.
(II) Extensive hydration takes place.
36. The stability of lyophilic colloids is due to (III) Migration of the particles under electric field.
(1) Charge on their particles (IV) Particles cannot be detected even under ultra-
(2) A layer of dispersion medium on their particles microscope.
(3) The smaller size of their particles
(4) The large size of their particles Properties applicable for lyophilic and lyophobic
colloidal sols are
37. The stability of the dispersed phase in a lyophobic
colloids is due to Lyophilic Lyophobic
(1) High viscosity of the medium (1) I and II III and IV
(2) The formation of electrical layer between two (2) I and III II and IV
p hases (3) II and IV I and III
(3) High surface tension of sol (4) II and III I and IV
(4) None of these
40. Gelatin is mostly used in making ice-cream in order to
38. Which one of the following is not a colloidal solution?
(1) Smoke (1) Prevent making of colloid
(2) Ink (2) To stabilise the colloid and prevent crystallisation
(3) Air (3) To stabilise mixture
(4) Blood (4) To enrich the aroma
41. The process of separation of colloids by passing 48. Smoke is a dispersion of
through semi permeable membrane is called (1) gas in gas
(1) Filtration (2) gas in solid
(2) Electrophoresis (3) solid in gas
(3) Dialysis (4) liquid in gas
(4) Ultrafiltration 49. The colloidal sols are purified by
42. A liquid aerosol is a colloidal system of (1) Peptisation
(1) A liquid dispersed in a solid (2) Coagulation
(2) A liquid dispersed in a gas (3) Dialysis
(3) A gas dispersed in a liquid (4) Flocculation
(4) A solid dispersed in a gas 50. Bredig’s arc method cannot be used to prepare colloidal
43. The stabilization of a dispersed phase in a lyophobic solution of which of the following
colloidal sol is due to (1) Pt (2) Fe
(3) A g (4) A u
(1) the adsorp tion of charged sub stances on
dispersed phase 51. Lyophilic sols are more stable than lyophobic sols
(2) the large electrokinetic potential developed in the because
colloid (1) The colloidal particles have positive charge
(3) the viscosity of the medium (2) The colloidal particles have negative charge
(4) the formation of an electrical layer between two (3) The colloidal particles are solvated
p hases (4) There are strong electrostatic repulsions between
the negatively charged colloidal particles
44. Size of colloidal particles varies from
(1) 10 –7 to 10–9 m 52. Lyophilic sols are more stable than lyophobic sols
(2) 10 –9 to 10–17 m because their particles are
(3) 10 –5 to 10–7 m (1) Positively charged
(4) 10 –4 to 10–10 m (2) Negatively charged
(3) All soluble
45. The stabilisation of a lyophobic colloid is due to: (4) Attract each other
(1) preferential adsorption of similar charged particle
on colloids surface. 53. Which one of the following statements is false for
hydrophilic sols?
(2) the large electrokinetic potential developed in the
(1) they do not require electrolytes for stability
colloid.
(2) their viscosity is of the order of that of water
(3) the formation of a covalent bond between two
(3) their surface tension is usually lower than that of
phases.
dispersion medium.
(4) the viscosity of the medium. (4) none of these
46. Which one is an example of multimolecular colloid
54. Which of the following statements is not correct for a
system?
lyophobic solution?
(1) Soap dispersed in water (1) It can be easily solvated
(2) Protein dispersed in water (2) It carries charges
(3) Gold dispersed in water (3) The coagulation of this sol is irreversible in nature
(4) Gum dispersed in water (4) It is less stable in a solvent
47. The number of phases in colloidal system are 55. Purification of colloids is done by the process of
(1) One (1) Electrophoresis
(2) Two (2) Electrodispersion
(3) Three (3) Peptization
(4) Four (4) Ultrafiltration
5.4.6 P.No.: 141

 Heterogeneous character : Colloidal sols are heterogeneous in character as they consist of two phases.
1. dispersed phase and
2. dispersion medium.
 Visibility : Due to scattering caused by the colloidal particles, it will appear as a bright spot moving
randomly.
 Filterability : Colloidal particles pass through an ordinary filter paper. However, the particle do not pass
through other fine membranes.
COLLIGATIVE PROPERTIES P.No.: 141

 Colloidal sols show the colligative properties viz. relative lowering of vapour pressure, elevation in boiling
point, depression in freezing point and osmotic pressure. However, due to high average molecular masses of
colloidal particles, mole fraction of the dispersed phase is very low. Hence, the values of the colligative
properties observed experimentally are very small. Only osmotic pressure measurements are used in deter-
mining the molecular mass of polymers.
OPTICAL PROPERTIES-TYNDALL EFFECT P.No.: 141

 Tyndall, in 1869, observed that if a strong beam of light is passed through a colloidal sol placed in a dark
place, the path of the beam gets illuminated. This phenomenon is called Tyndall effect, which is due to the
scattering of light by the colloidal particles.
 The illuminated path of beam is called Tyndall cone.
 This phenomenon is due to scattering of light from the surface of colloidal particles. In a true solution there
are no particles of sufficiently large diameter to scatter light & hence the beam is invisible.
Eye
microscope
Tyndall cone
Light source
Scattered light
True solution Colloidal solution

 The intensity of scattered light depends on the difference between the refractive indice of the D.P and
D.M., In lyophobic colloids, this difference is appreciable and therefore the tyndal effect is quite well de-
fined but in lyophilic sols the difference is very small and the tyndal effect is very weak.
 Thus in sols of silicic acid, blood serum, albumin, etc. there is little or no tyndal effect.
EXAMPLE OF TYNDALL EFFECT
 Blue colour of sky and sea water.  Visibility of tail of comets.
 Light thrown from a projector in cinema hall.  Appearance of dust particle in a semi darked room.
APPLICATION OF TYNDALL EFFECT :
 In making ultramicroscopes.
 In finding heterogenity of solution.
BROWNIAN MOVEMENT P.No.: 142

 Robert Brown, a botanist, discovered in 1827 that pollen grains placed
in water do not remain at rest but move about continuously
and randomly.
 Later on, this phenomenon was observed in case of colloidal par-
ticles when they were seen under an ultramicroscope. The particles
were seen to be in constant zig-zag motion as shown in fig. This zig-
zag motion is called Brownian movement. (Fig. Brownian movement)
 Brownian movement arises because of the impact of the molecules of the dispersion medium with the
colloidal particles.
 It has been postulated that the impact of the molecules of the dispersion medium on the colloidal particle are
unequal leading to zig-zag motion. However, as the size of the particle increases, the effect of the impacts
average out and the Brownian movement becomes slow. Ultimately, when the dispersed particle becomes
big enough to acquire the dimensions of suspension, no Brownian movement is observed.
 Factors Affecting Brownian Movement :
1. If particles is large then brownian movement becomes less.
2. Brownian movement increases with increasing temperature.
3. The brownian movement does not change with time and remains same for months or even for a year.
 Important :
1. In confirmation of kinetic energy.
2. Determination of Avogadro numbers.
3. Stability of colloidal solution : Brownian movement does not allow the colloidal particles to settle
down to gravity & thus is responsible for their stability.
ELECTRICAL PROPERTIES (ELECTROPHORESIS) P.No.: 143
 The particles of the colloids are electrically charged and carry positive or negative charge.
 The dispersion medium has an equal and opposite charge making the system neutral as a whole.
 Due to similar nature of the charge carried by the particles, they repel each other and do not combine to
form bigger particles.
 That is why, a sol is stable and particles do not settle down. Arsenious sulphide, gold, silver and platinum
particles in their respective colloidal sols are negatively charged while particles of ferric hydroxide,
aluminium hydroxide are positively charged.
 The existence of the electric charge is shown by the phenomenon of electrophoresis.
 It involves the 'movement of colloidal particles either towards the cathode or anode, under the influence of
the electric field'. The apparatus used for electrophoresis as shown in fig.
Electrode
Coagulated sol
particles
As2S3 sol
(negatively charged)
Fig.: A set up for electrophoresis.

 The colloidal solution is placed in a U-tube fitted with platinum electrodes. On passing an electric current,
the charged colloidal particles move towards the oppositely charged electrode.
 Thus, if arsenic sulphide sol is taken in the U-tube, in which negatively charge particle of arsenic sulphide
move towards the anode.
 Earlier this process was called cataphoresis because most of the colloidal sols studied at that time were
positively charged and moved towards cathode.
ELECTROSMOSIS P.No.: 143

 When movement of colloidal particles is prevented by some suitable means (porous diaphragm or semi
permeable members), it is observed that the D.M. begins to move in an electric field. This phenomenon is
termed as electromosis.
 Sedimentation potential or Dorn potential : When the charged colloidal particles are made to settle
down under centrifugal field, there occurs a charge separation and a potential difference is developed. This
effect is called Dorn effect and the potential difference thus developed is called Dorn potential or sedimen-
tation potential. This process is reverse of electrophoresis.
 Isoelectric point : The H+ concentration at which the colloidal particles have no charge is known as the
isoelectric point. At this point stability of colloidal particles becomes very less & do not move under influ-
ence of electric field.
 Streaming potential : A potential difference is developed across a porous partition when the dispersion
medium of a charged colloid is forced through it. This is called Streaming potential. This process is reverse
of electro-osmosis.
CHARGE ON COLLOIDAL PARTICLES P.No.: 143

Colloidal particles are either positively charged or negatively charged. This charge is due to preferential
adsorption of either positive or negative ions on their surface. There is adsorption of common ion present in
excess.
 Fe(OH)3 sol prepared by the hydrolysis of FeCl3 solution adsorbs Fe3+ and this is positively charged.
 Fe(OH3) + 3HCl ;
FeCl3 + 3H2O  Fe(OH)3  FeCl3   Fe(OH)3 | Fe3 : 3Cl 
Fixed part Diffused part
Positive charge on colloidal sol is due to adsorption of Fe3+ ion [common ion between Fe(OH)3 and FeCl3].
 As2S3 colloidal sol is obtained when As2O3 is saturated with H2S :
As2O3 + 3H2S  As2S3 + 3H2O.
2–
As2S3 adsorbs S ions (common between H2S and As2S3 and thus is negatively charged).
As2S3 + H2S  As2S3 | S2– : 2H+
 AgI in contact with AgNO3 forms positively charged colloidal sol due to adsorption of Ag+ ion.
AgI + AgNO3  [AgI]Ag+ : NO3–, AgI in contact with KI forms negatively charged colloidal sol due to
adsorption of I– ion
AgI + KI  AgI | I– : K+.
 SnO2 in acidic medium forms positively charged colloidal sol due to adsorption of Sn4+ formed.
SnO2 + 4H+  Sn4+ + 2H2O SnO2 + Sn4+  SnO2 + Sn4+
SnO2 in alkaline medium forms negatively charged colloidal sol due to adsorption of SnO32– formed.
SnO2 + 2OH–  SnO32– + H2O SnO2 + SnO32–  SnO2 + SnO32–
ELECTRIC DOUBLE LAYER THEORY OR HELM-HOLTZ ELECTRIC DOUBLE LAYER P.No.: 143
 The surface of colloid particles acquire a positive or negative charge by the selective (preferential) adsorp-
tions of common ions carrying positive or negative charge respectively to form first layer.
 This layer attract counter ions from D.M. form a second layer.
 The combination of two layers of opposite charge around the colloidal particle is called Helm-holtz electric
double layer.
 The first layer of ions is firmely held and is termed as fixed layer while the second layer is mobile which is
termed as diffused layer. The charge of opposite ions of fixed and diffused layer double layer results in a
difference in potential between two opposite charge layer is called the electrokinetic potential or zetapotential
Example : When silver nitrate solution is added to KI solution, the precipitation of AgI adsorb iodide ions
from the D.M with the formation of fixed layer and negatively charged colloidal solution form, however
when KI solution is added to AgNO3 solution positive charge sol result due to the adsorbs of Ag+ ions from
D.M.
AgI / I– AgI / Ag+
Negative charged Positively charged.
This fixed layer attracts counter ions from the medium forming a second layer.
Fixed layer
+
K
+
K
+
K
I– –
I
– I K
+
–
I– AgI I
K
+ I– I
–
– –
I I
– I K
+
Zetapotential K+ +
K
K
+
Diffused layer
COAGULATION / FLOCCULATION P.No.: 144

 The presence of small amounts of appropriate electrolytes is necessary for the stability of the colloids.
 However, when an electrolyte is added in larger concentration; the particles of the sol take up the ions
which are oppositely charged and thus get neutralised.
 The neutral particles then start aggregating giving particles of larger size which are then precipitated. This
process of aggregation of colloidal particles into an insoluble precipitate by the addition of some suitable
electrolyte is known as coagulation.
 At lower concentration of electrolytes, the aggregation of particles is called flocculation that can be re-
versed on shaking while at higher concentration of electrolyte, coagulation takes place and the same cannot
be reversed simply by shaking.
 The stability of the lyophobic colloids is due to presence of charge on colloidal particles. If, somehow, the
charge is removed, the particles will come near to each other to form aggregates and settled down under the
force of gravity.
+ + + + +
+ + + + ++ +
++
+ ++ +
+ ++ + + + + +
+ ++ + +
+ ++
+ + + + +
+ ++ +++ + + +
+ ++ +
+ ++
++ +
+ ++
+ ++ +
+ + + + ++ ++ ++ + + +
+
+ + +
+ ++
+
+
+ +
+ + ++ + +
+ + ++ + ++ +
+ +
++ + + + + + +
+ + + + +
+ + + + +
+ ++ + + +
+ +
+ + + + ++ +
+ + + + ++ +
++ + + + +
+ + +++ +
++
+
+ ++ + + +
+ ++ ++
+ ++ +
+ ++ +
+ + +
+ + +
+ ++
+ ++
+++
+ ++
+ +
+
+
+
Neutralised
sol particles Coagulated sol
 Coagulation of lyophobic sols can be carried out by the following methods.
1. By electrophoresis
2. By mutual precipitation : It is a process in which oppositely charged sol are mixed in proper propor-
tion to neutralise the charge of each other causing coagulation of both the sol.
Example : Positively charged Fe(OH)3 and negatively charged As2S3 colloidal particle containing sol
on mixing get coagulated.
3. By Prolonged Dialysis : On prolonged dialysis, traces of the electrolyte present in the sol are
removed almost completely and the colloidal unstable and ultimately coagulate.
4. By Boiling : Sols such as sulphur and silver halides dispersed in water may be coagulated by boiling
because increased collisions between sol particle and the water molecule removed the adsorbed elec-
trolytes. This takes away the charge from the particles and helps them to coagulate.
5. By cooling : Certain sol can also be coagulated by lowering temperature. For example, accumula-
tion of cream on the surface of milk on cooling. This is because at lower temperature the dispersion
medium molecules do not exert sufficient force on to the dispersed particles and hence the Brownian
motion becomes less effective.
6. By the addition of electrolyte : When excess of an electrolyte is added, the colloidal particles are precipitated.
COAGULATION VALUE OR FLOCCULATION VALUE P.No.: 144
 It needs to be noted that the coagulation of a colloidal solution by an electrolyte does not take place until
the added electrolyte has certain minimum concentration in the solution. The minimum concentration of
electrolyte in millimoles required to cause coagulation of one litre of colloidal solution is called coagula-
tion value. It is express in terms of millimoles/litre.
millim oles of electrolyte
Coagulation value = volumeof sol in litre
 Comparision of relative coagulating power of two electrolyte for the same colloidal solution : The
coagulation value decrease with increase in charge of the coagulating ion.
1
Coagulating power  coagulation value
coagulating power of electrolyte A coagulation value B

coagulating power of electrolyte B coagulation value A .
=
 Factor-Affecting Coagulations :
1. Nature of sols : The lyophobic colloid can easily coagulate because it is a less stable colloid, but
lyophilic colloids coagulate hardly by the addition of electrolyte due to protective layer of D.M.
surrounding the colloidal particle.
2. Nature of electrolyte : In equimolar electrolyte, strong electrolyte have greater coagulating power
than weak electrolyte. For example,
0.1 M NaCl > 0.1M CH3COOH.
HARDY-SCHULZE RULE : P.No.: 144

 According to this rule greater is the valency of coagulating ion, greater its power to cause precipitation. This
is known as Hardy-Schulze.
In case of positive charged sol, the coagulating power of anion is in the order of [Fe(CN)6]4– > PO43– >
SO42– > Cl–
In case of negative charged sol, the coagulating power of cation is in the order of Al3+ > Ba2+ > Na+.
 The coagulating power of bivalent ion is 20-80 times higher than monovalent ion and coagulating power of
trivalents is many times more than bivalent.
PROTECTIVE COLLOID P.No.: 145
 Lyophilic colloidal sols are much more stable than lyophobic colloidal sols.
 This is due to the extensive solvation of lyophilic colloidal sols, which forms a protective layer outside it and
thus prevents it from forming associated colloids.
 Lyophobic sols can easily precipitate by addition of small amount of an electrolyte. They can be prevented
from coagulation by previous addition of some lyophilic colloid.
 This is due to formation of a protective layer by lyophilic sols outside lyophobic sols. Process of protecting
the lyophobic colloid solution from precipitation by an electrolyte due to previous addition of some lyo-
philic colloid is called protection of colloid and lyophilic colloidal sols are called protective sols.
For example, Gelatin, Sodium caseinate, Egg albumin, Gum arabic, Potato starch etc.,
Gelatin (lyophilic) protects gold sol (lyophobic) colloids is expressed in terms of gold number.
GOLD NUMBER :
 Zsigmondy (1901) introduce a term called gold number it is defined as the minimum amount of the protective
colloid in milligrams which when added to 10 ml of a standard gold sol is just sufficient to prevent a colour
change from red to blue on the addition of 1 ml of 10% sodium chloride solution. It may be noted that
smaller of the gold number, greater will be protecting power of the protective colloid.
1
Protecting power  .
gold number
weight of lyophilicsol in mg 10

Gold Number = volume of gold sol in mL
 The gold numbers of a few protective colloids are as follows :
Gelatin Haemoglobin Egg albumin Gum arabic DextrinStarch
0.005 - 0.01 0.03 - 0.07 0.1 - 0.2 0.15 - 0.25 6 – 6.220 - 25
 Uses of protective action :

1. Gelatin is added in the preparation of ice cream to protect the particle of ice.
2. Protargol and Argyrol, is a silver sol protected by organic material used as eye drop.
5.5 EMULSIONS P.No.: 145
 Pair of immiscible liquid is called emulsion.

 Emulsion are unstable and some time they are separated into two layers on keeping still, for the stabilising of an
emulsion, a third component is added called emulsifying-Agent form an interfacial film between D.P. and D.M.
 Emulsion droplets are bigger than sol particles and can be seen under an ordinary microscope and some-
times even with a magnifying glass.
Example : Milk is an emulsion in which liquid fat is D.P. and liquid water is D.M. and casein is emulsifying
agent.
 Demulsification : The separation of an emulsion into its constituent liquids is called demulsification. Vari-
ous techniques employed for this are freezing, boiling, centrifugation, electrostatic precipitation or chemical
methods which destroys the emulsifying agents.
Demulsification can be brought about by :
1. Freezing
2. Heating
3. Centrifugal action (Separation of cream of milk done by centrifugation).
4. Removal of emulsifiers by adding a better solvent for them like alcohol, phenol etc, called demulsifiers.
 Types of emulsions : Depending on the nature of the dispersed phase, the emulsions are classified as :
(a) Oil in water emulsions (o/w) : This type of emulsions is formed when oil D.P. and water D.M.
For example, Milk and vanishing cream are oil - in - water type emulsions.
(b) Water in oil emulsions (w/o) : This type of emulsions is formed when water is D.P. and oil is D.M.
For example, Cold cream and cod liver oil.
 Inversion of phase : The conversion of emulsion of oil in water (o/w) into water in oil (w/o) or vice versa
is called the inversion of phase.
 Applications of emulsions :
1. Disinfactants like phenyl, dettol when mixed with water form emulsion.
2. Digestion of fat in small intestine occurs easily due to emulsion.
3. In metallurgical process the concentration of ore by froath floatation method is based upon emulsion.
4. Milk is an emulsion of liquid fat in water in which casein emulsifying agent.
5. Cleansing action of soap is due to formation of emulsions. Soaps and detergents emulsify the grease
along with the adhering dirt and carry them away in the wash water.
6. For concentrating ores, the finely powdered ore is treated with an oil. Oil forms emulsion with the ore
particles. When air is bubbled into the mixture, emulsion containing the particles of the mineral are
carried to the surface.
5.6 COLLOIDS AROUND US P.No.: 145
Colloids including emulsions find a number of uses in our daily life and industry. Some of the uses are given
below.
 In medicines : A wide variety of medicinal and pharmaceutical preparations are emulsions. Colloidial
medicines are easily adsorbed by the body tissue because of large surface area.
* Colloidal antimony is used in curing kalaazar.
* Milk of magnesia, an emulsion, is used for stomach disorder.
* Colloidal gold is used for intramuscular injection.
* Colloidal sulphur are used as Germicides.
* Argyrol is a silver sol used as an eye lotion.
* Colloidal Fe(OH)3 is given to arsenic poisoning patients as it adsorbs arsenic and then gets omited out.
 Tanning : Animal hides are colloidal in nature. Which contain positive charge colloidal particles of protein.
This hide is kept in a tank containing tannic acid, which contains negatively charge colloidal particle. There-
fore, mutual coagulation takes place this results in hardening of leather, this process is termed as tanning of
leather. Chromium salts are also used in place of tannic acid.
 Photographic plate & Film : Photographic plate or films are prepared by coating an emulsion of the light
sensitive silver bromide in gelatin over glass plates or celluloid films. Gelatin prevent the coagulation of
colloidal particle of AgBr.
 Rubber plating : The negatively charged rubber particles from rubber sol are deposited on wares and
handles of different tools. Rubber gloves are formed by rubber plating on suitable templates.
 Sewage disposal : Sewage water contains charged colloidal particles of dirt, rubbish, etc., and these do not
settle down easily. The particles can be removed by discharging them at electrodes. Dirty water is passed
through a tunnel fitted with metallic electrodes which are maintained at high potential difference. The par-
ticles migrate to the oppositely charged electrode, lose their charge and get coagulated. The deposited
matter is used as a manure and the water left behind is used for irrigation.
 Cottrell smoke precipitator : Smoke is a dispersion of negatively charged colloidal particles of carbon in
air and can be made free of these colloidal particles by passing it through cottrell precipitator as shown in
fig. installed in the chimney of an industrial plant. It consists of two metal discs charged to a high potential.
The carbon particles get discharged and precipitate, while gases come out from the chimney.
Gases free
from carbon
particles
Precipitated ash
Smoke
Fig. : Cottrell smoke precipitator.

 Formation of deltas : The river water contains colloidal particles of sand and clay which carry negative
charge. The sea water contains +ve ions such as Na+, Mg2+, Ca2+, etc. As the river water meets sea water,
these ions discharge the sand or clay particle which are precipitated in the form of delta.
 Artificial rain : Cloud consists of charge particle of water disperse in air. Rain is caused by aggregation of
these minute particles, artificial rain can be done by throwing electrified sand or Agl from aeroplanes,
colloidal H2O particle present in cloud will get coagulated by these sand or Agl particles to form bigger
water drops causing rain.
 Stop bleeding from a cut : Blood is a colloidal solution containing a –ve charge colloidal particle (Albu-
minoid), bleeding can be stopped by use of alum or FeCl3 solution. The addition of Al3+ or Fe3+ causes
coagulation of blood, so bleeding stops.
 Stop Screen : It is used warfare for concenalment and camouflage by spraying very fine particles of tita-
nium oxide from aeroplane. As titanium oxide is very heavy, the smoke screen drops down rapidly as a
curtain of dazzling whiteness. This is due to scattering of light by colloidal particles.
 Preparation of nano-materials : These materials are prepared for use as catalyst by using reverse
micelles.
 In disinfectants : The disinfectants such as dettol and lysol give emulsions of the oil-in-water type when
mixed with water.
 In metallurgical operations : Emulsions play an important role in industry. The metal ores are concen-
trated by froth-floatation process which involves the treatment of the pulverised ore in emulsion of pine oil.
 Building roads : Asphalt emulsified in water is used for building roads without the necessity of melting the
asphalt.
04 62. On addition of 1 ml solution of 10% NaCl to 10 ml gold

sol in the presence of 0.25g of starch, the coagulation
is just prevented. Starch has the following gold number
P.No.: 141-145
(1) 0.025 (2) 0.25
56. As2S3 sol has a negative charge. Capacity to precipitate
(3) 0.5 (4) 250
it is highest in
63. The average molecular mass of colloidal can be
(1) AlCl3 (2) Na 3PO 4
determined by
(3) CaCl2 (4) K2SO 4 (1) Tyndall effect
57. Which of the following is most effective in coagulating (2) Boiling of colloidal
a ferric hydroxide sol? (3) Osmotic pressure measurement
(1) KCl (2) KNO3 (4) Flocculation value
(3) K2SO 4 (4) K3[Fe(CN)6] 64. Ferric hydroxide sol is positively charged colloid. The
58. The minimum concentration of an electrolyte required
coagulating power of NO3 , SO 24 and PO34 would
to cause coagulation or flocculation of a sol is called its
flocculation value. It is expressed in be in the order
(1) mol L–1 (2) g L–1 (1) NO3 > SO 24  > PO34
(3) millimoles L –1
(4) equivalent L–1 (2) SO 24  > NO3 > PO34
59. Which of the following electrolytes is least effective (3) PO34 > SO 24  > NO3
in causing flocculation of ferric hydroxide sol?
(1) K2[Fe(CN)6] (2) K2CrO4 (4) NO3 = SO 24  = PO34
(3) KBr (4) K2SO 4 65. A negatively charged suspension of clay in water will
need for precipitation the minimum amount of
60. Sky looks blue due to
(1) Aluminium chloride
(1) Dispersion effect
(2) Potassium sulphate
(2) Reflection
(3) Sodium hydroxide
(3) Transmission
(4) Hydrochloric acid
(4) Scattering 66. Which type of property is the Brownian movement of
61. In which of the following Tyndall effect is not observed colloidal sol?
(1) Suspensions (2) Emulsions (1) Electrical (2) Optical
(3) Sugar solution (4) Gold sol. (3) Mechanical (4) Colligative
67. Movement of colloidal particles under the influence of 72. Milk can be preserved by adding a few drops of
electrostatic field is (1) Formic acid solution
(1) Electrophoresis (2) Electrolysis (2) Formaldehyde solution
(3) Dialysis (4) Ionisation
(3) Acetic acid solution
68. Which of the following is not represented by sols?
(4) Acctaldehyde solution
(1) Adsorption (2) Tyndall effect
73. Gold number is associated with
(3) Flocculation (4) Paramagnetism
69. Which of the following electrolytes have maximum (1) Only lyophobic colloids
coagulating power? (2) Only lyophilic colloids
(1) CCl4 (2) ZnCl2 (3) Both lyophobic and lyophilic colloids
(3) KCl (4) NaCl (4) None of these
70. Arsenic (III) sulphide forms a sol with a negative charge. 74. For coagulating As 2 S 3 colloidal sol. which of the
Which of the following ionic substances should be following will have the lowest coagulation value
most effective in coagulating the sol?
(1) NaCl (2) KCl
(1) KCl (2) MgCl 2
(3) BaCl2 (4) AlCl3
(3) Al 2(SO 4) 3 (4) Na 3PO 4
75. Which one o f the following substance gives a
71. The presence of colloidal particles of dust in air imparts
positively charged sol?
blue colour to the sky. This is due to
(1) Absorption of light (2) Reflection of light (1) Gold (2) A metal sulphide
(3) Refraction of light (4) Scattering light (3) Ferric hydroxide (4) An acidic dye
5.7 Synopsis
ADSORPTION  Concentration of the adsorbate is more on the
 Definition and Properties surface of the adsorbent than in the bulk.
 The accumulation of molecular species at the Chemisorption
surface rather than in the bulk of a solid or liquid.  Concentration of the adsorbate increases in
 Surface phenomena. the bulk after adsorption.
 Spontaneous, exothermic & leads to lowering Adsorption Isotherms
of entropy.
195 K
 Terminology b
q
 Adsorbate : Substance adsorbed. a
 Adsorbent : Substance on the surface of x 244 K 1
x Slope =
which adsorbate is adsorbed. 273 K log n
 Desorption : Reverse of adsorption.
m m 
 Occlusion : Adsorption of gases on the  log K (Intercept)
surface of metals. 
 Sorption : Adsorption and absorption take P log P
place simultaneously. Adsorption isotherm Freundlich isotherm
 Types CATALYSIS
Physisorption  Definition
 Molecules are held by weak van der Waals forces.  The phenomenon of enhancing the rate of a
 Low heat of adsorption and non-specific. chemical reaction by using catalyst.
 No compound is formed.  Terminology
 Descreases with increase in temperature.  Promoters : Substances that enthane the
 Forms multimolecular layer and is reversible. activity of a catalyst.
Chemisorption  Poisons : Substance which decrease the
 Molecules are held by strong chemical bonds. activity of a catalyst.
 High heat of adsorption and specific.  Activity : Capacity to increase the speed of
 Surface compounds are formed. the chemical reaction.
 Increases with increase layer & is irreversible.  Selectivity : Ability of a catalyst to direct
Positive adsorption the reaction to yield a particular product.
 Types – Water in oil type emulsions e.g., butter.
 Homogeneous catalysis : When the reac- Based on nature of interaction between dis-
tants and catalyst are in the same phase e.g., persed phase and dispersion medium :
oxidation of SO2 to SO3 in presence of NO  Lyophilic colloids : Liquid-loving, directly
as catalyst (lead chumber process) formed, reversible in nature, quite stable, can-
 Heterogeneous catalysis : When the re- not be easily congulated.
actants and catalyst are in different phasees  Lyophobic colloids : Liquid-hatingm, pre-
e.g., manufacture of NH3 from N2 and H2 pared by special methods, readily coagulated,
using Fe as catalyst. (Haber’s process) irreversible, not stable, and need stabilising
 Autocatalysis : One of the products formed agents for their preservation.
itself acts as a catalyst e.g., titration of Based on type of particles of the dispersed phase:
oxalic acid with KMnO 4 in presence of  Multimolecular colloids : Formed by ag-
dil.H2SO4. gregation of a large number of atoms or mol-
 Induced catalyst : One reaction influences ecules (diameter < 1 nm) held by weak van
the rate of other reaction, which does not der Waals forces.
occur under ordinary conditions e.g., oxidation  Macromolecular colloids : Formed by mol-
of sodium arsentite is induced by oxidation of ecules of large size.
sodium sulphite.  Associated colloids : Formed by substances
 Positive catalysis : Catalyst increases the which at low concentrations behave as nor-
speed of a reaction. mal strong electrolytes, but at higher concen-
 Negative catalysis : Catalyst decreases the tration exhibit colloidal behaviour due to the
speed of a reaction. formation of aggregates (called micelles).
 Important Processes and Properties
 Shape-Selective Catalysis :
 Tyndall effect : Scattering of light by the
 Depends upon the pore structure of catalyst
colloidal particles.
and size of reactant and product molecules.
 Brownian movement : Continuous zig-zag
 Zoolites are good shape-selective catalysis
movement of colloidal particles.
due to honey comb-like structures.
 Peptization : Converting a precipitate into
 Enzymes
colloidal sol by shaking it with dispersion
 Biocatalysts medium in the presence of a small amount of
 Highly efficient and specific in nature. electrolyte.
 Highly active under optimum temperature and  Dialaysis : Separation of colloidal particles from
pH. crystalloids by filtration using ultrafilter papers.
 Activity increases in the presence of activators  Coagulation : Setting of colloidal particles.
and co-enzymes.  Zeta potential : Potential difference
 Activity inhibited by inhibitors and poisons. between the fixed layer and the diffused layer
COLLOIDS of opposite charges, also called electrokinetic
 Definition potential.
 A heterogeneous system in which particle size Have a Look !
is between 1 and 1000 nm.  Higher the critical temperature of a gas, more
strongly it is adsorbed.
 Terminology  A more strongly adsorbable substance can displace
 Dispersed phase : Substance which is dis- a weakly adsorbed substance from the surface of
persed. It is a discontinuous phase. the adsorbent.
 Dispersion medium : Medium in which the  The minimum amount of an electrolyte (millimoles)
substance is dispersed. It is a continuous phase. that must be added to one litre of a colloidal solu-
 Classification : tion for complete coagulation is called the coagu-
Based on physical state of dispersed phase lation or flecculation or precipitatiton value of
and dispersion medium : the electrolyte and smaller the value, greater is its
 Sols : Solids in liquids e.g., paints coagulating power.
 Gels : Liquids in solids e.g., cheese  According to Hardy-Schulze rule, greater the va-
 Emulsions : Liquids in liquids. lency of th eflocculating ion added, greater is its
– Oil in water type emulsions e.g., milk power to cause precipitation.
1. Which of the following statements about physical 8. Which one is false in the following statement ?
adsorption is not correct ? (1) A catalyst is specific in its action
(1) It is usually monolayer (2) A very small amount of the catalyst alters the rate
(2) It is reversible in nature of a reaction
(3) It involves van der Waals interactions between (3) The number of free vacancies on the surface of
adsorbent and adsorbate the catalyst increases on sub-division
(4) It involves small enthalpy of adsorption as com- (4) Ni is used as a catalyst in the manufacture of am-
pared to chemisorption. monia
2. Which of the following statements regarding adsorp- 9. Softening of hard water is done using sodium alu-
tion is not correct ? minium silicate (zeolite). The causes :
(1) Extent of adsorption of gases on charcoal in- (1) adsorption of Ca 2+ and Mg 2+ ions of hard water
creases with increase in pressure of the gas replacing Na+ ions.
(2) Extent of adsorption is independent of temperature (2) adsorption of Ca 2+ and Mg 2+ ions of hard water
(3) Extent of chemisorption by a given mass of ad- replacing Al3+ ions.
sorbent is limited (3) both (A) and (B)
(4) Extent of adsorption is dependent on the nature (4) none of these
of adsorbent 10. Which requires catalyst ?
3. There is desorption of physical adsorption when: (1) S + O2  SO2 (2) 2SO2 + O2  2SO3
(1) temperature is increased (3) C + O2  CO2 (4) All
(2) temperature is decreased 11. A catalyst in a reaction :
(3) pressure is increased (1) increases the activation energy of the forward re-
(4) concentration is increased action.
4. The rate of chemisorption : (2) increases the activation energy of the backward
(1) decreases with increase of pressure reaction.
(2) increases with increase of pressure (3) increases the activation energy of both the reac-
(3) is independent of pressure tions.
(4) is independent of temperature (4) decreases the activation energy of both the reac-
tions.
5. Which of the following statements about chemisorp-
tion is not applicable? 12. A catalyst in a reaction changes which of the follow-
ing ?
(1) It involves chemical forces between adsorbent
and absorbate (1) Equilibrium constant
(2) It is irreversible in nature (2) Entropy
(3) It involves high heat of adsorption (3) Rate constant
(4) It involves low activation energy (4) Nature of products.
6. Which of the following is not characteristic of chemi- 13. Consider the following reactions ;
sorption? (i)  2SO
2SO2 + O2  3
(1) it is irreversible
(ii)  2NH
N2 + 3H2  3
(2) it is specific
(3) it is multilayer phenomenon  2NO
(iii) N2 + O2 
(4) heat of adsorption of about – 400 kJ  2HI
(iv) H2 + I2 
7. A catalyst increases rate of reaction by :
The reactions which require a catalyst are :
(1) decreasing enthalpy
(1) (i) and (iii)
(2) decreasing internal energy
(2) (ii) and (iv)
(3) decreasing activation energy
(3) (i) and (ii)
(4) increasing activation energy
(4) all of these
14. Which of the following kind of catalysis can be ex- 24. Colloidal gold is prepared by :
plained by the adsorption theory ? (1) mechanical dispersion
(1) Homogeneous catalysis (2) peptisation
(2) Acid-bas catalysis (3) Bredig's arc method
(3) Heterogeneous catalysis (4) hydrolysis
(4) Enzyme catalysis 25. Tyndall effect is observed in :
15. A biological catalyst is essentially : (1) solution (2) precipitate
(1) an enzyme (2) a carbohydrate (3) sol (4) vapour
(3) an amino acid (4) a nitrogeneous base 26. Lyophillic colloids are stable due to :
16. Colloidal solution of gold prepared by different meth- (1) charge on the particle
ods of different colours because of : (2) large size of the particle
(1) different diameters of colloidal gold particles (3) small size of the particle
(2) variable valency of gold
(4) layer of dispersion medium on the particles
(3) different concentration of gold particles
27. Peptization is a process of :
(4) impurities produced by different methods
(1) precipitation of colloidal particles.
17. An example of intrinsic colloid (lyophilic colloids) is :
(2) purification of colloids.
(1) As 2S 3 sol (2) Fe(OH)3 sol
(3) dispersing precipitate into colloidal sols.
(3) Egg albumin (4) Au sol
(4) movement of colloidal particles in the electrical field.
18. Which of the following sols is negatively charged?
28. Gold number of a lyophilic sol is such property that:
(1) Arsenious sulphide
(1) the larger its value, the greater is the peptising
(2) Aluminium hydroxide power
(3) Ferric hydroxide (2) the lower its value, the greater is the peptising
(4) Silver iodide in silver nitrate solution power
19. Peptisation is: (3) the lower its value, the greater is the protecting
(1) conversion of a colloidal into precipitate form power
(2) conversion of precipitate into colloidal sol (4) the larger its value, the greater is the protecting
(3) conversion of metal into colloidal sol by passage power
of electric current 29. Protective sols are :
(4) conversion of colloidal sol into macromolecules (1) lyophilic
20. Bleeding is stopped by the application of ferric chlo- (2) lyophobic
ride. This is because: (3) both (1) and (2)
(1) the blood starts flowing in opposite direction (4) none of (1) and (2)
(2) the blood reacts and forms a solid, which seals 30. Which of the following ions is most effective in the
the blood vessel coagulation of an arsenious sulphide solution ?
(3) the blood is coagulated and thus the blood ves- (1) K+ (2) Mg 2+
sel is sealed (3) Al 3+
(4) C
(4) the ferric chloride seals the blood vessel. 31. Which of the following ions is most effective in the
21. Which of the following is a hydrophilic colloidal sol ? coagulation of ferric hydroxide solution ?
(1) Barium sulphate sol (1) Cl¯ (2) Br–
(2) Arsenious sulphide sol (3) NO 2 ¯ (4) SO 42–
(3) Starch sol 32. Gold number gives :
(4) Silver iodide sol (1) the amount of gold present in the colloid.
22. Cloud is an example of : (2) the amount of gold required to break the colloid.
(1) solid dispersed in gas (3) the amount of gold required to product the colloid.
(2) liquid dispersed in gas (4) none of the above.
(3) liquid dispersed in solid 33. Gelatin is mostly used in making ice cream in order to:
(4) solid dispersed in liquid (1) prevent making of a colloid.
23. Which one among the following sols is hydrophobic ? (2) stabilize the colloid and prevent crystallization.
(1) Gum (2) Gelatin (3) stabilize the mixture.
(3) Starch (4) Sulphur (4) enrich the aroma.
34. Which one of the following will have the highest 43. Purification of colloids is done by the process of
coagulation power for a ferric hydroxide sol ? (1) Electrophoresis
(1) NaCl (2) BaCl2 (2) Electrodispersion
(3) K2CrO4 (4) K3[Fe(CN)6] (3) Peptization
35. Small liquid droplets dispersd in another liquid is called: (4) Ultrafiltration
(1) Suspension (2) Emulsion 44. Which of the following forms cationic micelles above
(3) Gel (4) True solution certain concentration?
36. At CMC, the surfactant molecules : (1) Urea
(1) Decomposes (2) Cetyltrimethylammonium bromide
(2) Become completely soluble (3) Sodium dodecyl sulphate
(3) Associate (4) Sodium acetate
(4) Dissociate 45. Fog is an example of
37. Some type of gels like gelatin loose water slowly. The (1) Solid dispersed in gas
process is known as : (2) Liquid dispersed in gas
(1) synerisis (2) thixotropy (3) Liquid dispersed in solid
(3) peptisation (4) imbibition (4) Solid dispersed in liquid
38. In which one of the following properties emulsions 46. Liquid-liquid sol is known as
differ from colloidal sols ? (1) aerosol (2) foam
(1) Tyndall effect (3) emulsion (4) gel
(2) Brownian movement 47. The ability of ion to bring about coagulation of a given
(3) Electrophoresis colloidal solution depends upon
(4) Size of the particles of the dispersed phase (1) Its size of ion
39. Cod liver oil is : (2) The magnitude of charge
(1) fat dispersed in water (3) The sign of charge
(2) water dispersed in fat (4) Both magnitude and sign of charge
(3) water dispersed in oil 48. A coagulating agent frequently added to water to
(4) fat dispersed in oil remove the suspended and colloidal impurities is
40. The efficiency of an enzyme in catalysing a reaction is (1) Mohr salt
due to its capacity (2) Alum
(1) To form a strong enzyme–substrate complex (3) Bleaching powder
(2) To decrease the bond energies o f substrate (4) Copper sulphate
molecule 49. Ferric chloride is applied to stop bleeding cut because
(3) To change the shape of the substrate molecule (1) Fe 3+ ion coagulates blood, which is a negatively
(4) To lower the activation energy of the reaction charged sol
41. Which of the following is true about catalyst? (2) Fe 3+ ion coagulates blood, which is a positively
(1) It initiates reaction charged sol
(2) It changes equilibrium point (3) Cl – ion coagulates blood, which is a positively
(3) It increase average kinetic energy charged sol
(4) It accelerates the rate of reaction (4) Cl – ion coagulates blood, which is a negatively
42. In which of the following processes, platinum is used charged sol
as a catalyst 50. Alum helps in purifying water by
(1) Oxidation of ammonia to form nitric acid (1) Forming Si complex with clay particles
(2) Hardening of oils (2) Sulphate part which combines with the dirt and
(3) Production of synthetic rubber removes it
(4) Synthesis of methanol (3) Aluminium which coagulates the mud particles
(4) Making mud water soluble
(Concept Builder)
1. Which of the following process does not occur at the 11. Which of the following is an example of absorption?
interface of phases? (1) Water on silica gel
(1) Crystallisation (2) Water on calcium chloride
(2) Heterogeneous catalysis (3) Hydrogen on finely divided nickel
(3) Homogeneous catalysis (4) Oxygen on metal surface
(4) Corrosion 12. On the basis of data given below predict which of the
2. At the equilibrium position in the process of adsorption: following gases shows least adsorption on a definite
(1) H > 0 (2) H = TS amount of charcoal?
(3) H > TS (4) H < TS Gas CO 2 SO 2 CH 4 H2
3. Which of the following interface cannot be obtained? Critical temp./K 304 630 190 33
(1) Liquid-liquid (2) Solid-liquid (1) CO 2 (2) SO
(3) Liquid-gas (4) Gas-gas (3) CH 4 (4) H2
4. The term ‘sorption’ stands for : 13. In which of the following reactions heterogeneous
(1) absorption catalysis involved?
(2) adsorption NO
(g )
(i) 2SO 2(g)  O 2(g)   2SO3(g)
(3) both absorption and adsorption
Pt
(4) desorption (ii) (s )
2SO2(g)   2SO3(g)
5. Extent of physisorption of a gas increases with :
Fe(s )
(1) increase in temperature (iii) N 2(g)  3H 2(g)   2NH3(g)
(2) decrease in temperature HCl
(l )
(3) decrease in surface area of adsorbent (iv) CH3COOCH3( l )  H 2 O( l )  
(4) decrease in strength of van der Waals forces CH3COOH(aq)  CH3OH (aq)
6. Extent of adsorption of adsorbate from solution phase (1) (ii), (iii) (2) (ii), (iii), (iv)
increases with : (3) (i), (ii), (iii) (4) (iv)
(1) increase in amount of adsorbate in solution 14. At high concentration of soap in water, soap behaves
(2) decrease in surface area of adsorbent as :
(3) increase in temperature of solution (1) molecular colloid
(4) decrease in amount of adsorbate in solution (2) associated colloid
7. Which one of the following is not applicable to the (3) macromolecular colloid
phenomenon of adsorption? (4) lyophilic colloid .
(1) H > 0 (2) G < 0 15. Which of the following will show Tyndall effect?
(3) S < 0 (4) H < 0 (1) Aqueous solution of soap below critical micelle
8. Which of the following is not a favourable condition concentration.
for physical adsorption? (2) Aqueous solution of soap above critical micelle
(1) High pressure concentration.
(2) Negative H (3) Aqueous solution of sodium chloride.
(3) Higher critical temperature of adsorbate (4) Aqueous solution of sugar.
(4) High temperature 16. Method by which lyophobic sol can be protected?
9. Physical adsorption of a gaseous species may change (1) By addition of oppositely charged sol
to chemical adsorption with : (2) By addition of an electrolyte
(1) decrease in temperature (3) By addition of lyophilic sol
(2) increase in temperature (4) By boiling
(3) increase in surface area of adsorbent 17. In physisorption, adsorbent does not show specificity
(4) decrease in surface area of adsorbent for any particular gas because :
10. Freshly prepared precipitate sometimes gets converted (1) involved van der Waals forces are universal
to colloidal solution by : (2) gases involved behave like ideal gases.
(1) coagulation (2) electrolysis (3) enthalpy of adsorption is low
(3) diffusion (4) peptisation (4) it is a reversible process.
18. Which of the following electrolytes will have maximum 22. Which of the following process is responsible for the
coagulating value for AgI/Ag + sol? formation of delta at a place where rivers meet the sea?
(1) Na 2 S (2) Na 3PO 4 (1) Emulsification (2) Colloid formation
(3) Na 2SO 4 (4) NaCl (3) Coagulation (4) Peptisation
19. A colloidal system having a solid substance as a 23. Which of the following curves is in accordance with
dispersed phase and a liquid as a dispersion medium is Freundlich adsorption isotherm?
classified as :
(1) solid sol (2) gel
log x/m
log x/m
(3) emulsion (4) sol
20. The values of colligative properties of colloidal
(1) (2)
solution are of small order in comparison to those
shown by tru e solutions of same co ncentration p p
because colloidal particles :
(1) exhibit enormous surface area
(2) remain suspended in the dispersion medium
log x/m
log x/m
(3) form lyophilic colloids
(4) are comparatively less in number (3) (4)
21. Arrange the following diagrams in correct sequence of p p
steps involved in the mechanism of catalysis, in
24. Which of the following process is not responsible for
accordance with modem adsorption theory.
the presence of electric charge on the sol particles?
(1) Electron capture by sol particles
A
(2) Adsorption of ionic species from solution
(3) Formation of Helmholtz electrical double layer
(i) (4) Absorption of ionic species from solution
B 25. Which of the following phenomenon is applicable to
the process shown in the figure?
A
(ii) B
Solution of
raw sugar
A (yellowish brown)
(iii) B
A Column of
animal charcoal
(iv) B
A
(v) Colourless
B solution of sugar
(1) i  ii  iii  iv  v
(2) i  iii  ii  iv  v
(3) i  iii  ii  v  iv (1) Absorption (2) Adsorption
(4) i  ii  iii  v  iv (3) Coagulation (4) Emulsification
• Instructions for Questions 1 to 10 8. Assertion : A gas with higher critical temperature gets
adsorbed to more extent than a gas with lower critical
Given below are two statements: One is labelled as Assertion
(A) and the other is labelled as Reason (R). temperature.
In the light of the above statements, choose the most Reason : The easily liquefiable gases get adsorbed to
appropriate answer from the options given below : more extent which have higher critical temperature.
(1) Both (A) and (R) are correct and (R) is the correct
9. Assertion : When AgNO3 is treated with excess of KI,
explanation of (A)
colloidal particles gets attracted towards anode.
(2) Both (A) and (R) are correct but (R) is not the correct
explanation of (A) Reason : Colloidal particles adsorb common ions and
(3) (A) is correct the (R) is not correct thus become charged.
(4) (A) is not correct but (R) is correct 10. Assertion : Tetraethyl lead minimises the knocking
effect when mixed with petrol.
1. Assertion : Gold number is the measure of protective
powers of different colloids. Reason : Because tetraethyl lead acts as a –ve catalyst.
Reason : The smaller the gold number of lyophilic
• Instructions for Questions 11 to 15
colloid, the smaller is its protective power.
2. Assertion : The property of adsorption is shown by Given below are two statements :
In the light of the above s tatements, choose the most
solids to a much larger extent than liquids.
appropriate answer from the options given below :
Reason : Solids, particularly when finely divided, have (1) Both Statement I and Statement II are correct
a large surface area. (2) Both Statement I and Statement II are incorrect
(3) Statement I is correct but Statement II is incorrect
3. Assertion : Aqueous gold colloidal solution is red in
(4) Statement I is incorrect but Statement II is correct
colour.
Reason : The colour arises due to scattering of light of 11. Statement I : Deep electric shock causes death of an
colloidal gold particles. animal.
4. Assertion : All colloidal dispersions give very low Statement II : Electric shock coagulate the blood.
osmotic pressure and show very small freezing point 12. Statement I : All colloidal dispersions give very low
depression or boiling point elevation. osmotic pressure and show very small freezing point
Reason : Tyndall effect is due to scattering of light depression or boiling point elevation.
from the surface of colloidal particles. Statement II : Tyndall effect is due to scattering of
light from the surface of colloidal particles.
5. Assertion : The Brownian movement is due to the
bombardment on colloidal particles by the molecules 13. Statement I : A catalyst is more effective in finely
of dispersion medium which are in the constant motion divided form.
like molecules in a gas. Statement II : Finely divided form has more surface
Reason : Brownian movement provides a visible proof area.
of the random kinetic motion of molecules in a liquid. 14. Statement I : The Brownian movement is due to the
6. Assertion : In the coagulation of negatively charged bombardment on colloidal particles by the molecules
arsenic sulphide sol, the coagulating power decreases of dispersion medium which are in the constant
in the order, Al3+ > Ba2+ > Na+. motion like molecules in a gas.
Reason : Generally greater the valency of coagulating Statement II : Brownian movement provides a visible
ion, the greater is its power of coagulation. proof of the random kinetic motion of molecules in a
liquid.
7. Assertion : Isoelectric point is pH at which colloidal
15. Statement I : In physisorption, adsorbtion increases
can move towards either of electrode
with increases in temperature.
Reason : At isoelectric point, colloidal particles become
Statement II : Physisorption is exothermic in nature.
electrically neutral.
(Direct from
NCERT)
Match the List – I and List – II and choose the correct (2) (a) – (iv); (b) – (i); (c) – (iii, iv); (d) – (ii)
combination from the options given. (3) (a) – (iii); (b) – (ii, iv); (c) – (i); (d) – (ii)
(4) (a) – (i); (b) – (ii); (c) – (iv, i); (d) – (iii, iv)
1. Match List – I with List – II
List – I List – II 4. Match the List – I with List – II and Select the correct
(a) Mist (i) Jellies answer:
(b) Rain (ii) Whipped cream List – I List – II
(c) Gel (iii) Aerosol (a) Coagulation (i) Scattering of
(d) Foam (iv) Solid or liquid light
dispersed in air (b) Dialysis (ii) Formation of
Choose the correct answer from the options given below : colloidal solution
(1) (a) – (iii, i); (b) – (ii); (c) – (iv); (d) – (iii, iv) from precipitation
(2) (a) – (i, ii); (b) – (iii, iv); (c) – (iii); (d) – (iv, i) (c) Peptization (iii) Purification of
(3) (a) – (ii); (b) – (iii); (c) – (i); (d) – (iv) colloids
(4) (a) – (iii, iv); (b) – (iii, iv); (c) – (i); (d) – (ii) (d) Tyndall effect (iv) Accumulation of
colloidal sols
2. Match List – I with List – II Choose the correct answer from the options given below :
List – I List – II (1) (a) – (iv); (b) – (iii); (c) – (ii); (d) – (i)
(a) Precipitation of (i) Peptisation (2) (a) – (i); (b) – (ii); (c) – (iv); (d) – (iii)
colloidal Sol (3) (a) – (i); (b) – (iv); (c) – (ii); (d) – (iii)
(b) Purification (ii) Coagulation (4) (a) – (iv); (b) – (i); (c) – (iii); (d) – (ii)
(c) Gold number (iii) Measure of
protective power 5. Match List – I with List – II
(d) Formation of Sol (iv) Dialysis List – I List – II
Choose the correct answer from the options given below : (a) Adsorption (i) Enthalpy of
(1) (a) – (ii); (b) – (iv); (c) – (i); (d) – (iii) adsorption is
(2) (a) – (ii); (b) – (ii); (c) – (iv); (d) – (iii) quite low
(3) (a) – (ii); (b) – (iv); (c) – (iii); (d) – (i)
(b) Physisorption (ii) Rate of adsorption
(4) (a) – (iii); (b) – (i); (c) – (iv); (d) – (ii) decreases as
pressure increase
3. Match List – I with List – II (c) Desorption (iii) Rate remains
List – I List – II same throughout
(a) BaSO4 (i) Inhibitor for the process
decomposition (d) Chemisorption (iv) Endothermic in
of H2O2 nature
(b) Acetamide (ii) Catalyst Choose the correct answer from the options given below :
(c) Zeolite (iii) Removes hardness (1) (a) – (iii); (b) – (i); (c) – (iv); (d) – (ii)
of water (2) (a) – (i); (b) – (ii); (c) – (iv); (d) – (iii)
(d) Nickel (iv) Poison for Pd in (3) (a) – (ii); (b) – (i); (c) – (iv); (d) – (iii)
Lindlar catalyst
(4) (a) – (ii); (b) – (iii); (c) – (i); (d) – (iv)
Choose the correct answer from the options given below :
(1) (a) – (iv); (b) – (iii); (c) – (ii, iii); (d) – (iv)
1. According to the adsorption theory of catalysis, the 8. Which one of the following statements is incorrect
speed of the reaction increases because about enzyme catalysis? [AIPMT-2012]
(1) Adsorption produces heat which increases the (1) Enzymes are mostly proteinous in nature
speed of the reaction [AIPMT 2003] (2) Enzyme action is specific
(2) Adsorption lowers the activation energy of the (3) Enzymes are denaturated by UV rays and at high
reaction temperature
(3) The concentration of reactant moleculer at the (4) Enzymes are least reactive at optimum temperature
active centres of the catalyst becomes high due
9. In Freundlich adsorption isotherm, the value of 1/n is
to adsorption
(1) between 0 and 1 in all cases [AIPMT-2012]
(4) In the process of adsorption, the activation energy
of the molecules becomes large (2) between 2 and 4 in allcases
2. Which of the following forms cationic micelles above (3) 1 in case of physical adsorption
certain concentration? [AIPMT-2004] (4) 1 in case of chemisorption
(1) Sodium ethyl sulphate 10. Which of the following statements is correct for the
(2) Sodium acetate (3) Urea spontaneous adsorption of a gas?
(4) Cetyl trimethyl ammounium bromide (1) S is negative and therefore, should be highly
positive [AIPMT-2014]
3. Which one of the following forms micelles in aqueous
solution above certain concentration? (2) S is negative and therefore, should be highly
negative
(1) Urea [AIPMT-2005]
(3) S is positive and therefore should be negative
(2) Dodecyl trimethyl ammounium chloride
(4) S is positive and therefore,  should also be
(3) Pyridinium chloride (4) Glucose
highly positive
4. For adsorption of a gas on a solid, the plot of log
11. Which property of colloidal solution is independent
(x / m) vs log p is linear with slope equal to (n being a
of charge on the colloidal particles? [AIPMT-2014]
whole number) [AIPMT-2006]
(1) Coagulation (2) Electrophoresis
(1) k (2) log k
(3) Electroosmosis (4) Tyndall effect
(3) n (4) 1 / n
12. The suspension of slaked lime in water is knows as
5. The Langmuir adsorption isotherm is deduced by using
the assumption that [AIPMT-2007] (1) Limewater [NEET-2016]
(1) the adsorption takes place in multilayers (2) Quicklime
(2) the adsorption sites are equivalent in their ability (3) Milk of lime
to adsorb the particles (4) aqueous solution of slaked lime
(3) the heat of adsorption varies with coverage 13. The coagulation values in milliomoles per litre of the
(4) the adsorbed molecules interact with each other electroytes used for the coagulation of As2 S3 are given
below [NEET-2016]
6. If x is amount of adsorbate and m is amount of
adsorbent, which of the following relations is not I. (NaCl) = 52,
related to adsorption process? [AIPMT-2011] II. (BaCl2) = 0.69
x III. (MgSO4) = 0.22
(1)  ƒ(T ) at constant P The correct order of their coagulating power is
m
x (1) I > II > III (2) II > I > III
(2) p  ƒ(T ) at constant   (3) III > II > I (4) III > I > II
m
x 14. Which one of the following charact eristics is
(3)  p T associated with adsorption ? [NEET-2016]
m (1) G,H and S all are negative
x
(4)  ƒ( p ) at constant T (2) G and H are negative but H is positive
m (3) G and S are negative but H is positive
7. The protecting power of lyophilic colloidal sol is
expressed in terms of [AIPMT-2012] (4) G is negative but and S are positive
(1) Coagulation value (2) Gold number 15. Fog is a colloidal solution of [NEET-2016]
(3) Critical micelle concentration (1) Gas in liquid (2) Solid in gas
(4) Oxidation number (3) Gas in gas (4) Liquid in gas
16. On which of the following properties does the coagu- 19. Shown below are adsorption isotherms for a gas ‘X’ at
lation power of an ion depend [NEET-2018] temperature T1, T2 and T3 [NEET-2022]
(1) Both magnitude and sign of the charge on the ion T1
(2) Size of the ion alone T2
(3) The magnitude of the charge on the ion alone T3
(4) The sign of charge on the ion alone x
17. Which mixture of the solutions will lead to the formation m
of negatively charged colloidal [AgI]I– solution?
[NEET-2019]
(1) 50 mL of 1 M AgNO3 + 50 mL of 1.5 M KI
(2) 50 mL of 1 M AgNO3 + 50 mL of 2 M KI p
(3) 50 mL of 2 M AgNO3 + 50 mL of 1.5 M KI x
p and represent pressure and extent of adsorption,
(4) 50 mL of 0.1 M AgNO3 + 50 mL of 0.1 M KI m
respectively. The correct order of temperatures for the
18. The right option for the statement “Tyndall effect is
given adsorption is
exhibited by”, is : [NEET-2021]
(1) T1 > T2 > T3 (2) T3 > T2 > T1
(1) NaCl solution (2) Glucose solution
(3) T1 = T2 = T3 (4) T1 = T2 > T3
(3) Starch solution (4) Urea solution
26. (4) 27. (3) 28. (3) 29. (1) 30. (3)
1. (2 2. (2) 3. (3) 4. (2) 5. (1)
6. (4) 7. (1) 8. (1) 9. (1) 10. (4) 31. (4) 32. (4) 33. (2) 34. (4) 35. (2)
11. (4) 12. (1) 13. (2) 14. (1) 15. (3) 36. (3) 37. (1) 38. (4) 39. (3) 40. (4)
41. (4) 42. (1) 43. (4) 44. (4) 45. (2)
16. (4) 17. (4) 18. (1) 19. (4) 20. (2) NCERT EXEMPLAR OBJECTIVE TYPE QUESTIONS
21. (4) 22. (3) 23. (3) 24. (1) 25. (1)
26. (3) 27. (4) 28. (1) 29. (3) 30. (3) 1. (3) 2. (2) 3. (4) 4. (3) 5. (2)
31. (2) 32. (3) 33. (4) 34. (2) 35. (3) 6. (1) 7. (1) 8. (4) 9. (2) 10. (4)
11. (2) 12. (4) 13. (1) 14. (2) 15. (2)
36. (2) 37. (2) 38. (3) 39. (3) 40. (2) 21. (2) 22. (3) 23. (3) 24. (4) 25. (2)
41. (3) 42. (2) 43. (4) 44. (1) 45. (1)
ASSERTION–REASON & STATEMENT QUESTIONS
46. (3) 47. (2) 48. (3) 49. (3) 50. (2)
51. (3) 52. (3) 53. (2) 54. (1) 55. (4) 1. (3) 2 (2) 3. (1) 4. (2) 5. (2)
6. (1) 7. (4) 8. (2) 9. (1) 10. (1)
DAILY PRACTICE PROBLEM (DPP) – 04
11. (1) 12. (2) 13. (1) 14. (2) 15. (4)
56. (1) 57. (4) 58. (3) 59. (3) 60. (4)
61. (3) 62. (4) 63. (3) 64. (3) 65. (1) MATRIX TYPE QUESTIONS
66. (3) 67. (1) 68. (4) 69. (2) 70. (3) 1. (4) 2 (3) 3. (2) 4. (1) 5. (1)
71. (4) 72. (2) 73. (2) 74. (4) 75. (3)
ARCHIVE QUESTIONS
MISCELLANEOUS QUESTIONS FROM NCERT
1. (2) 2. (4) 3. (2) 4. (4) 5. (2)
1. (1) 2. (2) 3. (1) 4. (2) 5. (4)
6. (3) 7. (2) 8. (4) 9. (1) 10. (2)
6. (3) 7. (1) 8. (4) 9. (3) 10. (2)
11. (4) 12. (3) 13. (3) 14. (1) 15. (4)
11. (4) 12. (3) 13. (3) 14. (3) 15. (1)
16. (3) 17. (1,2) 18. (3) 19. (2)
16. (1) 17. (3) 18. (1) 19. (2) 20. (3)
GENERAL PRINCIPLES
& PROCESSES OF
ISOLATION OF ELEMENTS
Chapter 06
Percentage of Questions in Last 34 Years’ in NEET / AIPMT from this Chapter
Percentage
A • Electrochemical series, Electro- 50%
potential, Nernst Equation
C. 23%
A. 50% B • Alkali Metals & Compounds 27%
B. 27%
C • Electrolysis 23%
WHAT DO YOU WANT TO KNOW? 6.6 OXIDATION REDUCTION
6.1 OCCURENCE OF METALS 6.7 REFINING
6.2 CONCENTRATION OF ORES 6.8 USES OF ALUMINIUM, COPPER, ZINC

6.2.1 Hydraulic Washing AND IRON
6.2.2 Magnetic Separation 6.9 SYNOPSIS
6.2.3 Froth Floatation Process
6.2.4 Leaching 6.10 MISCELLANEOUS Questions from NCERT
6.3 EXTRACTION OF CRUDE METAL FROM 6.11 NCERT EXEMPLAR

CONCENTRATED ORE OBJECTIVE TYPE QUESTIONS
6.4 THERMODYNAMIC PRINCIPLES OF 6.12 ASSERTION–REASON & statement Questions

METALLURGY 6.13 MATRIX TYPE QUESTIONS
6.4.1 Applications
6.14 ARCHIVE QUESTIONS
6.5 ELECTROCHEMICAL PRINCIPLES OF
METALLURGY 6.15 ANSWER KEY
8.4.1 Oxides and Oxoanions of Metals
Iron ore
Hametite (Fe2O 3)
Concentration
Gravity separation and Magnetic separation
Calcination
To drive away moisture
expell volatile impurities
Calcined ore + coke + limestone subjected to smelting in blast furnace
Iron oxides reduced by coke above 1073 K and by carbon monoxide
below 1073 K. Silica present as acidic impurity is removed as a slag
i.e., (calcium silicate)
Fe formed by the reducing action of CO

is spongy iron
Spongy iron + C, Si, Mn (impurities)
Pig iron 4% carbon
Pig iron heated with O2 is passed through

scrap iron + coke molten pig iron + lime
then alloyed with Cr, Mn
Cast iron
Steel
Heat in reverberatory furnace
lined with haematite
Wrought iron
Purest form of iron (0.2 to 0.5% of carbon)
soft malleable and ductile
electrolytic refining
liquation
distillation
refining by distribution law 5. Refining
1. crushing and grinding
zone refining
vapour-phase Gravity separation or
Mond process levigation or hydraulic
refining Metallurgy 2. concentration washing
van Arkel method magnetic separation
hand picking
4. conversion of metal
electrostatic separation
oxide to free metal
froth floatation
smelting leaching
3. conversion of
auto reduction metal to oxide
reduction with hydrogen
electrolytic reduction
reduction with powerful Calcination roasting
aluminothermy reducing agent
hydrometallurgical process
poling amalgamation
puddling oxidation of
bessemerisation impurities
cupellation
INTRODUCTION
 The branch of chemistry which deals with the method of extraction of metals from their ores. A few elements
like carbon, sulphur, gold and noble gases, occur in free state while others in combined forms in the earth’s
crust. The extraction and isolation of an element from its combined form involves various principles of
chemistry. A particular element may occur in a variety of compounds. The process of metallurgy and isolation
should be such that it is chemically feasible and commericially viable. Still, some general principles are
common to all the extraction processes of metals. For obtaining a particular metal, first we look for minerals
which are naturally occurring chemical substances in the earth’s crust obtainable by mining. Out of many
minerals in which a metal may be found, only a few are viable to be used as sources of that metal. Such
minerals are known as ores.
 Rarely, an ore contains only a desired substance. It is usually contaminated with earthly or undesired mate-
rials known as gangue. The extractin and isolation of metals from ores involve the following major steps:
 Concentration of the ore,
 Isolation of the metal from its concentrated ore, and
 Purification of the metal.
The entire scientific and technological process used for isolation of the metal from its ores is known as
metallurgy.
6.1 P.No.: 152
 The element which tends to form positive ion is called a metal.

 The compound of a metal found in nature is called a mineral.
 The minerals from which metal can be economically and conveniently extracted are called ores. An ore is
usually contaminated with earthy or undesired materials known as gangue. So all minerals are not ores but
all ores are minerals.
General Principles & Processes of Isolation of Elements 87
SOME IMPORTANT ORES OF METALS
Metal Ores Composition
Aluminium Bauxite AlOx(OH)3–2x [where 0 < x < 1] Al2O3
Diaspore Al2O3.H2O
Corundam Al2O3
Kaolinite (a form of clay) [Al2(OH)4 Si2O5]
Iron (Fe) Haematite (Fe2O3)
Magnetite (Fe3O4)
Limonite (2Fe2O3.3H2 O)
Iron pyrite (FeS2)
Siderite (FeCO3)
Copper (Cu) Copper pyrites (CuFeS2)
Malachite (CuCO3.Cu(OH)2)
Cuprite Cu2O
Zinc (Zn) Zinc blende (ZnS)
Zincite (ZnO)
Calamine (ZnCO3)
Lead Galena PbS
Anglesite PbSO4
Cerrusite PbCO3
Magnesium Carnallite KCl.MgCl26H2O (K2MgCl4.6H2O)
Magnesite MgCO3
Dolomite MgCO3CaCO3
Epsomsalt (Epsomite) MgSO47H2O
Langbeinite K2Mg2(SO4)3
Tin Cassiterite (Tin stone) SnO2
Silver Silver Glance (Argentite) Ag2S
Pyrargyrite (Ruby Silver) Ag3SbS3
Chlorargyrite (Horn silver) AgCl
Stefinite Ag5SbS3
Proustite Ag3AsS3
METALLURGY
 The scientific and technological process used for the extraction/isolation of the metal from its ore is called
as metallurgy.
 The isolation and extraction of metals from their ores involve the following major steps:
(A) Crushing of the ore. (B) Dressing or concentration of the ore.
(C) Isolation of the crude metal from its ore (D) Purification or refining of the metal
CRUSHING AND GRINDING

 The ore is first crushed by jaw crushers and ground to a powder (pulverisation of the ore) in equipments
like ball mills and stamp mills.
88 General Principles & Processes of Isolation of Elements
6.2 P.No.: 153

 The removal of unwanted useless impurities from the ore is called dressing, concentration or benefaction of
ore.
 It involves several steps and selection of these steps depends upon the difference in physical properties of
the compound of metal and that of gangue. Some of the important procedures are described below.
6.2.1 P.No.: 153

 It is based on the difference in the densities of the gangue and ore particles.
 In this, the powdered ore is agitated with water or washed with a upward stream of running water, the
lighter particles of sand , clay etc are washed away leaving behind heavier ore particles. For this either
hydraulic classifier or Wilfley table is used.
 This method is generally used for the concentration of oxide and native ores.
6.2.2 P.No.: 153

 It is based on differences in magnetic properties of the ore components.
 It is used when either the ore or the impurities associated with it are magnetic in nature.
 A magnetic separator consists of a belt (of leather or brass) moving over two rollers, one of which is
magnetic.
 When the powdered ore is dropped on the belt at the other end, magnetic component of the ore is attracted
by the magnetic roller and falls nearer to the roller while the non-magnetic impurities fall away from it. For
examples, Chromite ore(FeO.Cr2O3) is separated from non–magnetic silicious impurities and cassiterite
ore (SnO2) is separated from magnetic Wolframite (FeWO4 + MnWO4).
Figure : Electromagnetic separation
6.2.3 P.No.: 154

 This method is commonly used for the concentration of the low grade sulphide ores like galena, PbS (ore of
Pb) ; copper iron pyrites Cu2S.Fe2S3 or CuFeS2 (ore of copper) ; zinc blende, ZnS (ore of zinc) etc., and is
based on the fact that gangue and ore particles have different degree of wettability with water and pine oil;
the gangue particles are preferentially wetted by water while the ore particles are wetted by oil. In this
process one or more chemical frothing agents are added.
(a) Frothers
1. These form stable froth which rises to the top of the flotation cell. Oils like pine oil, camphor oil
etc., are used as frothers. These are added in small quantity.
2. The stabiliser are added to the frothers so that the froth can last for longer period.
(b) Collectors
1. Potassium or sodium ethyl xanthate is used as a collector.
2. These get attached with the particles of the sulphide ore and thus make them water-repellant.
Consequently the ore particles pass on into the froth.
3. Collectors are always added in small quantity.
(c) Activating and depressing agents.
1. When a mineral contains other minerals as impurities.
2. The addition of these agents activates or depresses the flotation property of other minerals present
as impurities and thus helps in separating the impurities. For example galena (PbS) usually contains
the minerals namely zinc blende (ZnS) and pyrites (FeS2) as impurities. Flotation is carried out by
using potassium ethyl xanthate (used as a collector) along with NaCN and Na2CO3 (used as
depressing agent).
3. The addition of NaCN and Na2CO3 depresses the flotation property of ZnS and FeS2 grains, so
mainly PbS passes into the froth when air is blown in. After PbS has been collected with the froth,
the process is repeated by adding CuSO4 (activator) which activates the flotation property of ZnS
grains which are now removed with the froth. The acidification of the remaining material left in
the flotation cell leads to the flotation of FeS2.
6.2.4 P.No.: 154

 Leaching is often used if the ore is soluble in some suitable solvent, e.g, acids, bases and suitable chemical
reagents.
 Leaching of alumina from bauxite :
1. The principal ore of aluminium, bauxite, usually contains SiO2, iron oxides and titanium oxide (TiO2)
as impurities. Concentration is carried out by digesting the powdered ore with a concentrated solution
of NaOH at 473 - 523 K and 35 - 36 bar pressure. This way, Al2O3 is leached out as sodium aluminate
(and also SiO2 as sodium silicate) leaving behind the impurities, iron oxide and titanium oxide.
Al2O3(s) + 2NaOH(aq) + 3H2O (l)  2Na [Al(OH)4] (aq)
2. The aluminate in solution is neutralised by passing CO2 gas and hydrated Al2O3 is precipitated. At this
stage, the solution is seeded with freshly prepared samples of hydrated Al2O3 which induces the
precipitation.
2Na[Al(OH)4] (aq) + CO2(g)  Al2O3.xH2O(s) + 2NaHCO3 (aq)
3. The sodium silicate remains in the solution and hydrated alumina is filtered, dried and heated to give
back pure Al2O3 :
Al2O3.xH2O(s)  Al2O3(s) + xH2O(g)
These steps comprises the Bayer’s process.
 Other examples : In the metallurgy of silver and that of gold, the respective metal / ore is leached with a
dilute solution of NaCN or KCN in the presence of air (or O2) from which the metal is obtained later by
displacement with zinc scrap.
4M(s) + 8CN– (aq) + 2H2O(aq) + O2(g)  4[M(CN)2]– (aq) + 4OH–(aq) (M = Ag or Au)
2[M(CN)2]–(aq) + Zn(s)  [Zn(CN)4]2–(aq) + 2M(s)
6.3 P.No.: 155
 The concentrated ore must be converted into a form which is suitable for reduction.
 Usually the sulphide ore is converted to oxide before reduction. Oxides are easier to reduce.
 Thus isolation of metals from concentrated ore involves two major steps as given below.
(i) Conversion to oxide (ii) Reduction of the oxide to metal.
CONVERSION TO OXIDE
 Conversion of ore into oxide is carried out in two ways depending upon the nature of ore.
 Calcination : It is a process of heating the concentrated ore strongly in a limited supply of air or in the
absence of air. The process of calcination brings about the following changes :
 The carbonate ore gets decomposed to form the oxide of the metal, e.g.,
 
FeCO3 (siderite)   FeO + CO2 ; PbCO3 (ceurssite)   PbO + CO2

CaCO3 (calcite ore / lime stone)   CaO + CO2

ZnCO3 (calamine)   ZnO + CO2
 Water of crystallisation present in the hydrated oxide ore gets lost as moisture, e.g.,

2Fe2O3.3H2O (limonite)   2Fe2O3(s) + 3H2O(g)

Al2O3.2H2O (bauxite)   Al2O3 (s) + 2H2O(g)
 Organic matter, if present in the ore, gets expelled and the ore becomes porous. Volatile impurities are
removed.
 Roasting : It is a process of heating the concentrated ore (generally sulphide ore) strongly in the excess of
air or O2 below its melting point. Roasting is an exothermic process once started it does not require additional
heating. Some of the reactions involving sulphide ores are :
 
2PbS + 3O2   2PbO + 2SO2 ; 2ZnS + 2O2   2ZnO + 2SO2 ;

2Cu2S + 3O2   2Cu2O + 2SO2
* Some times roasting may not bring about complete oxidation.
2CuFeS2 (copper pyrite) + 4O2  Cu2S + 2FeO + 3SO2
The reduction of the sulphide ore directly into metal by heating it in air or O2 is called by various names
like self-reduction, auto-reduction, air-reduction etc. The SO2 produced is utilised for manufacturing of
H2SO4.
REDUCTION OF A METAL OXIDE

 The free metal is obtained by reduction of a compound, using either a chemical reducing agent or electrolysis.
01 4. Which of the following is not an ore?

(1) Malachite (2) Calamine
1. Ore of which of the following element is a metalloid?
(3) Salt cake (4) Cerussite
(1) As (2) Na
5. Carnallite is a mineral of
(3) Au (4) Fe
(1) Ca (2) Na
2. The rocky and siliceous matter associated with an ore is
called: (3) Mg (4) Zn
(1) slag (2) mineral 6. Which of the following statement is correct?
(3) matrix or gangue (4) flux (1) Bauxite is an ore of aluminium
3. The most abundant element on earth crust is (2) Magnetite is an ore of manganese
(1) Hydrogen (2) Oxygen (3) Haematite is an ore of mercury
(3) Silicon (4) Carbon (4) Pyrites is an ore of phosphorus
7. Electrolytic reduction method is used for the extraction 11. Which of the following minerals is not an ore of
of aluminum?
(1) Highly electronegative elements (1) Bauxite (2) Gypsum
(2) Highly electropositive elements (3) Cryolite (4) Corundum
(3) Transition metals 12. The process of removing lighter gangue particles by wash-
(4) Metalloids ing in a current of water is called:
8. Which of the following metal is not found in free state? (1) levigation (2) liquation
(1) Na (2) Au (3) leaching (4) cupellation.
(3) Ag (4) Pb 13. Cryolite is
9. Metal which can be extracted from ail three dolomite, (1) Magnesium silicate
magnesite and carnallite is (2) Sodium borofluoride
(1) Na (2) K (3) Sodium aluminium fluoride
(3) Mg (4) Ca (4) Magnesium silicate
10. Which is not correct statement? 14. An example of halide ore is
(1) Cassiterite, chromite and haematite are concentrated (1) Galena (2) Bauxite
by hydraulic washing (Tabling) (3) Cinnabar (4) Cryolite
(2) Pure Al 2O 3 is obtained from the bauxite ore by 15. Which mineral has been named incorrectly?
leaching in the Bayer's process. (1) Bauxite: Al2O3.2H2O
(3) Sulphide ore is concentrated by calcination method. (2) Corundum: Al2O3
(4) Roasting can convert sulphide into oxide or sulphate (3) Cryolite: 3NaF.AlF3
and part of sulphide may also act as a reducing agent. (4) Feldspar: Be3Al2Si6O18
6.4 P.No.: 156
 Most metals of industrial importance are obtained by chemical reduction of their oxide and the free energy
changes occurring during these processes are of more fundamental importance. For a spontaneous reaction
the change in free energy G must negative, G = H – TS.
 It is sufficient to consider G because it is related to the equilibrium constant through, G = – RT ln K.
Here a negative value of G corresponds to K > 1 and, therefore, a favourable reaction. Reaction rates are
also relevant, but at high temperature reactions are often fast and we can normally assume that any
thermodynamically permissible process can occur.
 The problem of extracting a metal from its ore is essentially concerned with decomposing the oxide of the
metal (apart from simple binary compounds such as metal sulfides and chlorides that occur in nature).
 Most metal ores consist essentially of a metal oxide in association with one or more nonmetal oxides. Ores
like carbonates, sulphides etc., are also converted to oxides, prior to reduction.
The free energy of formation G is the standard free energy of the reaction.
y 2x 2
xM  O2   M x O y ....(1) or y M  O2   M x Oy
y ....(2)
2
 G is the free energy of formation per mole of O2 consumed.
 If the standard free energy of formation G has a negative sign at a given temperature, then the oxide can be
expected to form spontaneously from the metal plus oxygen. If G has a positive sign, the oxide will be
expected to decompose spontaneously to its elements.
 The free energy of formation of an oxide can now be determined, provided we know the entropy of forma-
tion.
G = H – TS ...(3)
In reaction (2) oxygen is used up in the course of reaction. Gases have a more random structure (less
ordered) than liquid or solids. In this reaction the entropy or randomness decreases, and hence S is negative
(provided that neither the metal nor its oxide MxOy are vaporized). Thus, if the temperature is raised then
TS becomes more negative. Since TS is subtracted in equation (3), G then becomes less negative.
Thus, the change in free energy
decreases with increase in temperature.
The free energy change that occurs
when 1 mol of common reactant (in
this case O2) is used may be plotted
graphically against temperature for
a number of reaction of metals to
their oxides. This graph is shown in
following figure and is called an
Ellingham diagram for oxides.
Similar diagrams can be produced for
1 mol of S, giving Ellingham diagram
for sulphides and similarly for
halides using 1 mol of halogen.
 This figure shows a number of oxide
plots with slopes defined by G / T
= – S. It is noted that the entropy
change in reaction (2) is roughly the
same for all metal oxides provided
that the boiling point of neither the
metal nor oxide is exceeded. Thus,
below the boiling point of metal the
slope of all the graphs are roughly
the same, since TS factor is same
whatever be the metal. Figure : Gibbs energy (G) vs T plots (schematic)
 When the temperature is raised a point for the formation of some oxides (Ellingham diagram)
will be reached where the graph crossed the G = 0 line. Below this temperature the free energy of formation
of oxide is negative, so the oxide is stable.
 Above this temperature the free energy of formation of the oxide is positive, and the oxide becomes unstable
and should decompose into metal and oxygen.
 This explains why HgO, for instance, decomposes spontaneously into its elements when heated. Theoretically,
all oxides can be decomposed to give metal and oxygen if a sufficiently high temperature can be attained. In
practice, that are easily attainable and these metals can be extracted by thermal decomposition of their
oxides.
 The diagram predicts that MgO and ZnO ought to decompose if heated strongly enough, but it does not hold
out much hope for obtaining say pure Mg by straight forward heating of the oxide to a high temperature
where the boiling point of the metal is exceeded. However the slope increases since the reaction is now
involving a larger entropy change as the randomness increases in reactants. For example,
2Mg (g) + O2 (g)  2 MgO(s)
Here, three moles of gas phases are converted into solid phase in the reaction. This takes place above
1120°C, which is the boiling point of Mg.
 Similarly Hg-HgO line changes slope at 365°C. Several of the plots show abrupt changes in the slopes.
These breaks occur at temperature at which the metal undergoes a phase transition.
 A smaller effect is seen at the melting point. If, however the oxide undergoes a phase change, there will be
an increase in the entropy of the oxide, and at such a point the curve becomes less steep. For example in the
case of Pb, the oxide (PbO) boils while lead is liquid. In these instances the entropy change becomes
positive for the reaction and hence the slope G/T changes sign, the situation reverting to normal once the
boiling point of Pb is reached.
 In principle, when the plot of one metal lies below that of another, the first metal is capable of reducing the
oxide of the second.
 A vertical line drawn on the Ellingham plot of the metal oxides at any T gives the sequence of the stabilities
of metal oxides. A metal forming a more stable oxide (higher – G) will be potential reducing agent for a
less stable oxide. If the two lines intersect, the free energy change for the reduction will be zero at that
temperature and equilibrium results, but a change of temperature will make the reaction proceed provided
no kinetic barriers (activation energy) exist. Thus, Mg metal will reduce CuO and FeO but not CaO. Also,
it is seen that at room temperature (27°C) the order of reducing ability approximates that of standard electrode
potential.
 Although the SiO2 line is above the MgO line, Si can successfully reduce MgO to free metal. Upto 1100°C,
the normal boiling point of Mg, the G plot for formation of SiO2 and MgO are parallel. However, above
1100°C the plot for MgO changes slope owing to the increased entropy effect, and above 1700ºC the reaction
between Si and MgO proceeds with decrease in free energy. In practice, the reaction is further enhanced by
the distillation of Mg metal from the reaction mixture.
2MgO + Si  2Mg + SiO2
CARBON OR CARBON MONOXIDE AS REDUCING AGENT :

 In figure the plot corresponding to the change C (s) + O2(g)  CO2(g) is shown by a horizontal line. For
this reaction S is relatively small because in this case one mole of gaseous product is formed while one
mole of gaseous reactant is used up. G for this reaction is almost independent of temperature.
 The plot for CO2 is relatively high in the figure, and at low temperature C will reduce only a few of metal
oxides shown. However, the slopes of the plots for several of the metals are such that they cross the CO2
plot; hence theoretically these metals can be reduced by C at elevated temperature.
 An alternative reaction involving carbon and oxygen is the formation of CO.
2 C (s) + O2(g)  2 CO(g)
Since two of gaseous product is formed from one mole of gaseous reactant, this process is accompanied by
an increase in entropy. Hence, the slope of the corresponding line is negative as shown by the downward
sloping line in the figure. If the temperature is high enough, C should reduce all the metal oxides, being
converted into CO. The plot for the reaction of CO with oxygen is also shown.
 There are three curves for carbon, corresponding to complete oxidation of C to CO2, partial oxidation to
carbon monoxide, and oxidation of CO to carbon dioxide. The three curves pass through a common point at
710°C. Thus, the free energies of formation of CO2 from carbon monoxide and carbon dioxide from carbon
are identical.
2CO (g) + O2 (g)  2 CO2(g) ; G = x kJ/mol
C(s) + O2 (s)  CO2 (s); G = x kJ/mol
 Subtracting one equation from the other and rearranging, the following is obtained :
 2CO(g) ; G = 0
CO2(g) + C(s) 
That is, an equilibrium is set. It is clear below a temperature of 710°C, CO is a more effective reducing
agent than carbon, but above this temperature the reverse is true. All three oxidation curves for the carbon
system lie above that for oxidation of zinc, until a temperature of approximately 1000°C is reached. At this
point C is thermodynamically capable of reducing ZnO to Zn. Since this temperature is greater than the
boiling point of Zn (907°C), it will be formed as a vapour. The overall equation for reduction is
ZnO(s) + C (s)  Zn(g) + CO(g)
 It is interesting to note that the value of carbon as reducing agent is due to marked increase in disorder that
takes place when carbon (an ordered solid) reacts with one mole of oxygen to give two moles of CO.
0
–100
O2
–200 2C

of O 2 O 2
–300 CO+
2 C + O 2  CO 2
–1
fGº/k Jm ol
2C +
–400 O2 
2CO
–500
–600
–700
0ºC 400ºC 800ºC 1200ºC

273 K 673 K 1073 K 1473 K
Tem perature (K)
 The net effect is an extra mole of gas and hence an increase in disorder (an increase in entropy). It is a fact
that in the region of 2000°C, C is thermodynamically capable of reducing most metal oxides to metal.
 Thus, for most metal oxides, a reducing agent is required and we should consider the overall reaction
obtained by subtracting the metal oxidation from one of carbon oxidation as
Goverall = G(C) – G(M)
02 (1) a sulphide ore cannot be reduced to metal at all

(2) no reducing agent is found suitable for reducing a
16. Which of the following represents the thermite reaction?
sulphide ore.
(1) 3Mn 3O2 + 8Al  9Mn + 4Al2O3
(3) the Gibbs free energy of formation of most sulphides
(2) MgCO3 + SiO2  MgSiO3 + CO2 are greater than that for CS2.
(3) Cu 2S + 2Cu2O  6Cu + SO2 (4) a metal oxide is generally less stable than the metal
(4) Fe2O3 + 3CO2  2Fe + 3CO2 sulphide.
17. In Ellingham diagram, the slope of the curve of the 21. A sulphide ore like ZnS is first roasted into its oxide prior
formation metal oxide: to reduction by carbon because:
(1) is mostly +ve (1) a sulphide ore cannot be reduced to metal at all
(2) is mostly –ve (2) no reducing agent is found suitable for reducing a
(3) depends on the type of metal sulphide ore.
(4) depends on the formula of metal oxide (3) the Gibbs free energy of formation of most sulphides
18. Carbon cannot be used in the reduction of Al2O3 because are greater than that for CS2.
(1) it is non-metal (4) a metal oxide is generally less stable than the metal
(2) the heat of formation of CO2 is more than that of sulphide.
Al2O3 22. According to Ellingham diagram the oxidation reaction
(3) pure carbon is not easily available of carbon and carbon monoxide may be used to reduce
(4) the heat of formation of Al2O3 is too high which one of the following oxides at the lowest
19. When compared to G° for the formation of Al2O3 the temperature?
G° for the formation of Cr2O3 is (1) Al2O3 (2) Cu2O
(1) Same (2) Lower (3) MgO (4) ZnO
(3) Higher (4) Unpredicted 23. Which metal has a greater tendency to form metal oxide?
20. A sulphide ore like ZnS is first roasted into its oxide prior (1) Cr (2) Ca
to reduction by carbon because: (3) Al (4) Fe
24. Select correct statement 27. The minimum voltage required to electrolyse alumina in
(1) In the decomposition of an oxide into oxygen and the Hall-Heroult process is [Given, G°f (Al2O3) = – 1520
solid/liquid metal, entropy increases. kJ/mol and G°f (CO2) = 394 kJ/mol]
(2) Decomposition of an oxide is an endothermic (1) 1.60 V (2) 1.575 V
change. (3) 1.312 V (4) –2.62 V
(3) To make G° negative, temperature should be high 28. The main reaction occurring in blast furnace during the
enough so that TS° > H°. extraction of iron from haematite is
(4) All statements are correct. (1) Fe2O3 + 3C  2Fe + 3CO
25. Ellingham diagram represents a graph of (2) FeO + SiO2  FeSiO3
(1) G vs T (2) S° vs T (3) Fe2O3 + 3CO  2Fe3O4 + CO2
(3) G° vs T (4) G vs P (4) CaO + SiO2  CaSiO3
26. Formation of metallic copper from sulphide ore in the 29. Which of the following statement is true?
normal thermometallurgical process essentially involves (1) Reduction of a metal oxide is easier if the metal
which of the following reactions formed is in liquid state at reduction temperature
3 (2) Reduction of metal oxide is normally less feasible
(1) CuS  O2  CuO  SO2 , CuO  C  Cu  CO
2 at high temperature
3 (3) The oxidation of CO into CO2 will have a negative
(2) CuS  O2  3Cu  SO2 , 2CuO  CuS  3CuO  SO2 slope on Ellingham diagram
2
(4) The reactive metals have positive slope for oxidation
(3) CuS  2O 2  CuSO 4
on Ellingham diagram whereas non-reactive metals
3 have a negative slope
(4) CuS  O2  CuO  SO 2
2
6.4.1 P.No.: 159

 Extraction of iron from ore haematite :
 Oxide ores of iron, after concentration
through calcination / roasting in
reverberatory furnace (to remove water, to
decompose carbonates and to oxidise
sulphides) are mixed with lime stone and
coke and fed into a Blast furnace from its
top with the help of a cup and cone
arrangement. Here, the oxide is reduced to
the metal.
 Thermodynamics helps us to understand
how coke reduces the oxide and why this
furnace is chosen. One of the main
reduction steps in this process is :
FeO(s) + C(s)  Fe(s/l) + CO (g) ...(1)
 It can be seen as a couple of two simpler
reactions. In one, the reduction of FeO is
taking place and in the other, C is being
oxidised to CO :
Figure : Blast furnace
1
FeO(s)   Fe(s)  O 2 (g); [G (FeO, Fe) ] ....(2)
2
1
C(s)  O 2 (g)  CO(g) ; [G (C, CO) ] ....(3)
2
When both the reactions take place to yield the equation (10), the net Gibbs energy change becomes:
G (C,CO) + G(FeO, Fe) = rG ....(4)
 Naturally, the resultant reaction will take place when the right hand side in equation (4) is negative. In
G° vs T plot representing reaction (2), the plot goes upward and that representing the change C  CO
(C, CO) goes downward. At temperatures above 1073 K (approx.), the C,CO line comes below the Fe,
FeO line
[G(C, CO) < G(Fe, FeO)].
 So in this range, coke will be reducing the FeO and will itself be oxidised to CO. In a similar way the
reduction of Fe3O4 and Fe2O3 at relatively lower temperatures by CO can be explained on the basis of
lower lying points of intersection of their curves with the CO, CO2 curve in the given figure.
 In the Blast furnace, reduction of iron oxides takes place in different temperature ranges. Hot air is
blown from the bottom of the furnace and coke is burnt to give temperature upto about 2200K in the
lower portion itself. The burning of coke therefore supplies most of the heat required in the process.
The CO and heat moves to upper part of the furnace. In upper part, the temperature is lower and the
iron oxides (Fe2O3 and Fe3O4) coming from the top are reduced in steps to FeO.
 Reactions involved :
 The reactions proceed in several stages at different temperatures. Since the air passes through in a few
seconds, the individual reactions does not reach equilibrium.
1. At 500 – 800 K (lower temperature range in the blast furnace)
3 Fe2O3 + CO  2 Fe3O4 + CO2 ; Fe3O4 + CO  3Fe + 4CO2
Fe2O3 + CO  2FeO + CO2
2. At 900 – 1500 K (higher temperature range in the blast furnace):
C + CO2  2 CO ; FeO + CO  Fe + CO2
 Limestone is also decomposed to CaO which removes silicate impurity of the ore as slag. The slag is in
molten state and separates out from iron.
CaCO3  CaO + CO2 ; CaO + SiO2  CaSiO3
 The iron obtained from blast furnace contains about 4% carbon and many impurities in smaller amount
(e.g., S, P, Si, Mn). This is known as pig iron and cast into variety of shapes.
 Cast iron is different from pig iron and is made by melting pig iron with scrap iron and coke using hot
air blast. It has slightly lower carbon content (about 3%) and is extremely hard and brittle.
 Further Reductions :
 Wrought iron or malleable iron is the purest form of commercial iron and is prepared from cast iron by
oxidising impurities in a reverberatory furnace lined with haematite. This haematite oxidises carbon to
carbon monoxide:
Fe2O3 + 3C  2Fe + 3 CO
 Limestone is added as a flux and sulphur, silicon and phosphorus are oxidised and passed into the slag.
The metal is removed and freed from the slag by passing through rollers.
EXTRACTION OF COPPER
 From cuprous oxide [copper (I) oxide] :
 In the graph of rG° vs T for formation of oxides the Cu2O line is almost at the top. So it is quite easy
to reduce oxide ores of copper directly to the metal by heating with coke (both the lines of C, CO and
C, CO2 are at much lower positions in the graph particularly after 500 - 600K). However most of the
ores are sulphide and some may also contain iron. The sulphide ores are roasted / smelted to give
oxides :
2Cu2S + 3O2  2Cu2O + 2SO2
 The oxide can then be easily reduced to metallic copper using coke:
Cu2O + C  2Cu + CO
 From copper glance / copper pyrite (self reduction) :
 In actual process the ore is heated in a reverberatory furnace after mixing with silica. In the furnace,
iron oxide ‘slags of’ as iron silicate and copper is produced in the form of copper matte. This contains
mostly Cu2S and some FeS.
2CuFeS2 + 4O2  Cu2S + 2FeO + 3SO2
Cu2S + FeO + SiO2  FeSiO3 (fusible slag) + Cu2S(matte)
 Copper matte is then charged into silica lined convertor (Bessemer convertor). Some silica is also
added and hot air blast is blown to convert the remaining FeS2, FeO and Cu2S/Cu2O to the metallic
copper. Following reactions take place :
2FeS + 3O2  2FeO + 2SO2 ; FeO + SiO2  FeSiO3
2Cu2S + 3O2  2Cu2O + 2SO2 ; 2Cu2O + Cu2S  6Cu + SO2 (self reduction)
 The solidified copper obtained has blistered appearance due to the evolution of SO2 and so it is called
blister copper.
EXTRACTION OF ZINC FROM ZINC BLENDE

 The ore is roasted in presence of excess of air at temperature 1200 K.
1200 K
2ZnS + 3O2  2ZnO + 2SO2 ; ZnS + 2O2  ZnSO4 ; ZnSO4  2ZnO + 2SO2 + O2
The reduction of zinc oxide is done using coke. The temperature in this case is higher than that in case of
copper. For the purpose of heating, the oxide is made into brickettes with coke and clay.
coke, 673
ZnO + C   Zn + CO
The metal is distilled off and collected by rapid chilling.
03 (3) The copper pyrite is concentrated by froth floatation

process.
(4) Copper is obtained by self-reduction in Bessemer
30. Select correct matching
converter.
(1) Pyrometallurgy: Extraction of Fe
35. Flux added in the extraction of iron is
(2) Electrometallurgy: Extraction of Al
(1) Silica (2) Feldspar
(3) Hydrometallurgy: Extraction of Au
(3) Limestone (4) Flint
(4) All of the above are correct
36. Copper and tin are refined by:
31. In extraction of copper, we use
(1) liquation (2) cupellation
(1) Cu 2S (2) Pyrites
(3) bessemerisation (4) poling
(3) Silver argentocyanide (4) CuFeS2
37. In the manufacture of iron from haematite, the function
32. In the extraction of Cu the reaction takes place in of lime-stone is as
Bessemer converter is:
(1) A reducing agent (2) Flux
(1) 2Cu 2O + Cu2S  6Cu + SO2
(3) Slag (4) Gangue
(2) 2CuFeS2 + O2  Cu2S + FeS + SO2
38. Blister copper is:
(3) 2Cu 2S + 3O2  2Cu 2O + 2SO2
(1) impure copper
(4) 2FeS + 3O2  2FeO + 2SO2.
(2) obtained in self-reduction process during
33. Copper pyrites are concentrated by bessemerisation
(1) Electromagnetic method (3) both (1) and (2) are correct
(2) Gravity method (4) none of these
(3) Froth floatation process 39. The slag obtained during the extraction of copper from
(4) All of the above methods copper pyrites is composed mainly of
34. Which of the following statement is incorrect about the (1) CaSiO3 (2) FeSiO3
extractive metallurgy of copper? (3) CuSiO3 (4) SiO2
(1) Matte chiefly consists of iron sulphide and some 40. The reaction 2ZnS + 3O 2  2ZnO + 2SO 2 in the
ferrous oxide. metallurgical process of zinc is called
(2) The impurity of iron sulphide is removed as fusible (1) Calcination (2) Cupellation
slag, FeSiO3 during roasting.
(3) Smelting (4) Roasting
41. In blast furnace, the highest temperature is in (3) Sn, Zn (4) Al, Ag
(1) Reduction zone (2) Slag zone 43. During extraction of Fe; slag obtained is
(3) Fusion zone (4) Combustion zone (1) FeO (2) FeSiO3
42. In which of the following pair of metals, both are (3) MgSiO3 (4) CaSiO3
commercially extracted from their respective ores by self- 44. Silver from argentiferous lead is obtained by
reduction method? (1) Pattinson's process (2) Parke's process
(1) Zn, Cu (2) Pb, Cu (3) Cyanide process (4) Both (1) and (2)
6.5 P.No.: 162
 Electrolytic reduction can be regarded as a technique for driving a reduction by coupling it through electrodes
and external circuitry to a reactive or a physical process with a more negative G.
 The free energy available from the external source can be assessed from the potential it produces across the
electrodes using the thermodynamic relation :
G = nFE ...(i)
where n is the number of electrons transferred, F is Faraday’s constant (F = 96.5 kcal/mol) and E° is
electrode potential of the redox coupled formed in the system.
Hence, the total Gibb’s energy of the coupled internal and external process is
G + G (external) = G – nFEext
 If the potential difference of the external source exceeds
G
E ext 
nF
the reduction is thermodynamically feasible; thus, the overall process occurs with a decrease in free energy.
More reactive metals have large negative values of the electrode potential. So their reduction is difficult. If
the difference of two E° values corresponds to a positive E° and consequently negative G° in equation (i),
then the less reactive metal will come out of the solution and the more reactive metal will go to the solution,
e.g.,
Cu2+ (aq) + Fe(s)  Cu(s) + Fe2+ (aq)
n+
 In simple electrolysis, the M ions are discharged at negative electrodes (cathodes )and deposited there.
Precautions are taken considering the reactivity of the metal produced and suitable materials are used as
electrodes. Sometimes a flux is added for making the molten mass more conducting.
EXTRACTION OF ALUMINIUM
 It involves the following processes
 Purification of Bauxite
(i) Bayer’s Method (ii) Hall's Method (iii) Serpeck’s Method
(used for red bauxite containing Fe2 O3 and (used for red bauxite containing Fe2O3 and (used for white bauxite containing
silicates as impurities) silicates as impurities) silica as impurities)
Al2O3 . 2H2O + 2NaOH Al 2O3 . 2H2O + Na2CO3
Al2O3 . 2H2O + 3C + N2
2NaAlO2 (soluble) + CO2 + 2H2O
2NaAlO2 (soluble) + 3H2O 2AlN + 3CO + 2H2O
Fe2O3 insoluble separated as red mud by 2NaAlO2 + 3H2O + CO2 2AlN + 3H2O  Al(OH)3 + NH3
filteration Solution is diluted with water and 2Al(OH)3 + Na2CO3 SiO2 + 2CO  2CO2 + Si
seeded with freshly prepared Al(OH)3. It induces Silicone volatilises at this temp.
1473 K 
the precipitation of Al(OH)3. Al(OH)3 is filtered 2Al(OH)3 Al2O3 + 3H2O .
2Al(OH)3 Al2O3 + 3H2O

leaving behind silicates in solution.
NaAlO2 + 2H2O  NaOH + Al(OH)3 
2Al(OH)3 Al2O3 + 3H2O
ELECTROLYTIC REDUCTION (HALL-HEROULT PROCESS)
 The purified Al2O3 is mixed with Na3AlF6 (cryolite) or CaF2 (fluorspar) ) which lowers the melting point of
the mixture and brings conductivity. The fused matrix is electrolysed. Steel cathode and graphite anode are
used. The graphite anode is useful here for reduction to the metal. The overall reaction may be taken as :
2Al2O3 + 3C  4Al + 3CO2
 The electolysis of the molten mass is carried out in an electrolytic cell using carbon electrodes. The oxygen
liberated at anode reacts with the carbon of anode producing CO and CO2. This way for each kg of aluminium
produced, about 0.5 kg of carbon anode is burnt away. The electrolytic reactions are :
Cathode : Al3+ (melt) + 3e–  Al (l)
Anode : C(s) + O2– (melt)  CO(g) + 2e–
C(s) + 2O2– (melt)  CO2 (g) + 4e–
Electric Frozen crust of
insulation alumina and electrolyte Control
lamp
Carbon Copper +
anode clamp
Iron
pot
Molten Electrolyte Dynamo
–
(Al 2O 3 + Na3AlF6)
Molten
Carbon lining aluminium
(cathode)
SOME OF THE METALS OBTAINED BY HYDROMETALLURGY
 Copper from low grade ores and scraps :
 Leaching of cuprite (Cu2O) or copper glance (Cu2S) with dil. H2SO4 in presence of air, gives a solution
of CuSO4 and the impurities present in the ores remain undissolved in the acid. Leaching of malachite
green, Cu(OH)2. CuCO3 with dil. H2SO4 also gives a solution of CuSO4.
2Cu2O (cuprite) + 4H2SO4 + O2  4CuSO4 (solution) + 4H2O
 Copper metal can be recovered from CuSO4 solution (obtained as above) either by electrolysing it
(cathode is of Cu-metal and anode is of lead) Cu-metal is collected at cathode or by treating it with
scrap iron which, being more reactive than Cu, displaces Cu from CuSO4 solution and Cu gets
precipitated (Metal displacement method).
CuSO4 (aq) + Fe(s)  FeSO4 (aq) + Cu(s)  ; Cu2+ (aq) + H2(g)  Cu(s) + 2H+ (aq)
 Leaching of low grade ores and scraps can be carried out using bacteria.
6.6 P.No.: 163

 Besides reductions, some extractions are based on oxidation particularly for non-metals.
 A very common example of extraction based on oxidation is the extraction of chlorine from brine (chlorine
is abundant in sea water as common salt).
2Cl– (aq) + 2H2O (l)  2OH–(aq) + H2(g) + Cl2(g)
 The G° for this reaction is + 422 kJ. When it is converted to E° (using G° = – nE°F), we get E° = –2.2 V.
Naturally, it will require an external e.m.f. that is greater than 2.2 V. But the electrolysis requires an excess
potential to overcome some other hindering reactions. Thus, Cl2 is obtained by electrolysis giving out H2
and aqueous NaOH as by products. Electrolysis of molten NaCl is also carried out. But in that case, Na
metal is produced and not NaOH.
04 (1) Aluminium (2) Thorium

(3) Heated Pt gauge (4) Carbon
45. Aluminothermic process is used for the extraction of
48. Identify the process to which the following reaction
metals, whose oxides are
belongs:
(1) Fusible
Al2O3.2H2O + Na2CO3  2NaAlO2 + 2H2O + CO2
(2) Not easily reduced by carbon
2NaAlO2 + 2H2O + CO2  50  60 C
(3) Not easily reduced by hydrogen  Al2O3.2H2O + Na2CO3
(4) Strongly basic (1) Hall's process (2) Baeyer's process
46. The function of fluorspar in the electrolytic reduction of (3) Serpeck's process (4) None of these
alumina dissolved in fused cryolite (Na3AlF6) is: 49. For extraction of sodium from NaCl, the electrolytic
(1) as a catalyst mixture NaCl + Na 3 AlF 6 + CaCl 2 is used. During
(2) to lower the temperature of the melt and improve extraction process, only sodium is deposited on cathode
the conductivity of cell but K and Ca do not because
(3) to decrease the rate of oxidation of carbon at the (1) Na is more reactive than K and Ca
anode (2) Na is less reactive than K and Ca
(4) to decrease the rate of oxidation of carbon at the (3) NaCl is less stable than Na3AlF6 and CaCl2
cathode (4) the discharge potential of Na+ is less than that of K+
47. The substance used in the thermite process of reducing and Ca2+ ions.
metal ores is
6.7 P.No.: 164
 Metals obtained by reduction processes still contain some objectionable impurities and have to be refined.
 Refining techniques vary widely from metal to metal and also depend on the use to which a metal has to be
put. Sometimes during refining some substances may have to be added to impart some desirable characteristic
to the metal. In some cases a metal is refined to recover some valuable by products, for example, Ag, Au, Pt
etc., may be present as impurities. Numerous techniques are available, including the following :
Liquation Process
 This process is used for the purification of the metal, which itself is readily fusible, but the impurities
present in it are not, i.e., the impurities are infusible. In other words, we can say that the melting point of
the metal to be purified should be lower than that of each of the impurities associated with the metal.
 This process is used for the purification of Sn and Zn, and for removing Pb from Zn-Ag alloy, which is
obtained at the end of Parke’s process and contains Pb as impurity.
Distillation Process
 This process is used to purify those metals which themselves are volatile and the impurities in them are
nonvolatile and vice-versa. Zn, Cd and Hg are purified by this process.
Zone Refining Method (Fractional Crystallisation Method)
 This process is used when metals are required in very high purity, for specific application. For example
pure Si and Ge are used in semiconductors and hence are purified by this method.
 Zone refining method is based on the principle that an impure molten metal on gradual cooling will deposit
crystals of the pure metal, while the impurities will be left in the remaining part of the molten metal.
 Germanium metal, which is used in semiconductor devices, is refined (purified) by the zone refining method.
 The impure germanium metal to be refined is taken in the form of a rod.
 A circular heater H is fitted around this rod and this heater is slowly moved along the length of the rod.
When the heater is at the extreme left end of the impure germanium rod, it melts a narrow zone (narrow
region) of the germanium rod at that place.
 Now, when the heater moves on a little to the right side, then the molten metal at the previous position cools
down and crystallizes to give pure metal at region X of the rod.
 The impurities, which were initially present in region X of germanium rod, now pass on to the region Y in
the adjacent molten zone. Now, as the heater is shifted more and more to the right side on the germanium
rod, the impurities also keep on shifting to the right side in to the newer and newer molten zones. Ultimately,
the impurities reach the extreme right end Z of the germanium rod. This end Z of the germanium rod
containing all the impurities is then discarded. The remaining rod is now of highly pure germanium metal.
In addition to germanium, silicon and gallium used as semiconductors are also refined by the zone refining
method.
Chromatographic Methods
 This method is based on the principle that different components of a mixture are differently adsorbed on an
adsorbent. The mixture is put in a liquid or gaseous medium which is moved through the adsorbent.
 Different components are adsorbed at different levels on the column. Later the adsorbed components are
removed (eluted) by using suitable solvent (eluant).
 Depending upon the physical state of the moving medium and the adsorbent material and also on the process
of passage of the moving medium, the chromatographic method is given the name. In one such method the
column of Al2O3 is prepared in a glass tube and the moving medium containing a solution of the components
is in liquid form. This is an example of column chromatography.
 This is very useful for purification of the elements which are available in minute quantities and the impurities
are not very different in chemical properties from the element to be purified. There are several
chromatographic techniques such as paper chromatography, column chromatography, gas chromatography,
etc. Procedures followed in column chromatography have been depicted in the following figures.
Electrolytic Refining
 Some metals such as Cu, Ni, and Al are refined electrolytically.
 The Hooper process is a process for the electrolytic refining of aluminum. Impure Al forms the anode and
pure Al forms the cathode of the Hooper’s cell which contains three liquid layers. The bottom layer is
molten impure Al, the middle is a fused salt layer containing aluminum fluoride, and the top layer is pure
Al. At the anode (bottom layer), Al passes with solution as aluminum ion (Al3+), and at the cathode (top
layer), these ions are reduced to the pure metal. In operation, molten metal is added to the bottom of the cell
and pure aluminum is drawn off the top.
At anode : Al  Al3+ + 3e–
At cathode : Al3+ + 3e–  Al
 Copper obtained from the reduction of ores must be purified for use in making electrical wiring because
impurities increase its electrical resistance.
 Impure Cu obtained from ores is converted to pure Cu in an electrolyte cell that has impure copper as the
anode and pure copper as the cathode.
 The electrolyte is an aqueous solution of CuSO4. At the impure Cu anode, Cu is oxidized along with the
more easily oxidized metallic impurities such as Zn and Fe.
 The less easily oxidized impurities such as Ag, Au, and Pt fall to the bottom of the cell as anode mud, which
is reprocessed to recover the precious metals. At the pure Cu cathode, Cu2+ ions get reduced to pure copper
metal, but the less easily reduced metal ions (Zn2+, Fe2+ etc.) remain in the solution.
Anode (oxidation) : M (s)  M2+ (aq) + 2e– ; (M = Cu, Zn, Fe)
Cathode (reduction) : Cu2+ (aq) + 2e–  Cu(s)
 Thus, the net cell reaction simply involves transfer of Cu metal from the impure anode to the pure cathode,
Cu obtained by this process is 99.95% pure.
Vapour Phase Refining
 In this method, the metal is converted into its volatile compound and then collected. It is then heated so that
it gets decomposed to give pure metal. So, following two requirements are essential for vapour phase
refinning.
1. The metal should form a volatile compound with an available reagent.
2. The volatile compound should be easily decomposable, so that the recovery is easy.
 Extraction of Nickel (Mond’s process) : Nickel forms a complex, the tetracarbonylnickel (0), [Ni(CO)4]
with carbon monoxide. This substance is readily volatilized (boiling point 43°C). This complex on heating
decomposes, giving pure metal and CO, which is recycled. The sequence of reaction is
H2O(g) + C  CO(g) + H2 ; Ni(s) + 4 CO(g) 
50 C
 [Ni(CO4)] (g)
[Ni (CO)4](g)  200 C
 Ni + 4CO (g)
 Van Arkel–De Boer process : Small amounts of very pure metals (Ti, Zr, or Bi) can be produced by this
method. This process is based on the fact that iodides are the least stable of the halides. The impure element
is heated with iodine, producing a volatile iodide, TiI4, ZrI4, or BiI3. These are decomposed by passing the
gas over an electrically heated filament of tungsten or tantalum that is white hot. The element is deposited
on the filament and the iodine is recycled.
50  250 C 1400 C
Impure Ti + 2I2   TiI4 
Tungsten filament
 Ti  2I 2
The method is very expensive and is employed for the preparation of very pure i.e. ultra pure metal for
specific use.
6.8 P.No.: 166
 Aluminium :
1. Aluminium foils are used as wrappers for chocolates.
2. The fine dust of the metal is used in paints and lacquiers.
3. Aluminium being highly reactive is used in the extraction of chromium and manganese from their
oxides.
4. Wires of aluminium are used as electricity conductors.
5. Alloys containing aluminium, being light, are very useful e.g.: used in body of aircraft, in utensils etc.
 Copper :
1. Copper is used for making wires used in electrical industry and for water and steam pipes.
2. It is used in several alloys that are rather tougher than the metal itself e.g.: brass (with zinc), bronze
(with tin) and coinage alloy (with nickel).
 Zinc :
1. Zinc is used for galvanising iron.
2. It is used in large quantities in batteries, as a constituent of many alloys, e.g.: brass, (Cu, 60%, Zn
40%) and german silver (Cu 25-30%, Zn 25-30%, Ni 40-50%).
3. Zinc dust is used as a reducing agent in the manufacture of dye-stuffs, paints, etc.
 Iron :
1. Cast iron is used for casting stoves, railway sleepers, gutter pipes, toys etc.
2. It is used in the manufacture of wrought iron and steel.
3. Wrought iron is used in making anchors, wires, bolts, chains and agricultural implements.
4. Steel finds a number of uses. Nickel steel is used for making cables, automobiles and aeroplane parts,
pendulum, measuring tapes, chrome steel for cutting tools and crushing machines, and stainless steel
for cycles, automobiles, utensils pens, etc.
(1) Right end, if zone is travelling from left to right

04 (2) Left end, if zone is travelling from left to right
50. Which of the following is not a refining process? (3) Left end, if zone is travelling from right to left
(1) Dressing (2) van Arkel process (4) Centre, if zone is travelling from any side
(3) Cementation (4) Poling 53. During the process of electrolytic refining of copper, some
metals present as impurity settle as anode mud. These
51. In electro-refining the impure metal is made as
are
(1) Cathode (2) Anode
(1) Fe and Ni (2) Ag and Au
(3) Electrolyte (4) Both (1) and (3)
(3) Sn and Ag (4) Pb and Zn
52. In zone refining, pure metal is obtained at the
6.9 Synopsis
 Occurrence : Oxygen is most abundant non-metal while aluminium is the most abundant metal. Hydrogen
is most abundant in cosmic region and water (oceans). More electropositive metals occur as oxides or
chlorides while less electropositive metals occur as sulphides.
 Minerals are the naturally occurring solid substances in the form of which a metal exist in earth’s crust.
 Ores are those minerals from which a metal can be extracted, conveniently, economically and in large
amounts.
 Gangue or matrix is the term used for impurities (earthy impurities) associated with ore.
 Flux are the substances used to convert infusible mass into fusible mass called slag. For an acidic impurity,
basic flux like MgO, CaO, etc., are used and for a basic impurity, acidic flux like SiO2 is used.
 Metallurgy refers to complete scientific and technological process used for the extraction of an element in
its pure form from its ores. If it is done in aqueous medium, term hydrometallurgy is involved, it is called
electrometallurgy.
 Ore dressing or concentration is the pretreatment of ores based on physical properties and without bringing
out any major chemical change in the ore. In case of heavy ores (like tin stone, chromite) gravity separation
is used, for magnetic substances (to separate them from non-magnetic substance) magnetic separation is
used. In case of sulphide ores, Froth floatation process is used. Leaching is done for Ag, Au, Al etc.
 Calcination is the process of heating of concentrated ore below its melting point in absence of air while
roasting is the process of heating of concentrated ore below its melting point in excess of air. Both the
processes are carried out in reverberatory furnce.
 Ellingham diagrams are the plots of Gibbs free energy change for the formation of metal oxides against
temperature and for a reaction to be spontaneous, the net G of the two sub reactions must be negative.
However, from these diagram, no idea is obtained about the rate (speed) of reaction.
 Smelting is the process of reduction of oxides of less electropositive metals by coke or CO. It is carried out
in blast or reverberatory furnace.
 If oxide is reduced by its own, the process is called auto or self reduction. If aluminium is used as reductant
the process is called Goldschmidt alumino thermic process. In case of highly electropositive elements,
electrolytic reduction is used. Hydrogen and other metals like Mg, Na, can also be used as reductant in
some cases.
 Refining is the process of purification of metal and is done by distillation (for Zn, Hg, Cd), liquation (for
Sn), electrolysis (for Cu, Ag, Au, Pb, Zn, Al), vapour phase refining (Mond’s process) for Ni and van Arkel
method (for Ti or Zr). Zone refining (for Si, Ge, B etc.) poling (for Cu), Cupellation (for Ag), chromatography
etc.
Metal Occurrence
Copper Copper pyrites, CuFeS2 copper glance, Cu2S
Malachite CuCO3.Cu(OH)2, cuprite, Cu2O
Zinc Zinc blende or sphalerite, ZnS calamine, ZnCO 3, zincite, ZnO
Aluminium Bauxite, Al2O3.xH2O cryolite, Na3AlF6
Iron Haematite, Fe2O 3 magnetite, Fe3O 4
Tin Cassiterite (tie stone) SnO 2
Silver Aregentite Ag2S, horn silver AgCl
USES OF IMPORTANT METALS

Metal Uses
Copper Wire, pipe, calorimeters, alloys etc.
Zin Alloys, galvanisation, as reductant.
Aluminium Paint, food packaging electric wires, utensils etc.
Iron Steel, railway sleepers, gutter pipes utensis etc.
1. Which of the following statements is incorrect? 10. Which of the following statements is incorrect?
(1) Silver glance mainly contains silver sulphide. (1) Beneficiation of ores involve the processes which
(2) Copper pyrites mainly contains CuFeS2. are used for the removal of unwanted impurities.
(3) Zinc blende mainly contains ZnSO4. (2) In metallurgy, flux is a substance which is used to
(4) Magnetite is the mixed oxide of FeO and Fe2O3 i.e. convert infusible impurities to fusible mass.
Fe3O4. (3) Aluminium is extracted by the electrolysis of
2. Among the following statements, the incorrect one is : alumina.
(1) calamine and siderite are carbonates (4) In smelting processes the metal is obtained in fused
(2) argentite and bauxite are oxides state.
(3) zinc blende and galena are sulphides 11. Which of the following processes are used for the
extraction of Mg and Ag respectively?
(4) malachite and azurite are ores of copper
(1) Carbon reduction and cyanide process.
3. Dolomite is mineral whose formula is :
(1) CaMg(CO3)2 (2) MgCO3 (2) Cyanide process and electrolytic reduction.
(3) CaCO3.MgCO3 (4) MgSO4.7H2O (3) Electrolytic reduction and cyanide process.
4. Magnetic separation process is not used for the (4) Carbon monoxide reduction and cyanide process.
concentration of : 12. Slag formed during smelting process in the extraction of
(1) cassiterite (2) bauxite Fe (from haematite) and Cu (from copper pyrites) are
respectively :
(3) haematite (4) chromite
(1) both CaSiO3 (2) both FeSiO3
5. Froth floatation process for the concentration of sulphide
ores is an illustration of the practical application of: (3) CaSiO3 and FeSiO3 (4) FeSiO3 and CaSiO3
(1) adsorption (2) absorption 13. When bauxite is heated with carbon in the atmosphere of
(3) sedimentation (4) coagulation nitrogen, products formed are :
6. Which one of the following is not a method of (1) Al + CO (2) Al + CO2
concentration of ore ? (2) Al + CO + CO2 (4) AlN + CO
(1) electromagnetic separation 14. Bauxite is leached with :
(2) smelting (1) KCl (2) NaCN
(3) gravity separation (3) NaOH (4) Na2SO4
(4) froth floatation process 15. Leaching the silver and gold metal with CN– :
7. Froth floatation process used for the concentration of (1) is oxidation reaction
sulphide ore : (2) is complexation reaction
(1) is based on the difference in wetability of different (3) is reduction reaction
minerals. (4) is both (1) and (2)
(2) uses Xanthates and fatty acids as collector. 16. Leaching of low grade copper ores is carried out by :
(3) uses NaCN as depressant in the mixture of ZnS and (1) sulphuric acid (2) sodium hydroxide
PbS when ZnS forms soluble complex and PbS
(3) sodium sulphate (4) sodium nitrate
forms froth.
17. Which of the following reactions represents Goldschmidt
(4) All are correct statements.
aluminothermite process?
8. The reason, for floating of ore particles in concentration
(1) 2Al + HCl  2AlCl3 + 3H2
by froth floatation process is that :
(2) Al2O3 + 2NaOH + 2H2O  2NaAlO2 + 3H2O
(1) they are light (2) they are insoluble
(3) 2Al + N2  2AlN
(3) they are charged (4) they are hydrophobic
(4) 2Al + Cr2O3  2Cr + Al2O3
9. In which of the following metallurgical processes leaching
is not involved ? 18. Calcium is extracted by the electrolysis of :
(1) Al from Al2O3 (1) fused mixture of CaCl2 and CaF2
(2) Ag from Ag2S (2) fused mixture of CaCl2 and NaF
(3) Mg from MgCl2 (anhydrous) (3) aqueous solution of CaCl2
(4) From low grade copper ore and scrapes (4) aqueous solution of Ca3(PO4)2 solution
19. The materials which are added along with the calcined 25. Which one of the following reactions occurs during
iron ore into the blast furnance in the extraction of iron smelting in the reduction zone at lower temperature (in
from haematite ore are : iron metallurgy) ?
(1) coke and silica (1) CaO + SiO2  CaSiO3 (slag)
(2) coke and lime stone (2) Fe2O3 + 3C  2Fe + CO
(3) lime stone and silica (3) 3Fe2O3 + CO  2Fe3O4 + CO2
(4) coke and borax (4) CO2 + C  2CO
20. In the extraction of aluminium 26. Extraction of silver from Ag2S by the use of sodium
Process X : employed for red bauxite to remove iron oxide cyanide is an example of :
(main impurity) (1) roasting
Process Y : (Serpeck’s process) : used for white bauxite (2) hydrometallurgy
to remove Z (main impurity) then, (3) electrometallurgy
Select correct option for the process X and impurity Z. (4) smelting
(1) X = Hall and Heroult’s process and Z = SiO2 27. In the purification of aluminium by Hoope’s process,
(2) X = Bayer’s process and Z = SiO2 impurities of silicon and copper are added to molten
(3) X = Serpeck’s process and Y = iron oxide aluminium in order to :
(4) X = Bayer’s process and Y = iron oxide (1) make the melt conducting
21. Which of the following statements is correct regarding (2) lower the melting point of the melt
the slag obtained during the extraction of a metal like (3) smooth deposit of aluminium
copper or iron ? (4) make the melt heavier
(1) The slag is lighter and has lower melting point than 28. Which method is not correctly matched for refining of
the metal crude metals ?
(2) The slag is heavier and has lower melting point than (1) Distillation : zinc and mercury
the metal (2) Liquation : tin
(3) The slag is lighter and has higher melting point than (3) Van Arkel : titatnium
the metal
(4) Mond process : lead
(4) The slag is heavier and has higher melting point than
29. Silver ore dissolves in dilute solution of NaCN in the
the metal
presence of air to form :
22. Choose the correct option using the code regarding
(1) AgCN (2) [Ag(CN)2] –
roasting process.
(3) AgCNO (4) [Ag(CN)3]3–
I. It is the process of heating the ore in air in a
reverberatory furnace to obtain the oxide. 30. Which of the following metals may be present in the anode
mud during electror-fining of copper?
II. It is an exothermic process.
I. Gold ; II. Iron,
III. It is used for the concentration of sulphide ore.
III. Silver ; IV. Magnesium
IV. It removes easily oxidisable volatile impurities
present in the concentrated ore. (1) I and II (2) II and IV
(1) I, II and III (2) I, II and IV (3) I and III (4) III and IV
(3) I, III and IV (4) I, II, III and IV 31. Which one of the following processes involves the
principle of fractional crystallisation for the refining of
23. A sulphide ore like ZnS is first roasted into its oxide prior
impure metals ?
to reduction by carbon because :
(1) Parke’s process
(1) a sulphide ore cannot be reduced to metal at all
(2) Mond’s process
(2) no reducing agent is found suitable for reducing a
sulphide ore. (3) Van Arkel process
(3) the Gibb’s free energy of formation of most (4) Zone refining
sulphides are greater than that for CS2. 32. Which does not represent correct method ?
(4) a metal oxide is generally less stable than the metal (1) TiCl2 + 2Mg  Ti + 2MgCl2 : Kroll
sulphide. (2) Ni(CO)4  Ni + 4CO : Mond
24. In the metallurgy of iron, the upper layer obtained in the
bottom of blast furnace mainly contains : 1
(3) Ag2CO3  2Ag + CO2 + O : Van Arkel
(1) CaSiO3 (2) spongy iron 2 2
(3) Fe2O3 (4) FeSiO3 (4) ZrI4  Zr + 2I2 : Van Arkel
33. Match column I with column II and select the correct (3) PbS forms soluble complex Na2[Pb(CN)4] while ZnS
answer using the codes given below the lists : forms froth
Column I Column II (4) NaCN is never added in froth floatation process
I. Cyanide process. A. Ultra pure Ge 38. Gravity separation method is based upon:
II. Froth floatation B. Pine oil. (1) preferential washing of ores and gangue particles.
process. (2) difference in densities of ore particles and
III. Electrolytic C. Extraction of Al. impurities.
reduction. (3) difference in chemical properties of ore particles and
impurities.
IV. Zone refining. D. Extraction of Au.
(4) none of these.
(1) I–(C), II–(A), III–(D), IV-(B)
39. Which of the following statement is incorrect?
(2) I–(D), II–(B), III–(C), IV–(A)
(1) Silver glance mainly contains silver sulphide
(3) I–(C), II–(B), III–(D), IV-(A)
(2) Gold is found in native state
(4) I–(D), II–(A), III–(C), IV-(B)
(3) Zinc blende mainly contains zinc chloride
34. Which of the following is obtained by zone refining
(4) Copper pyrites also contain Fe2S3
method?
40. Among the following statements, the incorrect one is
(1) Highly pure ore
(1) Calamine and siderite are carbonates
(2) Highly pure aluminium
(2) Argentite and cuprite are oxides
(3) Ultra pure oxide
(3) Zinc blende and pyrites are sulphides
(4) Ultra pure metals used as semi-conductors
(4) Malachite and azurite are ores of copper
35. Which of the following is not an ore? 41. Which one of the following is correct?
(1) Bauxite (2) Malachite (1) A mineral cannot be an ore
(3) Zinc blende (4) Pig iron (2) An ore cannot be a mineral
36. Which is not a mineral of aluminium? (3) All minerals are ores
(1) Anhydrite (2) Bauxite (4) All ores are minerals
(3) Corundum (4) Diaspore 42. In the manufacture of iron limestone added to the blast
37. NaCN is sometimes added in the froth flotation process furnace, the calcium ion ends in the form of
as a depressant when ZnS and PbS minerals are expected (1) Slag (2) Gangue
because: (3) Calcium metal (4) CaCO3
(1) Pb(CN)2 is precipitated while no effect on ZnS 43. In smelting the furnace most suitable is
(2) ZnS forms soluble complex Na2[Zn(CN)4] while PbS (1) Reverberatory furnace (2) Blast furnace
forms froth (3) Open hearth furnace (4) Muffle furnace
(Concept Builder)
1. In the extraction of chlorine by electrolysis of brine, 8. In the metallurgy of aluminium :

(1) oxidation of Cl– ion to chlorine gas occurs. (1) Al3+ is oxidized to Al(s)
(2) reduction of Cl– ion to chlorine gas occurs. (2) graphite anode is oxidized to carbon monoxide and
(3) For overall reaction ?has negative value. carbon dioxide
(4) a displacement reaction takes place. (3) oxidation state of oxygen changes in the reaction at
2. When copper ore is mixed with silica in a reverberatory anode
furnace, copper matte is produced. The copper matte (4) oxidation state of oxygen changes in the overall
contains : reaction involved in the process.
(1) sulphides of copper (II) and iron (II) 9. Electrolytic refining is used to purify which of the
(2) sulphides of copper (II) and iron (III) following metals?
(3) sulphides of copper (I) and iron (II) (1) Cu and Zn (2) Ge and Si
(4) sulphides of copper (I) and iron (III) (3) Zr and Ti (4) Zn and Hg
3. Which of the following reaction is an example of 10. Extraction of gold and silver involves leaching the metal
autoreduction? with CN– ion. The metal is recovered by :
(1) Fe3O4 + 4CO  3Fe + 4CO2 (1) displacement of metal by some other metal from the
(2) Cu 2O + C  2Cu + CO complex ion
(2) roasting of metal complex
2 2
(3) Cu (aq)  Fe(s)  Cu (s)  Fe(aq) (3) calcinations followed by roasting
(4) thermal decomposition of metal complex
1 1
(4) Cu 2O  Cu 2S  3Cu  SO2
2 2
Note: Answer the questions 11-13 on the basis of given figure.
4. A number of elements are available in the earth’s crust
but most abundant elements are :
(1) Al and Fe (2) Al and Cu
(3) Fe and Cu (4) Cu and Ag
5. Zone refining is based on the principle that :
(1) impurities of low boiling metals can be separated
by distillation
(2) impurities are more soluble in molten metal than in
solid metal
(3) different components of a mixture are differently
adsorbed on an adsorbent
(4) vapour of volatile compound can be decomposed
in pure metal
6. In the extraction of copper from its sulphide ore, the metal
is formed by the reduction of Cu2O with
(1) FeS (2) CO
(3) Cu 2S (4) SO2
7. Brine is electrolysed by using inert electrodes. The
reaction at anode is :
 1
(1) Cl(aq )  Cl 2(g)  e ; E ocell  1.36 V 11. Choose the correct option of temperature at which carbon
2
reduces FeO to iron and produces CO.
(2) 2H 2O(l )  O2(g)  4H   4e ; E cell
o
 1.23 V (1) Below temperature at point A
(2) Approximately at the temperature corresponding to

(3) Na (aq)  e  Na (s) ; E cell
o
  2.71 V point A
(3) Above temperature at point A but below temperature
 1 at point D
(4) H(aq)  e  H 2(g ) ; Ecell
o
 0.00 V
2 (4) Above temperature at point A
12. Below point ‘A’ FeO can : (2) Gº value for the overall reduction reaction with a
(1) be reduced by carbon monoxide only mixture of 1 mol carbon and 1 mol oxygen is
(2) be reduced by both carbon monoxide and carbon positive.
(3) be reduced by carbon only (3) Gº value for the overall reduction reaction with a
(4) Cannot be reduced by both carbon and carbon mixture of 2 mol carbon and 1 mol oxygen will be
monoxide positive.
13. For the reduction of FeO at the temperature corresponding (4) Gº value for the overall reduction reaction with
to point D, which of the following statement is correct? carbon monoxide is negative.
(1) Gº value for the overall reduction reaction with
carbon monoxide is zero.
• Instructions for Questions 1 to 10 8. Assertion : Wrought iron is prepared from cast iron by
Given below are two statements : one is labelled as Assertion oxidising impurities in a reverberatory furnace lined with
(A) and the other is labelled as Reason (R). haematite.
In the light of the above s tatements, choose the most Reason : Haematite oxidises carbon to carbon monoxide.
appropriate answer from the options given below : 9. Assertion : Sulphide ores of Zn and Pb are generally
(1) Both (A) and (R) are correct and (R) is the correct converted into their respective oxides, prior to reduction.
explanation of (A) Reason : The zinc oxide and lead oxide are reduced by
(2) Both (A) and (R) are correct but (R) is not the correct carbon to their respective free metals.
explanation of (A)
10. Assertion : CuFeS2 is concentrated by froth floatation
(3) (A) is correct the (R) is not correct
method
(4) (A) is not correct but (R) is correct
Reason : CuFeS2 is main ore of copper
1. Assertion : In extraction of copper from chalcopyrite after

roasting in supply of air at moderate temperature, the • Instructions for Questions 11 to 15
temperature of the roasting ore is increased above the Given below are two statements :
fusion temperature and then silica is added in
In the light of the above s tatements, choose the most
reverberatory furnace.
Reason : In the extraction of copper from chalcopyrites
(1) Both Statement I and Statement II are correct
during smelting, the impurity of iron oxide is removed as
fusible slag (FeSiO3) in blast furnace or reverberatory (2) Both Statement I and Statement II are incorrect
furnace. (3) Statement I is correct but Statement II is incorrect
2. Assertion : Extraction of zinc from sphalerite ore (4) Statement I is incorrect but Statement II is correct
involves the roasting followed by reduction with coke.
Reason : Zinc can be extracted by hydrometallurgy. 11. Statement I : In the smelting of copper ore coke is added
3. Assertion : Silica is added as a flux in reverberatory in the blast furnace.
furnace, in the extraction of copper from copper pyrites.
Statement II : Coke reduces, CuO into Cu.
Reason : Silica decreases the melting point of the ore
12. Statement I : Extraction of iron metal from iron oxide
and increases the conductivity.
ore is carried out by heating with coke.
4. Assertion : During calcination the ore is heated well

below its melting point in the limited supply of air or Statement II : The reaction Fe2O3(s)   Fe(s) + 3/
absence of air. 2O2(g) is a spontaneous process at standard condition.
Reason : The process of calcination is carried out for 13. Statement I : All the ores are mineral.
sulphide ores.
Statement II : Most of the ores contains metals in
5. Assertion : Electropositive metals like Mg, Al are combined state
extracted by electrolysis of their salt solutions.
14. Statement I : In the extraction of Ag the complex
Reason : Highly electropositive metals cannot be reduced Na[Ag(CN)2] is reacted with Zn.
by chemical reduction methods.
Statement II : Zn is transition metal according to
6. Assertion : In Hall - Heroult process aluminium is electronic theory
extracted by the electrolytic reduction of alumina
dissolved in molten cryolite or fluorspar. 15. Statement I : Thermite mixture Fe2O3 + Al (powder) is
used in the welding.
Reason : The cryolite or fluorspar lower the melting point
of melt and make it more conducting. Statement II : Al is a good reductant.
7. Assertion : Wolframite impurity is separated from tin
stone (SnO2) by magnetic separation.
Reason : Tin stone is ferromagnetic and is attracted by
the magnet.
(Direct from
NCERT)
Match the List – I and List – II and choose the correct Choose the correct answer from the options given below :
combination from the options given. (1) (a) – (i); (b) – (ii); (c) – (i, iii); (d) – (i, iv)
(2) (a) – (ii), (b) – (iii), (c) – (i); (d) – (iv)
1. Match the name of the processes given in List – I with
Type(s) of metallurgical methods given in List – II. (3) (a) – (iii), (b) – (ii), (c) – (iv); (d) – (i)
(4) (a) – (iv, v), (b) – (ii), (c) – (i, ii); (d) – (iv)
(a) Hall-Heroult (i) Molten Al2O3 + Na3AIF6 4. Match the following:
process electrolysis. List - I List - II
(b) Dow’s sea water (ii) Molten MgCl2 + CaCl2
process + NaCl electrolysis. (a) Reduction of oxides with Al (i) Ti
(b) Reduction of chlorides with Mg (ii) Cu
(c) Hoop’s process (iii) Molten impure aluminium
+ fluorides of Na+, Ba2+ and at higher temperature
(c) Autoreduction of sulphides (iii) Cr
Al3+ electrolysis.
during reduction
(d) Mac-Arthur (iv) Complex formation and
Forrest process displacement method. (d) Strong heating of metal oxides (iv) Ag
Choose the correct answer from the options given below : Choose the correct answer from the options given below :
(1) (a) – (i); (b) – (ii); (c) – (iii); (d) – (iv) (1) (a) – (iii), (b) – (iv), (c) – (i), (d) – (ii)
(2) (a) – (ii), (b) – (iii), (c) – (i); (d) – (iv) (2) (a) – (iv), (b) – (iii), (c) – (ii), (d) – (i)
(3) (a) – (iii), (b) – (ii), (c) – (iv); (d) – (i) (3) (a) – (iii); (b) – (iv); (c) – (ii); (d) – (iv)
(4) (a) – (iv, v), (b) – (ii), (c) – (i, ii); (d) – (iv) (4) (a) – (iv, v), (b) – (ii), (c) – (i, ii), (d) – (iii)
2. Match the following : 5. Match the following:

List – I List – II List - I List - II
(a) Extracted by the reduction (i) Ag
(a) Pb3O4+ dil. HNO3  (i) Metal oxides

of ore by carbon
(b) LiNO3   (ii) NO2
(b) Extracted by the formation (ii) Zn

(c) NaNO3  (iii) O2
 soluble complex

(d) Pb(NO3)2  (iv) Metal nitrites or metal (c) By product as anode mud of (iii) Fe

nitrates electrolytic refining of Cu
(d) Metals involve in parke’s process (iv) Au
(1) (a) – (i); (b) – (ii); (c) – (i, ii, iii)); (d) – (i, ii, iii) Choose the correct answer from the options given below :
(2) (a) – (iv), (b) – (i, ii, iii), (c) – (ii), (d) – (i, ii, iii) (1) (a) – (iv), (b) – (iii), (c) – (ii, iii), (d) – (ii)
(3) (a) – (iii), (b) – (ii), (c) – (i, ii, iii), (d) – (i, ii, iii) (2) (a) – (ii, iii); (b) – (i, iv); (c) – (i, iv); (d) – (i, ii)
(4) (a) – (i, iv); (b) – (i, ii, iii); (c) – (iii, iv); (d) – (i, ii, iii) (3) (a) – (ii, iii), (b) – (iii), (c) – (ii, iii), (d) – (i)
(4) (a) – (ii), (b) – (ii, iii), (c) – (iii), (d) – (ii, iii)
List - I List - II
(a) PbS  PbO (i) Roasting
(b) CaCO3  CaO (ii) Calcination
(c) ZnS  Zn (iii) Carbon reduction
(d) Cu 2S  Cu (iv) Self reduction
1. The method of zone refining of metals is based on the 8. Which one of the following is a mineral of iron?
principle of [AIPMT-2003] [AIPMT-2012]
(1) Greater noble character of the solid metal than that (1) Malachite (2) Cassiterite
of the impurity (3) Pyrolusite (4) Magnetite
(2) Greater solubility of the impurity in the molten state 9. Aluminium is extracted from alumina (Al 2 O 3 ) by
than in the solid electrolysis of a molten mixture of [AIPMT-2012]
(3) Greater mobility of the pure metal than that of (1) Al2O3 + HF + NaAlF4
impurity (2) Al2O3 + CaF2 + NaAlF4
(4) Higher melting point of the impurity than that of (3) Al2O3 + Na3AlF6 + CaF2
the pure metal (4) Al2O3 + KF + Na3AlF6
2. A solid compount X on heating gives CO 2 gas and a 10. Roasting of sulphides gives the gas X as a byproduct.
residue mixed with water forms Y. On passing an excess This is a colourless gas with choking smell of burnt
of CO2 through Y inwater, a clear solution Z is obtained. sulphur and causes great damage to respiratory organs as
On boiling Z, compound X is reformed. The compound a result of acid rain. Its aqueous solution is acideic acts
X is [AIPMT-2004] as a reducing agent and its acid has never been insolated.
(1) Ca(HCO3)2 (2) CaCO3 The gas X is [NEET-2013]
(3) Na2CO3 (4) K2CO3 (1) H2S (2) SO2
3. Which of the following statements, about the advantage (3) CO2 (4) SO3
of roasting of sulphide ore before reduction is not true? 11. In the extraction of copper from its sulphide ore, the metal
[AIPMT-2007] finally obtained by the reduction of cuprous oxide with
(1) Carbon and hydrogen are suitable reducing agents [AIPMT-2015]
for metal sulphides (1) iron (II) sulphide (2) carbon monoxide
(2) The fG° of the sulphide is greater than those for (3) copper (I) sulphide (4) sulphur dioxide
CS2 and H2S
12. Match items of Column I with the items of Column II
(3) The fG° is negative for roasting of sulphide ore to and assign the correct code. [NEET-2016]
oxide
Column I Column II
(4) Roasting of the sulphide to the oxide is
(a) Cyanide process 1. Ultrapure Ge
thermodynamically feasible
(b) Froth floatation 2. Dressing of ZnS
4. Sulphide ores of metals are usually concentrated by froth
process
floatation process. Which one of the following sulphide
ores offers an exception and is concentrated by chemical (c) Electrolytic reduction 3. Extraction of Al
leaching [AIPMT-2007] (d) Zone refining 4. Extraction of Au
(1) Argentite (2) Galena 5. Purification of Ni
(3) Copper pyrite (4) Sphalerite (1) a - 2, b - 3, c - 1, d - 5
5. Which of the following pairs of metals is purified by van (2) a - 1, b - 2, c - 3, d - 4
Arkel method ? [AIPMT-2011] (3) a - 3, b - 4, c - 5, d - 1
(1) Zr and Ti (2) Ag and Au (4) a - 4, b - 2, c - 3, d - 1
(3) Ag and Au (4) Ni and Fe 13. Extraction of gold and silver involves leaching with CN–
6. Which of the following elements is present as the impurity ion. Silver is later recovered by [NEET-2017]
to the maximum extent in the pig iron? [AIPMT-2011] (1) liquation (2) distillation
(1) Carbon (2) Silion (3) zone refining (4) displacement with Zn
(3) Phosphorus (4) Manganese 14. Identify the correct statement from the following
7. In the extraction of copper from its sulphide ore, the metal [NEET-2020]
is finally obtained by the reduction of cuprus oxide with (1) Pig iron can be moulded into a variety of shapes.
[AIPMT-2012] (2) Wrought iron is impure iron with 4% carbon.
(1) copper (I) sulphide (Cu2S) (3) Blister copper has blistered appearance due to
(2) Sulphur dioxide evolution of CO2.
(3) Iron sulphide(FeS) (4) Vapour phase refining is carried out for Nickel by
(4) Carbon Monoxide (CO) Van Arkel method.
15. Match the elements in Column I with methods of 17. Match List-I with List-II. [NEET-2022]
purification in Column II. [NEET-2020] List-I (Ores) List-II (Composition)
Column I Column II (a) Haematite (i) Fe3O4
(a) Boron (i) Van Arkel method (b) Magnetite (ii) ZnCO3
(b) Tin (ii) Mond’s process (c) Calamine (iii) Fe2O3
(c) Zirconium (iii) Liquation (d) Kaolinite (iv) [Al2(OH)4Si2O5]
(d) Nickel (iv) Zone refining Choose the correct answer from the options given below:
(1) (a)-(iv) (b)-(iii) (c)-(i) (d)-(ii) 4 (1) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii)
(2) (a)-(iv) (b)-(iii) (c)-(ii) (d)-(i) (2) (a)-(i), (b)-(iii), (c)-(ii), (d)-(iv)
(3) (a)-(i), (b)-(ii), (c)-(iii), (d)-(iv)
(3) (a)-(ii) (b)-(i) (c)-(iv) (d)-(iii)
(4) (a)-(iii), (b)-(i), (c)-(ii), (d)-(iv)
(4) (a)-(iii) (b)-(iv) (c)-(i) (d)-(ii)
18. Which one of the following is not a calcination reaction?
16. Which one of the following methods can be used to obtain

highly pure metal which is liquid at room temperature ? 4 (1) ZnCO 3   ZnO  CO 2 [NEET-2022]
[NEET-2021] 
(2) Fe2O3 .xH 2O   Fe 2O3  xH 2O
(1) Electrolysis

(2) Chromatography (3) CaCO3 .MgCO3   CaO  MgO  2CO 2
(3) Distillation 
(4) CaCO3  2HCl   CaCl2  H 2O  CO 2
(4) Zone refining
6.15
21. (1) 22. (4) 23. (3) 24. (1) 25. (3)
1. (1) 2. (3) 3. (2) 4. (3) 5. (3)
6. (1) 7. (2) 8. (1) 9. (3) 10. (3) 26. (2) 27. (4) 28. (4) 29. (2) 30. (3)
11. (2) 12. (1) 13. (3) 14. (4) 15. (4) 31. (4) 32. (3) 33. (2) 34. (4) 35. (4)
36. (1) 37. (2) 38. (2) 39. (3) 40. (2)
DAILY PRACTICE PROBLEM (DPP) – 02 41. (4) 42. (1) 43. (2)
21. (3) 22. (2) 23. (2) 24. (4) 25. (3)
26. (2) 27. (1) 28. (3) 29. (1) 1. (1) 2. (3) 3. (4) 4. (1) 5. (2)
6. (3) 7. (1) 8. (2) 9. (1) 10. (1)
DAILY PRACTICE PROBLEM (DPP) – 03 11. (4) 12. (1) 13. (1)
30. (4) 31. (4) 32. (1) 33. (3) 34. (1) ASSERTION–REASON & STATEMENT QUESTIONS
35. (3) 36. (4) 37. (2) 38. (3) 39. (2)
40. (4) 41. (4) 42. (2) 43. (4) 44. (3) 1. (4) 2. (3) 3. (3) 4. (3) 5. (4)
6. (2) 7. (3) 8. (2) 9. (1) 10. (2)
45. (2) 46. (2) 47. (1) 48. (1) 49. (4)
MATRIX TYPE QUESTIONS
50. (3) 51. (2) 52. (2) 53. (2) ARCHIVE QUESTIONS
MISCELLANEOUS QUESTIONS FROM NCERT 1. (2) 2. (2) 3. (1) 4. (1) 5. (1)
1. (3) 2. (2) 3. (1) 4. (2) 5. (1) 6. (1) 7. (1) 8. (4) 9. (3) 10. (2)
6. (2) 7. (4) 8. (4) 9. (3) 10. (3) 11. (3) 12. (4) 13. (4) 14. (1) 15. (2)
11. (3) 12. (3) 13. (4) 14. (3) 15. (4) 16. (3) 17. (4) 18. (4)
114 Coordination Compounds
COORDINATION
COMPOUNDS
Chapter 09
%
C. 1 0
A. VBT, CFT 48%
B. Introduction, Nomenclature, Isomerism 42%

A. 48% B. 42%
C. Organometallic Compounds 10%
WHAT DO YOU WANT TO KNOW? 9.4.5 Geometrical Isomerism

9.4.6 Optical Isomerism
9.0 INTRODUCTION 9.5 BONDING IN COORDINATION COMPOUNDS
9.1 WERNER’S THEORY OF COORDINATION 9.5.1 Valance Bond Theory
COMPOUNDS 9.5.2 Magnetic Properties of Coordination
9.2 DEFINITION OF SOME IMPORTANT Compounds
TERM PERTAINING TO COORDINATION 9.5.3 Limitations in Valence Bond Theory
COMPOUNDS 9.5.4 Cristal Field Theory
9.3 NOMENCLATURE OF COORDINATION 9.5.5 Colour in Coordination Compounds
COMPOUNDS 9.5.6 Limitations of Crystal Field Theory Page
9.3.1 Writing the Formulas of Mononuclear 9.6 BONDING IN METAL CARBONYLS
Coordination Entities 9.7 STABILITY OF COORDINATION COMPOUNDS
9.3.2 Writing the Name of Mononuclear 9.8 APPLICATIONS OF COORDINATION AND
Coordination Compounds ORGANOMETALLIC COMPOUNDS
9.3.3 Writing the Name of Polynuclear
9.9 SYNOPSIS
Coordination Compounds
9.4 ISOMERISM IN COORDINATION 9.11 NCERT Exemplar Questions
COMPOUNDS 9.12 Assertion-Reason and Statement
9.4.1 Ionisation Isomerism Based Questions from NCERT
9.4.2 Solvate Hydrate Isomerism 9.13 Matrix Based Questions
9.4.3 Linkage Isomerism 9.14 ARCHIVE QUESTIONS
9.4.4 Coordination Isomerism 9.15 ANSWER KEY
Coordination Compounds 115
Stability
Colour COORDINATION COMPOUNDS Applications
VBT CFT
Features Tetrahedral Octahedral

Bonding in Field Field
metal
Geometry
carbonyls
Spectrochemical Series
Inner/Outer
Weak field Strong Field

High/Low spin
Magnetic Properties
ISOMERISM
Structural Stereo
Isomerism Isomerism
Ionisation
Linkage Geometrical (cis-trans) Optical (object - mirror image)
Hydrate
Square planar complexes Octahedral complexes Criteria
Co-ordination
Ma2b2 Ma4b2 Examples
Ma2bc Ma3b3
M(XY)2 M(XX)2b2
M(XX)2bc
Double salts MOLECULAR Complex salts

K2SO4.Al2(SO4)3.24H2O ADDITION K4[Fe(CN)6]
COMPOUNDS
Or
Co-ordination compounds
Complex ion Neutral
EAN rule Werner’s theory
Monodentate Central metal ion Neutral
Application Assumptions
Bidentate Co-ordination number Neutral
Examples
Tridentate Ligands
Nomenclature Explanations
Polydentate Chelating agents
Ambidentate Co-ordination sphere Cationic Anionic Neutral
complexes complexes complexes
Chelating Ionisation sphere
 The concept of co-ordination compounds arises from the complex formation tendency of transition elements.
 These compounds play a vital role in our lives, as chlorophyll of plants, vitamin B12 and haemoglobin of animal
blood are the co-ordination compounds of Mg, Co and Fe respectively.
 The co-ordination compounds play important role in analytical chemistry, polymerisation reactions, metallurgy
and refining of metals, photography, water purification etc.
 Co-ordination compounds also find many applications in electroplating, textile dyeing and medicinal chemistry.
ADDITION COMPOUNDS :
 They are formed by the combination of two or more stable compounds in stoichiometric ratio.
Addition Compounds
Double salts Coordination compounds

(Complexes)
 Double salts : Those addition compounds which lose their identity in solutions are called double salts. For
example, when K2SO4 solution is added to Al2 (SO4)3 solution, the species formed when dissolved in water gives
tests of K+, Al3+ and SO42– ions.
K2SO4 + Al2(SO4)3 + 24H2O  K2SO4.Al2(SO4)3.24H2O (aq.)  2K+ (aq.) + 2Al+3 (aq.) + 4SO42– (aq.)
Other examples are carnallite (KCl. MgCl2 . 6H2O), Mohr’s salt [FeSO4 . (NH4)2SO4 . 6H2O], potash alum
[KAl(SO4)2.12H2O] etc.
 COORDINATION COMPOUNDS : Those addition compounds which retain their identity (i.e. doesn’t lose
their identity) in solution are called coordination compounds. For example, when KCN solution is added to
Fe(CN)2 solution, the species formed when dissolved in water no longer gives tests of Fe2+ and CN–.
Fe(CN)2 + 4KCN  Fe(CN)2 . 4KCN or K4 [Fe(CN)6] (aq.)   4K+ (aq.) + [Fe(CN)6]4– (aq.)
Other examples are,  [Cu(NH3)4]2+ (aq.) + SO42– (aq.)
[Cu(NH3)4]SO4 (aq.) 
 2K+ (aq.) + [Zn(CN)4]2– (aq.)
K2[Zn(CN)4] (aq.) 
1. Coordination compounds are also acid-base adducts and are frequently called complexes or, if charged then
complex ions.
2. Coordination compound is defined as a species in which metal atom or ion is attached to group of neutral
molecules / ions by coordinate covalent bonds.
9.1 WERNER’S THEORY OF COORDINATION COMPOUNDS P.No.: 244
 Several theories were proposed but none of them could satisfactorily explain the observed properties of
Co(III) ammines and of other similar compounds like Pt(IV) ammines which had been prepared by them. It
was only in 1893, that Werner presented a theory known as Werner's coordination theory which could
explain all the observed properties of complex compounds. According to him most elements exhibit two
types of valencies : (a) Primary valency and (b) Secondary valency.
 Primary valency :
1. This corresponds to the oxidation state of the metal ion.
2. This is also called as the principle, ionisable or ionic valency.
3. It is satisfied by the negative ions and its attachment with the central metal ion is shown by dotted
lines.
 Secondary or auxiliary valency :
1. It is also termed as the coordination number (usually abbreviated as CN) of the central metal ion.
It is non-ionic or non-ionisable (i.e. coordinate covalent bond type).
2. This is satisfied by either negative ions or neutral molecules having lone pair of electrons (e.g.,
H2O, NH3 etc.) or even sometimes by some positive groups.
3. The ligands which satisfy the coordination number are directly attached to the metal atom or ion
and shown by thick lines.
4. Every element tends to satisfy both its primary and secondary valencies. In order to meet this
requirement a negative ion may often show a dual behaviour, i.e. it may satisfy both primary and
secondary valencies since in every case the fulfillment of coordination number of the central
metal ion appears essential. This dual behaviour is represented by both thick and dotted lines. For
example, [CoCl(H2O)5]Cl2 is represented as
H2O
H2O H2O
Cl Co Cl
Cl H2O
H2O
5. Every metal has a fixed number of secondary valencies, e.g., cobalt(III) and platinum(IV) have
six secondary valencies and copper(II) four.
6. The coordination number of a metal in a particular oxidation state is generally fixed but certain
oxidation states of certain metals have found to possess more than one coordination number.
7. The ions/groups bound by the secondary valencies have characteristic spatial arrangements corre-
sponding to different coordination number. In the modern terminology, such spatial arrangements
are called coordination polyhedra and various possibilities are
C.N. = 2 linear C.N. = 3 Triangular
C.N. = 4 tetrahedral or square planar C.N. = 6 octahedral.
8. To distinguish between the two types of valencies, Werner introduced the square brackets [ ] to
enclose those atoms making up the coordination complex and which are, therefore, not ionized.
9. On the basis of the above postulates Werner formulated the coordination compounds, CoCl3 .
6NH3, CoCl3 . 5NH3 and CoCl3 . 4NH3 as : [Co(NH3)6]Cl3, [Co(NH3)5Cl]Cl2 and [Co(NH3)4Cl2]Cl
respectively; the species within the square brackets being the coordination entities (complexes)
and the ions outside the square brackets the counter ions. He further postulated that octahedral,
square, planar and tetrahedral geometrical shapes are more common in coordination compounds
of transition metals. Thus, [Co(NH3)6]3+, [CoCl(NH3)5]2+, [CoCl2(NH3)4]+ are octahedral entities,
while [Ni(CO)4] and [PtCl4]2– are tetrahedral and square-planar respectively.
Secondary valency
S.No. Werner complex Modern notation Ionisation Primary valency satisfied by
satisfied by
1 CoCl3.6NH3 [Co(NH3)6]Cl3 [Co(NH3)6]3++3Cl– six (NH3) three (Cl–)
three (Cl–) including one (Cl–)
2 CoCl3.5NH3 [Co(NH3)5Cl]Cl2 [Co(NH3)5Cl]2++2Cl– five (NH3) and one (Cl–)
with dual nature
three (Cl–) including
3 CoCl3.4NH3 [Co(NH3)4Cl2]Cl [Co(NH3)4Cl2]++ Cl– four (NH3) and two (Cl–)
two (Cl–) with dual nature
4 CoCl3.3NH3 [Co(NH3)3Cl3] [Co(NH3)3Cl3] three (NH3) and three (Cl–) three (Cl–) all with dual nature
10. From the above table it is clear that (i) the solution conductivities of complexes 1, 2 and 3
correspond to 1 : 3, 1 : 2 and 1 : 1 electrolyte respectively and thus the increasing order of the
conductivity can be represented as CoCl3.3NH3 < CoCl3. 4NH3 < CoCl3.5NH3 < CoCl3.6NH3 and
(ii) the complexes 1, 2 and 3 will react with silver nitrate and give 3, 2 and 1 mole of the white
precipitate of silver chloride respectively.

Consider the following complexes :
(i) K2PtCl6 (ii) PtCl4 . 2NH3 (iii) PtCl4 . 3NH3 (iv) PtCl4 . 5NH3
their electrical conductance in aqueous solutions are :
(A) 256, 0, 97, 404 (B) 404, 0, 97, 256 (C) 256, 97, 0, 404 (D) 404, 97, 256, 0
(A)
The electrical conductance of the complexes depend upon the number of ions given by them in the aqueous
solutions.

(i) K2[PtCl6]  aq
 + 2–
 2K (aq) + [PtCl6] (aq)

(ii) [Pt(NH3)2Cl4] aq

 [Pt(NH3)2Cl4] (aq)

(iii) [Pt(NH3)3Cl3]Cl aq
 + –
 [Pt(NH3)3Cl3] (aq) + Cl (aq)

(iv) [Pt(NH3)5Cl]Cl3  aq
 3+
 [Pt(NH3)5Cl] + 3Cl
–
Complex Number of ions Expected electrical conductance

(i) K2[PtCl6] 3 256
(ii) [Pt(NH3)2Cl4] 0 0
(iii) [Pt(NH3)3Cl3]Cl 2 97
(iv) [Pt(NH3)5Cl]Cl3 4 404
So, the correct option is (A).
01 (3) 1 (4) 5
7. An excess of AgNO3 is added to 100 mL of a 0.01 M
1. Which of the following has the highest molar conductivity solution of dichlorotetraaquachromium (III) chloride. The
in solution? number of moles of AgCl precipitated would be:
(1) [Pt(NH3)6]Cl4 (2) [Pt(NH3)5Cl]Cl3 (1) 0.002 (2) 0.001
(3) [Pt(NH3)4Cl2]Cl2 (4) [Pt(NH3)3Cl3]Cl (3) 0.003 (4) 0.01
2. An imperfect complex of a complex compound is 100% 8. One mole of complex compound Co(NH3)5Cl 3 gives 3
ionized; the compound is called: moles of ions on dissolution in water. One mole of same
(1) acid salt (2) complex salt complex reacts with two moles of AgNO3 to yield two
moles of AgCl(s). The complex is:
(3) double salt (4) normal salt
(1) [Co(NH3)4Cl2]Cl.NH3
3. Some salts although containing two different metallic
elements give test for one of them in solution. Such salts (2) [Co(NH3)4Cl]Cl2.NH3
are: (3) [Co(NH3)5Cl]Cl2
(1) double salts (2) complex salts (4) [Co(NH3)3Cl3].2NH3
(3) normal salts (4) none of these 9. Formation of complex compound can be detected by
4. Which of the following will exhibit maximum ionic (1) Change in colour
conductivity? (2) Change in solubility
(1) [Co(NH3)6]Cl3 (2) [Cu(NH3)4]Cl2 (3) Change in pH
(3) [Ni(CO)4] (4) K4[Fe(CN)6] (4) Change in electrical conductivity
5. Aqueous solution of which of the following complexes 10. Which of the following is the most likely structure of
would exhibit the highest molar conductance? CrCl3.6H2O, if 1/3 of total chlorine of the compound is
(1) K4[Fe(CN)6] (2) K2[PtCl4] precipitated by adding AgNO3 to its aqueous solution:
(3) [Cr(NH3)3Cl3] (4) [Co(NH3)6]Cl3 (1) CrCl3·6H2O
6. Number of ions produced when [Cu(NH 3 ) 4 ]Cl 2 is (2) [Cr(H2O)3Cl3](H2O)3
dissolved in water is/are (3) [CrCl2(H2O)4]Cl2H2O
(1) 3 (2) 2 (4) [CrCl.(H2O)5]Cl2H2O
sdfs
9.2 P.No.: 247
 Effective Atomic Number Rule given by Sidgwick :

 Effective Atomic Number (EAN) = No. of electron present on the metal atom/ion + No. of electrons
donated by ligands to it.
OR
 Effective Atomic Number (EAN) = Atomic no. of central metal – Oxidation state of central metal +
No. of electrons donated by ligands.
 The complexes in which the EAN of the central atom equals the atomic number of the next noble gas,
are found to be extra stable.
Note : The EAN rule is generally found to be not valid in case of most of the complexes but in case of metal
carbonyls this rule is found to be valid in all cases except one or two exceptions.

Calculate the effective atomic number of the metal atoms in the following complexes / complex ions.
(a) [Cr(CO)6] (b) [Fe(CN)6]3– (c) [Co(CN)6]4– (d) [Ni(NH3)6]2+
[Cr = 24 ; Fe = 26; Co = 27 and Ni = 28 as atomic numbers]
(a) 36 (b) 35 (c) 37 (d) 38

EAN = Number of electrons in metal atom or ion + Number of electrons donated by ligands to metal.
(a) [Cr0(CO)6] ; EAN = 24 + 12 = 36 ; (b) [FeIII(CN)6]3– ; EAN = 23 + 12 = 35
(c) [CoII(CN)6]4–; EAN = 25 + 12 = 37 ; (d) [NiII(NH3)6]2+; EAN = 26 + 12 = 38
COORDINATION ENTITY / COORDINATION SPHERE P.No.: 247

 A coordination entity constitutes a central atom/ion, usually of a metal, to which are attached a fixed
number of other atoms or groups each of which is called a ligand. Ligand may be neutral or charged.
Examples being: [Co(NH3)6]3+, [PtCl4]2–, [Fe(CN)6]3–, [NiCl2(OH2)4].
 The central atom / ion and the ligands attached to it are enclosed in square bracket and is collectively called
as coordination sphere.
Note : The remaining ions apart from complex ions i.e. outside the coordination sphere are called counter
ions, free ions or ionisable ions. For example, in K4[Fe(CN)6], the potassium is counter ion of coordina-
tion entity [Fe(CN)6]4–.
CENTRAL ATOM / ION P.No.: 247

 In a coordination entity–the atom / ion around which a fixed number of ligands are bound in a definite
geometrical arrangement, is called the central atom or ion. For example, the central atom / ion in the
coordination entities : [NiCl2(OH2)4], [CoCl(NH3)5]2+ and [Fe(CN)6]3– are Ni2+, Co3+ and Fe3+, respectively.
 These central atoms / ions are also referred to as Lewis acids since they accept lone pairs from the ligands.
LIGANDS P.No.: 247

 The neutral molecules, anions or cations which are directly linked with central metal atom or ion in the
coordination entity are called ligands.
 These may be simple ions such as Br–, small molecules such as H2O or NH3, larger molecules such as
H2NCH2CH2NH2 or N(CH2CH2NH2)3 or even macromolecules such as proteins.
 When a ligand is attached to a metal ion through a single donor atom, as with Cl–, H2O or NH3, the ligand is
said to be unidentate. Similarly when a ligand is bound through two donor atoms (in a single ligand), as in
H2NCH2CH2NH2 (ethane-1, 2-diamine) or C2O42– (oxalate), the ligand is said to be bidentate and when
several donor atoms are present in a single ligand as in N (CH2CH2NH2)3 or ethylenediaminetetraacetic acid
(EDTA), the ligand is said to be polydentate.
CHELATE LIGAND P.No.: 247

 Chelate ligand is a di or polydentate ligand which uses its two or more donor atoms to bind a single metal
ion producing a ring. The complex formed is referred to as a chelate complex and the process of chelate
formation is called chelation. The number of such ligating groups is called the denticity of the ligand.
Chelate rings may have any number of atoms; the most common contain five or six atoms, including the
metal ion. Smaller rings have smaller angles and distances that lead to strain; larger rings frequently result
in crowding both within the ring and between adjoining ligands. Some ligands can form more than one ring;
ethylene diaminetetracetate (EDTA) can form five by using the four carboxylate groups and the two amine
nitrogens as given in the structures.
–
O H—O H 2
H3C — C == N N == C — CH3 Cl N
2+
Ni CH 2
Pt
H3C — C == N N == C — CH3 N CH
Cl 2
– H2
O—H O
 The chelate complexes are more stable than similar complexes containing unidentate ligands. The greater
stability of the chelate complex in comparison to normal complex is called chelate effect. For example,
 [Ni(NH3)6]2+ (aq)
Ni2+ (aq) + 6 NH3 (aq)  Kformation = 108
Ni2+ (aq) + 3 NH2CH2CH2NH2(aq)   [Ni(en)3]2+ (aq) Kformation = 1018
The five and six membered rings are more stable.
DENTICITY AND CHELATION P.No.: 247
 Common Monodentate Ligands
Common Name IUPAC Name Formula

methyl isocyanide methylisocyanide CH3NC
triphenyl phosphine triphenyl phosphine/triphenyl phosphane PPh 3
pyridine pyridine C5H5N (py)
ammonia ammine NH3
methyl amine methylamine MeNH 2
water aqua or aquo H2 O
carbonyl carbonyl CO
thiocarbonyl thiocarbonyl CS
nitrosyl nitrosyl NO
fluoro fluoro or fluorido* F–
chloro chloro or chlorido* Cl–
bromo bromo or bromido* Br–
iodo iodo or iodido* I–
cyano cyanido or cyanido-C* (C-bonded) CN–
isocyano isocyanido or cyanido-N* (N-bonded) NC–
thiocyano thiocyanato-S(S-bonded) SCN–
isothiocyano thiocyanato-N(N-bonded) NCS–
cyanato (cyanate) cyanato-O (O-bonded) OCN–
isocyanato (isocyanate) cyanato-N (N-bonded) NCO–
NCO
hydroxo hydroxo or hydroxido* OH–
nitro nitrito–N (N–bonded) NO2–
nitrito nitrito–O (O–bonded) ONO–
nitrate nitrato NO3–
amido amido NH2–
imido imido NH2–
nitride nitrido N3–
azido azido N3 –
hydride hydrido H–
oxide oxido O2–
peroxide peroxido O22–
superoxide superoxido O2 –
acetate acetato CH3COO –
sulphate sulphato SO42–
thiosulphate thiosulphato S2O 32–
sulphite sulphito SO32–
hydrogen sulphite hydrogensulphito HSO3–
sulphide sulphido or thio S2–
hydrogen sulphide hydrogensulphido or mercapto HS–
thionitrito thionitrito (NOS)–
nitrosylium nitrosylium or nitrosonium NO+
nitronium nitronium NO2+
* The 2004 IUPAC draft recommends that anionic ligands will end with-ido.
 Common Chelating Amines

Chelating
Common Name IUPAC Name Abbreviation Formula
Points
1,2-ethanediamine/
bidentate ethylenediamine en NH2,CH2CH2NH2
ethane-1,2-diamine
NH2–CH–CH2–NH2
bidentate propanediamine 1,2-propanediamine pn
CH3
[N-(2-aminoethyl)-1
tridentate diethylenetriamine 2-ethanediamine or dien NH2CH2CH2NHCH2CH2NH2
diethylenetriamine
triethylenetetraamine trien NH 2CH 2CH 2NHCH 2CH 2
tetradenate NHCH2CH2NH2
tren NH2CH2CH2NCH2CH2NH2
triaminotriethylamine
CH2CH2NH 2
1,4,7,10 pentaazatridecane NH 2CH 2CH 2NHCH 2CH 2
pentadentate tetraethylenepentaamine
or tetraethylenepentaamine NHCH2CH2NHCH 2CH2NH2
– –
1,2–ethanediyl (dinitrilo) OOCH2C CH2COO
hexadentate ethylenediaminetetraacetate tetraacetate or EDTA NCH2CH2N
ethylenediaminetetraacetate –
OOCH2C CH2COO–
FLEXIDENTATE LIGAND P.No.: 247
 It is not necessary that all the donor items present in the polydentate ligands should form coordinate bonds
with the central metal atom or ion i.e. a polydentate ligand which is found to have different denticity in
different coordination compounds is called a flexidentate ligand. Note that in a particular complex denticity
of a particular ligand is fixed, it can not be flexible in the same compound.
 EDTA can act as hexa, penta as well as tetra dentate ligand. For example ; EDTA usually acts as hexadentate
ligand but in [Cr(III)(OH)(EDTA)]2– and [Co(III)Br(EDTA)]2– as pentadentate and in [Pd(II)H2(EDTA)]0 as
a tetradentate ligand.
 Sulphate ion, SO42– can also be mono or bi dentate ligand. For example ; O
+
+
NH 3 S
en
O O O O
NH3
Co3+ S Co
3+
O
O O NH3 NH3
en
NH3
AMBIDENTATE LIGAND P.No.: 247
 Ligands which can ligate through two different atoms present in it are called ambidentate ligands.
Examples of such ligands are the CN–, NO2– and SCN¯ ions. NO2– ion can coordinate through either the
nitrogen or the oxygen atoms to a central metal atom/ion. Similarly, SCN¯ ion can coordinate through the
sulphur or nitrogen atom.
 Such possibilities give rise to linkage isomerism in coordination compounds. For example ;
O
M N nitrito-N
O
MO—N=O nitrito-O
M  SCN thiocyanato or thiocyanato-S
M  NCS isothiocyanato or thiocyanato-N
Note : Although ambidentate ligands have two or more donor atoms but during complex formation only one
donor atom can be used by them.
COORDINATION NUMBER P.No.: 247
 The coordination number of the central atom/ion is de- Some common co-ordination number of
termined by the number of sigma bonds between the important metals are as given below
ligands and the central atom/ion i.e. the number of Metal Coordination Metal Coordination
ligand donor atoms to which the metal is directly Number Number
attached. Pi-bonds, if any, between the ligating atom Cu +
2, 4 Ni 2+
4, 6
and the central atom/ion are not considered for the de- Ag +
2 Fe 2+
4, 6
termination of coordination number. The sigma Au + 2, 4 Fe 3+ 6
bonding electrons may be indicated by a pair of dots,
Hg 22+ 2 Co 2+ 4, 6
preceding the donor atom in the ligand formula as in :
Cu 2+ 4, 6 Co 3+ 6
[Co (: NH3)6]3+, [Fe (: CN)6]3–, [Ni (: CO)4], [Co (: Cl4)]2–. Ag 2+
4 Al 3+ 6
 Coordination number of 6 (most common), 4 (after 6) Pt 2+
4 Sc 3+
6
and 2 ( after 4) are the most common coordination num- Pd 2+ 4 Pt 4+ 6
bers and odd coordination numbers are generally not Mg 2+
6 Pd 4+
6
found (rare).
COORDINATION POLYHEDRON P.No.: 248

 The spatial arrangement of the ligand atoms which are directly attached to the central atom/ion gives a
coordination polyhedron about the central atom. Figure below shows the shapes of tetrahedral, square
planar, octahedral, square pyramidal and trigonal bipyramidal coordination polyhedra. [Co(NH3)6]3+ has an
octahedral geometry, while [PtCl4]2– and Ni(CO)4, are square planar and tetrahedral, respectively.
L
L L L
L L L
L L
L L
M M L
M M
L L L L M L
L L L
L Square planar L L L
Tetrahedral Octahedral Square pyramidal Trigonal bipyramidal
entity
entity entity entity entity
OXIDATION NUMBER OF CENTRAL ATOM P.No.: 248

 The oxidation number of the central atom is defined as the charge it would carry if all the ligands are
removed along with the electron pairs that are shared with the central atom.
 Metal oxidation number is represented by a Roman numeral in parentheses following the name of the
coordination entity. For example oxidation number of iron in [Fe(CN)6]3– is +3 and it is written as Fe(III).
HOMOLEPTIC AND HETEROLEPTIC COMPLEXES P.No.: 248

 Complexes in which a metal is bound to only one type of donor groups, e.g., [Cr(NH3)6]3+, are known as
homoleptic. Complexes in which a metal is bound to more than one type of donor groups, e.g., [Co(NH3)4Br2]+,
are known as heteroleptic.
02 17.
(3) 36 (4) 32
In the complex [Pt(py)4][PtCl4], the oxidation numbers
11. The oxidation number of Co in the complex ion of Pt atom in former and latter part of the compound
[CoCl(NH3)5]+2 is: are respectively
(1) +2 (2) +3 (1) 0 and 0 (2) +4 and +2
(3) +4 (4) +6 (3) +2 and +2 (4) 0 and +4
12. Which is a pair of ambidentate ligands among the 18. Which of the following is correct value of x in Cr(CO)x?
following? (1) 2 (2) 4
(1) CN–, NO2– (2) NO3–, NO2– (3) 6 (4) unpredictable
(3) CNS–, C2O4–2 (4) C2O4–2, SO4–2 19. The EAN of platinum in potassium hexachloroplatinate
13. What is the coordination number of Cr in K3[Cr(Ox)3] (IV) is:
(1) 6 (2) 4 (1) 86 (2) 46
(3) 3 (4) 2 (3) 36 (4) 84
14. The EAN of nickel in Ni(CO)4 is: 20. Which one is bidentate ligand?
(1) 38 (2) 36 (1) C2O4– (2) NH2.CH2.CH2.NH2
(3) 28 (4) 54 (3) None of these (4) Both (1) and (2)
15. NH2 . NH2 serves as: 21. The value of x on the [Ni(CN)4] x is:
(1) monodentate ligand (2) Both (1) and (3) (1) +2 (2) 0
(3) bridging ligand (4) chelating ligand (3) –2 (4) +4
16. What is the EAN of central metal in [Ni(gly)2] (At. No. 22. Coordination number of Ni in [Ni(C2O4)3] 4– is:
of Ni = 28) (1) 3 (2) 4
(1) 30 (2) 34 (3) 5 (4) 6
23. The oxidation state of oxygen in O2[PtF6] is (3) c, a (4) a, b

(1) zero (2) – 1/2 25. The complex that violates the EAN:
(3) +1 (4) + 1/2 (1) potassium ferrocyanide
24. Among the properties (a) reducing (b) oxidizing (c) (2) nickel carbonyl
complexing, the set of properties shown by CN– towards (3) potassium ferricyanide
metal species is: (4) cobalt (III) hexaammine chloride
(1) a, b, c (2) b, c
9.3 NOMENCLATURE OF COORDINATION COMPOUNDS P.No.: 248
9.3.1
 The following rules are followed while writing the formulas :

1. The central atom is placed first.
2. The ligands are then placed in alphabetical order. The placement of a ligand in the list does not depend
on its charge.
3. Polydentate ligands are also placed alphabetically. In case of abbreviated ligand, the first letter of the
abbreviation is used to determine the position of the ligand in the alphabetical order.
4. The formula for the entire coordination entity, whether charged or not, is enclosed in square brackets.
When ligands are polyatomic, their formulae is enclosed in parentheses. The abbreviations of the
ligands are also enclosed in parentheses.
5. There should be no space between the ligands and the metal within a coordination sphere.
6. When the formula of a charged coordination entity is to be written without that of the counter ion, the
charge is indicated outside the square brackets as a right superscript with the number before the sign.
For example, [Co(H2O)6]3+, [Fe(CN)6]3– etc.
7. The charge of the cation(s) is balanced by the charge of the anion(s).
9.3.2
 The following rules are followed when naming coordination compounds :

 Like simple salts the cation is named first in both positively and negatively charged coordination entities.
Examples : [Ag(NH3)2]Cl, diamminesilver(I) chloride. K3[Fe(CN)6], potassium hexacyanidoferrate (III).
 The ligands are named in an alphabetical order (according to the name of ligand, not the prefix) before
the name of the central atom / ion. Examples :
1. [Pt(NH3)BrCl(CH3NH2)], amminebromidochloridomethylamineplatinum(II).
2. [Co(H2O)2(ox)2]–, diaquabis(oxalato)cobaltate(III).
 Names of the anionic ligands end in – o and those of neutral ligands are the same except aqua for H2O,
ammine for NH3, carbonyl for CO, thiocarbonyl for CS and nitrosyl for NO. But names of cationic
ligands end in–ium.
Some more important examples of neutral and cationic ligands are :
tetraphosphorus — P4
dioxygen — O2
octasulphur — S8
urea — CO(NH2)2
hydrazinium — N2H5 +
 Prefixes mono, di, tri, etc., are used to indicate the number of the one 2 di bis
kind of ligands in the coordination entity. When the names of the ligands 3 tri tris
include a numerical prefix or are complicated or whenever the use of 4 tetra tetrakis
normal prefixes creates some confusion, it is set off in parentheses and
5 penta pentakis
the second set of prefixes is used.
6 hexa hexakis
7 hepta heptakis
Examples ;
1. [CoCl2(NH2CH2CH2NH2)2]+, dichloridobis(ethane-1,2-diamine)cobalt(III).
2. [NiCl2(PPh3)2], dichloridobis(triphenylphosphine)nickel(II).
 Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by Roman
numeral in the parentheses after the name of metal.
 If the complex ion is a cation, the metal is named same as the element. For example, Co in a complex
cation is called cobalt and Pt is called platinum. If the complex ion is an anion, the name of the metal
ends with the suffix - ate. For example, Co in a complex anion, [Co(SCN)4]2– is called cobaltate. For
some metals, the Latin names are used in the complex anions.
iron (Fe) ferrate lead (Pb) plumbate
silver (Ag) argentate tin (Sn) stannate
gold (Au) aurate
Examples ;
1. [Co(NH3)4Cl2]+, pentaamminechloridocobalt(III).
2. (NH4)2 [Co(SCN)4], ammonium tetrathiocyanato-S-cobaltate(II).
 The neutral complex molecule is named similar to that of the complex cation.
Example ; [CrCl3(py)3], trichloridotris(pyridine)chromium(III).
 The prefixes cis- and trans- designate adjacent and opposite geometric locations. For examples,
[Pt(NH3)2Cl2], cis- and trans-diamminedichloridoplatinum(II),
[CoCl2(NH3)4]+, cis- and trans-tetraamminedichloridocobalt(III).
cis– trans–
9.3.3
 Ist case : The name of a bridge complex is prefixed by µ–.
If the situation on both sides of the bridge is symmetrical then we can write the name of remaining complex
at one place like
5
(NH3 )5 Cr — OH — Cr(NH3 )5  Cl5
µ–hydroxidobis(pentaamminechromium(III)) chloride
OR we could also have written the name of one side of the bridge ligand and then the name of bridge ligand
and then the other side of the bridge, like
5
(NH3 )5 Cr — OH — Cr(NH3 )5  Cl5
pentaamminechromium(III)–µ–hydroxidopentaamminechromium(III) chloride
 IInd case : If the compound is unsymmetrical on both sides of the bridge then we have to follow the second
rule, i.e. write the name of one side then that of the bridge and then that of the second side, like
OH–
(H2O)4 Co Cr (NH3)4 (SO4)2
NH2
tetraaquacobalt(III)–µ–amido–µ–hydroxidotetramminechromium(III) sulphate

Write the structural formula corresponding to each of the following IUPAC names :
(a) potassium tetracyanidozincate (II) (b) tetracarbonyl nickel (0)
(c) potassium tetracyanonickelate (0) (d) potassium tris(oxalato)aluminate (III)
(a) K2[ZnII(CN)4] (b) [Ni0(CO)4] (c) K4[Ni0(CN)4] (d) K3[AlIII(C2O4)3]

Refer IUPAC rule.

Write IUPAC names of the following :
(a) [Cr(acac)3] (b) [V(H2O)6]Cl3 (c) (NH4)3[Co(C2O4)3](d) K2 [CrO4]
(a) tris (acetylacetonato) chromium(III)

(b) hexaaquavanadium (III) chloride
(c) ammonium tris(oxalato)cobaltate(III) or ammonium trioxalatocobaltate(III)
(d) potassium tetraoxidochromate(VI)
Refer IUPAC nomenclature rule.
03 (3) NaFe[Fe(CN)6] (4) Na2[Fe(CN)6 NO2]

32. The IUPAC name of [Co(NH3)3 (NO2)3] is
26. The IUPAC name of the coordination compound
K3[Fe(CN)6] is : (1) triamminetrinitro-N-cobalt (III)
(1) potassium hexacyanidoferrate (II) (2) trinitrotriammine cobalt (II)
(2) potassium hexacyanidoferrate (III) (3) trinitrotriammine cobalt (III) ion
(3) potassium hexacyanoiron (II) (4) trinitrotriammine cobaltate (III)
(4) tripotassium hexacyanidoiron (II) 33. The IUPAC name of K4[Fe(CN)6] 3 is
27. The IUPAC name for the complex [Co(NO2)(NH3)5]Cl2 (1) potassium hexacyanidoferrate (II)
is
(2) potassium ferrocyanide
(1) nitro-N-pentaamminecobalt (III) chloride
(3) tetrapotassium hexacyanidoferrate (II)
(2) nitro-N-pentaamminecobalt (II) chloride
(3) pentaammine nitro-N-cobalt (II) chloride (4) tetrapotassium ferroushexacyanide (II)
(4) pentaammine nitro-N-cobalt (III) chloride 34. The correct nomenclature for Fe4[Fe(CN)6] 3 is
28. Which among the following will be named as dibromido- (1) ferroso-ferric cyanide
bis-(ethylenediamine) chromium (III) bromide? (2) ferric–ferrous hexacyanate
(1) [Cr(en)3]Br3 (2) [Cr(en)2Br2]Br (3) iron (III) hexacyanidoferrate (II)
(3) [Cr(en)Br4]– (4) [Cr(en)Br2]Br
(4) hexacynoferrate (III–II)
29. The formula of the complex tris (ethylenediamine)
35. The IUPAC name of compound Na3[Co(ONO6] will be
cobalt (III) sulphate is
(1) [Co(en) 2SO4] (2) [Co(en) 3SO4] (1) hexanitritocobalt (III) sodium
(3) [Co(en)3] 2SO 4 (4) [Co(en)3] 2 (SO4)3 (2) sodium cobalt nitrite
30. The IUPAC name of the complex [Pt(NH3)2Cl2] is (3) sodium hexanitrocobaltate (III)
(1) platinum (II) diammino dichloride (4) sodium hexanitrito-o-cobaltate (III)
(2) diammine dichlorido platinum (II) 36. IUPAC name of [Co(ONO)(NH3)5Cl2] is
(3) bis (ammino) dichloro platinum (IV) (1) pentaammine nitro cobalt (III) chloride
(4) dichloro diammine platinum (II) (2) pentaammine nitrito-o-cobalt (III) chloride
31. The formula of sodium nitroprusside is (3) pentaammine nitroso cobalt (III) chloride
(1) Na4[Fe(CN)5NOS] (2) Na2[Fe(CN)5 NO] (4) pentaammine oxo-nitro cobalt (III) chloride
37. According to IUPAC nomenclat ure sodium 39. IUPAC name of K3[Al(C2O4)3] is called
nitroprusside is named as (1) potassium alumino oxalato
(1) sodium pentacyanonitrosyl ferrate (III) (2) potassium aluminium (III) trioxalate
(2) sodium nitroferricyanide (3) potassium trioxalato aluminate (III)
(3) sodium nitroferrocyanide (4) potassium trioxalato aluminate (IV)
(4) sodium pentacyanonitrosyl ferrate (II) 40. The IUPAC name of K3[Ir(C2O4)3] is
38. The proper name for K2[PtCl6] is (1) potassium trioxalato iridium (III)
(1) potassium platinum hexachloride (2) potassium trioxalato iridate (III)
(2) potassium hexachlorido platinum IV (3) potassium tris (oxalato) iridium (III)
(3) potassium hexachlorido platinate IV (4) potassium tris (oxalato) iridate (III)
(4) potassium hexachlorido platinum
9.4 ISOMERISM IN CO ORDINATION COMPOUNDS P.No.: 251
STRUCTURAL ISOMERISM
9.4.1 IONISATION ISOMERISM P.No.: 253
 This type of isomerism occurs when the counter ion in a coordination compound is itself a potential ligand
and can displace a ligand which can then become the counter ion. For example, following complexes show
ionisation isomerism.
[Co(NH3)5SO4]NO3 and [Co(NH3)5NO3]SO4
[Co(NH3)4(NO2)Cl]Cl and [Co(NH3)4Cl2]NO2.
[Co(NH3)4(H2O)Cl]Br2 and [Co(NH3)4BrCl]Br.H2O. [Also an example of hydrate isomers.]
[Pt(NH3)4Cl2]Br2 and [Pt(NH3)4Br2]Cl2.
[CoCl(en)2(NO2)]SCN, [Co(en)2(NO2)SCN]Cl and [Co(en)2(SCN)Cl]NO2
9.4.2 SOLVATE / HYDRATE ISOMERISM P.No.: 254

 It occurs when water forms a part of the coordination entity or is outside it.
 This is similar to ionisation isomerism. Solvate isomers differ by whether or not a solvent molecule is
directly bonded to the metal ion or merely present as free solvent molecules in the crystal lattice. For
example, CrCl3 . 6H2O exists in three distinct isomeric forms : [Cr(H2O)6]Cl3, violet ; [CrCl(H2O)5]Cl2.H2O,
blue green : [CrCl2(H2O)4]Cl.2H2O, dark green. These three cationic isomers can be separated by cation ion
exchange from commercial CrCl3.6H2O. A fourth isomer [Cr(H2O)3Cl3], yellow green also occurs at high
concentration of HCl.
 Apart from their distinctive colours, the three isomers can be identified by the addition of excess of aqueous
silver nitrate to their aqueous solutions, which precipitates chloride in the molar ratio of 3 : 2 : 1 respectively.
Complex Reaction with AgNO3 Reaction with conc. H2SO4 (dehydrating agent)
[Cr(H2O)6]Cl3 in the molar ratio of 3 : 1 No water molecule is lost or no reaction
[CrCl(H2O)5]Cl2.H2O in the molar ratio of 2 : 1 one mole of water is lost per mole of complex
[CrCl2(H2O)4]Cl2.H2O in the molar ratio of 1 : 1 two mole of water are lost per mole of complex
Other examples are :
[Co(NH3)4(H2O)Cl]Cl2 and [Co(NH3)4Cl2]Cl.H2O
[Co(NH3)5(H2O)](NO3)3 and [Co(NH3)5(NO3)](NO3)2.H2O.
9.4.3 LINKAGE ISOMERISM P.No.: 253

 In some ligands, like ambidentate ligands, there are two possible coordination sites. In such cases, linkage
isomerism exist. e.g., NO2 group can be bonded to metal ions through nitrogen (– NO2) or through oxygen
(– ONO). SCN too can be bonded through sulphur (– SCN) thiocyanate or through nitrogen (– NCS)
isothiocyanate. For example : [Co(ONO)(NH3)5] Cl2 and [Co(NO2) (NH3)5] Cl2.
9.4.4 COORDINATION ISOMERISM P.No.: 253

 Coordination compounds made up of cationic and anionic coordination entities show this type of isomer-
ism due to the interchange of ligands between the cation and anion entities. Some of the examples are :
1. [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
2. [Cu(NH3)4][PtCl4] and [Pt(NH3)4][CuCl4]
3. [Co(NH3)6][Cr(SCN)6] and [Cr(NH3)4(SCN)2][Co(NH3)2(SCN)4]
4. [Pt(NH3)4][PtCl6] and [Pt(NH3)4Cl2][PtCl4]
Such isomers are expected to have significant differences in their physical and chemical properties.
STEREOISOMERISM P.No.: 251

 The isomers in which atoms are bonded to each other in the same order but that differ in the arrangement of
these atoms in the space are called as stereoisomers and the phenomenon as stereoisomerism.
9.4.5 GEOMETRICAL ISOMERISM
This type of isomerism arises in heteroleptic complexes due to different possible geometric arrangements
of theligands. Geometrical isomerism is common among coordination compounds with coordination
numbers 4 and 6.
 Coordination Number Four :
1. Tetrahedral Complex : The tetrahedral compounds can not show geometrical isomerism as we all
know that all four positions are equivalent in tetrahedral geometry.
2. Square Planar Complex : In a square planar complex of
Cl NH3 Cl NH3
formula [Ma2b2] [a and b are unidentate], the two ligands
‘a’ may be arranged adjacent to each other in a cis isomer, Pt Pt
or opposite to each other in a trans isomer as depicted. Cl NH3 NH3 Cl
cis– trans–
Geometrical isomers (cis and trans) of Pt(NH3)2Cl2.
Square planar complex of the type Ma 2bc (where a, b, c are unidentates) shows two geometrical
isomers.
a b a c
M M
a c b a
cis– trans–
Square planar complex of the type Mabcd (where a,b,c,d are unidentates) shows three geometrical
isomers.
a b a d a b
M M M
d c c b c d
aTc aTb aTd
Example is [Pt(NH3)BrCl(py)]. Three isomers of the complex [Pt(NH3)(NH2OH)(py)(NO2)]+ have been
isolated and identified.
Square planar complex of the type M(AB)2 (where A A A B
AB are unsymmetrical bidentates) shows two geo-
metrical isomers. Example is [Pt(gly)2] in which gly M M
is unsymmetrical ligand.
B B B A
Similarly, M(AB)(CD) also shows two geometrical cis– trans–
isomers.
Note : M(AA) 2, (where AA are symmetrical bidentates) does not show geometrical isomerism. e.g.,
[Cu(en)2]2+ [Pt(ox)2]2–, etc.
 COORDINATION NUMBER SIX : Geometrical isomerism is also possible in octahedral complexes.
+ +
Cl Cl
NH3 Cl NH 3 NH3
Co Co
NH3 NH3 NH3 NH3
NH3 Cl
cis– trans–
Geometrical isomers (cis and trans) of [Co(NH3)4Cl2]+
Number of possible isomers and the spatial arrangements of the ligands around the central metal ion for the
specific complexes are given below.
 Complexes containing only unidentate ligands Unsymmetrical bidentate ligands also show fac-
1. Ma2b4 – 2 (aa)(bb)(bb) mer isomerism.
(ab)(ab)(bb) 4. Ma3b2c – 3 (aa)(ab)(bc)
2. Ma4bc – 2 (aa)(aa)(bc) (aa)(bb)(ac)
(aa)(ab)(ac) (ab)(ab)(ac)
3. Ma3b3
5. Ma3bcd – 4 (aa)(ab)(cd)
Complexes of the formula Ma3b3, where a
(aa)(ac)(bd)
and b are monodentate ligands, may show
(aa)(ad)(bc)
two isomeric forms called fac– and mer–.
(ab)(ac)(ad)
Facial isomers have three identical ligands
on one triangular face where as meridional 6. Ma2b2c 2 – 5 (aa)(bb)(cc)
isomers have three identical ligands in a (aa)(bc)(bc)
plane bisecting the molecule. Similar isomers (bb)(ac)(ac)
are possible with some chelating ligands. (cc)(ab)(ab)
NH3 NH3 (ab)(ac)(bc)
O2N NH 3 H3 N NO2
Co Co 7. Ma2b2cd – 6
O2N NH 3 O2 N NO2
NO2 NH3 8. Ma2bcde– 9
fac– mer– 9. Mabcdef, [Pt(py)(NH3)(NO2)(Cl)(Br)(I)]– 15
The facial(fac) and meridional(mer) Note : Ma6 and Ma5b have only one form.
isomers of [Co(NH3)3(NO2)3].
 Compounds containing bidentate ligand and 2. M(AA)a2b2 – Three geometrical isomers are
unidentate ligands possible.
1. M(AA)a3b – Two geometrical isomers are a a b
possible. A b A a A a
b a
A a A a M M M
M M A b A b A a
A A a b b
a b aTa aTb bTb
a a Note : With [M(AA)b4], only one form is pos-
bTa aTa sible. M(AA)abcd have six geometrical isomers.
3. M(AA)2a2 – Two geometrical isomers are possible.
Cl Cl
Cl
en Co en Co en
Cl
en
Geometrical isomers (cis and trans) of [CoCl2(en)2]

Draw stereoisomer of the compound [PtCl2(NH3)(OH2)] ?
Ma2bc have cis- and trans isomers.
48. Out of the following which will not show geometrical

04 isomerism?
41. The total number of possible isomers of the complex (1) [Pt(NH3)2Cl2] (2) [Co(en)2Cl2]Cl
compound [Cu 11(NH3)4] [Pt11Cl4] is (3) [Co(NH3)3Cl3] (4) [Cr(NH3)4Cl2]Cl
(1) 3 (2) 6 49. [Co(NH3)4Cl2]Cl exhibits
(3) 5 (4) 4 (1) optical isomers
42. The number of isomers possible for square planar (2) ionisation isomerism
complex K2(PdClBr2SCN] is: (3) linkage isomerism
(1) 2 (2) 4 (4) geometrical isomerism
(3) 3 (4) 6 50. The type of isomerism present in nitro pentaammino
43. [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br are the examples chromium (III) chloride is:
of: (1) Optical (2) Linkage
(1) linkage isomerism (3) Ionisation (4) Polymerisation
(2) geometrical isomerism 51. The most stable ion is:
(3) optical isomerism (1) [Fe(C2O4)3] 2– (2) [Fe(Cl)6]3–
(4) ionization isomerism (3) [Fe(CN)6] 3–
(4) [Fe(H2O)6] 3+
44. Geometrical isomerism is found in coordination 52. Which one o f the following compl ex ions has
compounds having coordination number: geometrical isomers?
(1) 6 (2) 3 (1) [Co(en)3] 3+ (2) [Ni(NH3)5Br]+
(3) 4 (tetrahedral) (4) 2 (3) [Co(NH3)2(en)2] 3+ (4) [Cr(NH3)4(en)] 3+
45. The type of isomerism shown by [Co(en)2(NCS)2]Cl and 53. Which of the following pairs represents linkage
[Co(en)2(NCS)Cl]NCS is: isomers?
(1) ionization (1) [Cu(NH3)4] [PtCl4] and [Pt(NH3)4] [CuCl4]
(2) coordination (2) [Pd(PPh3)2 (NCS)2 and [Pd(PPh3)2(SCN)2]
(3) linkage (3) [Co(NH3)5] NO3SO4 and [Co(NH3)5SO4]NO3
(4) all of these (4) [PtCl2(NH3)4]Br and [PtBr2(NH3)4Cl2
46. Which one of the following square planar complexes 54. The number of geometrical isomers of [Co(NH3)3(NO3)3]
will form two geometrical isomers? are:
(1) M A 4 (2) MA 3 B (1) 0 (2) 2
(3) MAB 3 (4) MA 2B 2 (3) 3 (4) 4
47. The square planar complex (MABCD) can show 55. A square planar complex is represented as:
(1) two optical isomers (1) Geometrical isomers
(2) three geometrical isomers (2) Optical isomerism
(3) two geometrical isomers (3) Linkage isomerism
(4) three optical isomers (4) None
9.4.6 OPTICAL ISOMERISM

 A coordination compound which can rotate the plane of polarised light is said to be optically active.
 When the coordination compounds have same formula but differ in their ability to rotate directions of the
plane of polarised light are said to exhibit optical isomerism and the molecules are optical isomers.
 Optical isomers are mirror images that cannot be superimposed on one another.
 These are called as enantiomers. The molecules or ions that cannot be superimposed are called chiral. This
is due to the absence of elements of symmetry in the complex.
 The two forms are called dextro(d) and laevo(l) depending upon the direction they rotate the plane of
polarised light in a polarimeter (d rotates to the right, l to the left).
OCTAHEDRAL COMPLEX :
 Optical isomerism is common in octahedral complexes involving didentate ligands. For example, [Co(en)3]3+
has d and l forms as given below.
en en
3+ 3+
en Co Co en
en en
dextro mirror laevo
d and l of [Co(en)3]3+
 Cis-isomer of [PtCl2(en)2]2+ show optical isomerism as shown below because of the absence of plane of
symmetry as well as centre of symmetry.
2+ 2+
Cl Cl Cl
Cl
en Pt Pt en
en en
dextro mirror laevo
d and l of cis-[PtCl2(en)2]2+
 But trans isomer of [PtCl2(en)2]2+ does not show optical isomerism.
 cis-[Co(NH3)2Cl2(en)]+ can show optical isomerism due to the absence of plane of symmetry as well as
centre of symmetry.
+ +
Cl Cl Cl
Cl
en Co3+ Co3+ en
NH3 NH 3 NH3 NH
3
dextro mirror laevo

TETRAHEDRAL COMPLEX :
 Optical isomerism is expected in tetrahedral (i) For example [As(III)(CH )(C H )(S)(C H COO)]2+,
3 2 5 6 4
complexes of the type [Mabcd] analogous to tet- shows optical isomerism as given below.
rahedral carbon atom.
a a 2+ 2+
S S
M M As As
d b b d H3 C C 2H 5 H 5C2 CH3
–
c c C6H4COO– C 6H 4COO
Mirror plane Mirror plane
 Here it may be noted that 4 different groups round the central metal ion are not the only requirement to
make the complex to show mirror-image isomerism. All that is required is that the molecule should be
asymmetric (i.e., unsymmetrical), i.e., it should have no plane of symmetry so that it can exist in two
mirror-image forms.
05 Cl CH = CH Cl Cl
56. Which of the following is not optically active? (1) Pt (2) Pt

(1) [Co(en)3] 3+ (2) [Cr(ox)3]3– Cl Cl Cl Cl
+
(3) cis-[CoCl2(en)2] (4) trans-[CoCl 2(en) 2] + H3N Cl H3N Cl
57. Which of the following types of octahedral complexes
does not show optical isomerism? (3) Pt (4) Pt
(1) MA 2X 2Y 2 (2) [Pt(NH)3)4]2+ H3N Cl Cl NH3
n+
(3) [M(AA) 3] (4) [M(AA) 2X 2] n+ 62. [Co(en)3] 3+ ion is expected to show
58. Type of isomerism which is shown by [PtCl 2Br 2] 2– is (1) two optically active isomers: d and l forms
also observed in: (2) d, l and meso forms
(1) (CoCl2Br2] 2– (2) [Co(en)3] 3+ (3) four optically active isomers: cis, d and l isomers
(3) [PtCl4Br2] 2– (4) [PtCl3 (NO2)] 2– and trans d and l isomers
59. Which of the following statements is not true about (4) none of these
the complex ion [Pt(en)2Cl2] 2+? 63. In which case racemic mixture is obtained on mixing its
(1) It has two geometrical isomers: cis and trans. mirror images in 1:1 molar ratio?
(2) Both the cis and trans isomers display optical (1) Cr(en)3] 3+
activity.
(2) [Ni(DMG)2]
(3) Only the cis isomer displays optical activity.
(3) cis-[Cu(Gly)2]
(4) Only the cis isomer has non-superimposable
(4) All the three
mirror image
64. The complex that exists as a pair of enantiomers is
60. Tris (ethylenediamine) cobalt (III) cation, [Co(en)3] 3+,
can have (1) trans-[Co(H2NCH2 CH2 CNH2)2Cl2] +
(1) three stereoisomers, all chiral and optically active (2) [Co(H2 NCH2 CH2 NH2)3] 3+
(2) two chiral stereo isomers (enantiomers) and one (3) [Pt(PPh3) (Cl) (Br) (CH3)] –
achiral (4) cis–[CoNH3)4Cl2]+
(3) three stereoisomers, all achiral 65. Which one of the following has largest number of
(4) two stereoisomers, both achiral isomers?
61. Which of the following is considered to be an (1) [Co(en)2Cl2]+ (2) [Co(NH3)5Cl]2+
2+
anticancer species? (3) [Ir(PR3)2H(CO)] (4) [Ru(NH3)4Cl2]+
66. Which of the following complexes exhibit optical
isomerism? A
(1) Trans-tetraamminedithiocyanatochromium (III) F B
ion M
(2) Cis-diamminedicarbonatocobaltate (III) ion E C
(3) Trans-diamminedicarbonatocobaltate (I) ion D
(4) Cis-bis (glycinato) platinum (II)
(1) optical isomerism only
67. Which of the following will show optical isomerism?
(2) both optical and geometrical isomerism
(1) [Cu(NH3)4]2+ (2) [ZnCl4] 2–
3–
(3) geometrical isomerism only
(3) [Cr(C2O4)3] (4) [Co(CN)6]3–
(4) none of the above
68. Which of the following complex species is not expected
70. Which of the following has on optical isomer? (en =
to exhibit optical isomerism?
ethylenediamine)?
(1) Co(en)3Cl2]+ (2) [Co(en)2 Cl2]+
(1) [Zn(en)(NH3)2] 2+ (2) [Co(en)3] 3+
(3) [Co(NH3)3Cl3] (4) [Co(en)(NH3)Cl2]+ 3+
(3) [Co(H2O) 4(en)] (4) [Zn(en) 2] 2+
69. The complex shown below can exhibit
9.5 BONDING IN COORDINATION COMPOUNDS P.No.: 254
 Alfred-Werner described the bonding characteristic in coordination compounds. But this theory failed to
explain certain basic questions like :
1. Why only certain elements possess the remarkable property of forming compounds?
2. Why the bonds in coordination compounds have directional properties?
3. Why coordination compounds have the characteristic magnetic and optical properties?
Many theories/approaches have been put forward to explain the nature of bonding in coordination
compounds; these are valence bond theory (VBT), crystal field theory (CFT), ligand field theory (LFT) and
molecular orbital theory (MOT).
9.5.1 P.No.: 254

 The valence bond theory, VBT, was extended to coordination compounds by Linus Pauling in 1931.
 The formation of a complex involves reaction between a lewis base (ligand) and a lewis acid (metal or
metal ion) with the formation of a coordinate-covalent (or dative) bonds between them.
 The model utilizes hybridisation of (n – 1) d, ns, np or ns, np, nd orbitals of metal atom or ion to yield a set
of equivalent orbitals of definite geometry to account for the observed structures such as octahedral, square
planar and tetrahedral, and magnetic properties of complexes. The number of unpaired electrons, measured
by the magnetic moment of the compounds determines which d-orbitals are used.
 These hybrid orbitals are allowed to overlap with ligand orbitals that can donate electron pairs for bonding.
Following table provides the types of hybridisation with different coordination number.
Coordination number of metal Type of hybridisation Shape of complex
3
4 sp Tetrahedral
4 dsp2 Square planer
5 sp3d Trigonal bipyramidal
6 3 2 Octahedral
sp d
6 d2sp3 Octahedral
 It is to be noted that the type of hybridisation of metal and shape of complex involved can be predicted
conveniently, if some characteristic of the complex like magnetic nature, geometry or whether exhibits
isomerism or not, etc., be known.
BONDING IN COMPOUNDS WITH COORDINATION NUMBER SIX P.No.: 254
 In the diamagnetic octahedral complex, [Co(NH3)6]3+, the cobalt ion is in +3 oxidation state and has the
electronic configuration represented as shown below.
4s 4p
Co3+,[Ar]3d6
[Co(NH3)6]3+
(inner orbital or d2sp3 hybrid orbital

low spin complex) Six pairs of electrons from six NH3 molecules.
 Thus, the complex has octahedral geometry and is diamagnetic because of the absence of unpaired electron.
Since in the formation of complex the inner d-orbital (3d) is used in hybridisation, the complex is called an
inner orbital or low spin or spin paired complex.
 The complex [FeF6]4– is paramagnetic and uses outer orbital (4d) in hybridisation (sp3d2) ; it is thus called
as outer orbital or high spin or spin free complex. So,
3d 4s 4p 4d
Fe2+, [Ar]3d6
[FeF6]4–
sp3d2 hybrid orbitals
Six pairs of electrons from six F– ions.
BONDING IN COMPOUNDS WITH COORDINATION NUMBER FOUR
 In the paramagnetic and tetrahedral complex [NiCl4]2–, the nickel is in +2 oxidation state and the ion has
the electronic configuration 3d8. The hybridisation scheme is as shown in figure.
3d 4s 4p
2+ 8
Ni , [Ar]3d
[NiCl4]2–
sp3 hybrid orbitals

Four pairs of electrons from four Cl– ions.
 The compound is paramagnetic since it contains two unpaired electrons.
 Similarly complex [Ni(CO) 4] has tetrahedral geometry and is diamagnetic as it contains no unpaired
electrons. The hybridisation scheme is as shown in figure.
3d 4s 4p
Ni0, [Ar] 3d8 4s2
[Ni(CO)4]
sp3 hybrid orbitals
Four pairs of electrons from four CO molecules.
 Complexes of Pd(II) and Pt (II) are usually four-coordinate, square planar, and diamagnetic and this
arrangement is often found for Ni(II) complexes as well, e.g., in [Ni(CN)4]2– (here nickel is in +2 oxidation
state and has electronic configuration 3d8). In as much as the free ion is in the ground state each case is
paramagnetic, the bonding picture has to include pairing of electrons as well as ligand-metal-ligand bond
angles of 90° and this occurs via hybridisation of one (n – 1) d, one ns and two np orbitals to form four
equivalent dsp2 hybrid orbitals directed toward the corners of a square. These orbitals then participate in
covalent coordinate s bonds with the ligands, the bonding electron pairs being furnished by the ligands. The
hybridisation scheme for [PtCl4]2– is as shown in figure.
5d 6s 6p
Pt2+, [Xe]4f14 5d8
[PtCl4]2–
dsp2 hybrid orbitals
Four pairs of electrons from four Cl– ions.
Similarly the hybridisation scheme for [Ni(CN)4]2– is as shown in figure.
3d 4s 4p
Ni2+, [Ar]3d8
[Ni(CN)4]2–
Four pairs of electrons from four CN– ions.
 It is found that [Cu(NH3)4]2+ is square planar and paramagnetic with one unpaired electron in 4p-orbital.
The hybridisation scheme is as follow.
3d 4s 4p
Cu2+, [Ar]3d9
[Cu(NH3)4]2+
Four pairs of electrons from four NH3 molecules.
3–
Note : [Ni(CN)5] is found to be diamagnetic with 2 types of Ni – C bond lengths, out of which four bond
lengths are found to be equal and the fifth one is different. The hybridisation scheme for [Ni(CN)5]3– is as
shown in figure.
3d 4s 4p
2+ 8
Ni , [Ar]3d
[Ni(CN)5]3–
Five lone pairs of electrons from five CN – ions.
CN
CN CN
Ni square pyramidal.
CN CN
9.5.2 P.No.: 256

 Additional information for understanding the nature of coordination entities is provided by magnetic sus-
ceptibility measurements.
 We have noted that coordination compounds generally have partially filled d orbitals and as such they are
expected to show characteristic magnetic properties depending upon the oxidation state, electron configu-
ration, coordination number of the central metal and the nature of the ligand field.
 It is experimentally possible to determine the magnetic moments of coordination compounds which can be
utilized for understanding the structures of these compounds.
 The number of unpaired electrons in any complex can be easily calculated from the configuration of the
metal ion, its coordination number and the nature of the ligands involved( strong or weak from the spectro-
chemical series) and after that the magnetic moment of the complexes can be easily calculated using ;
Magnetic Moment = n( n  2) Bohr Magneton ; n = number of unpaired electrons

For metal ions with upto three electrons in the d-orbitals like Ti3+, (d1) ; V3+ (d2) ; Cr3+ (d3) ; two vacant d-
orbitals are easily available for octahedral hybridisation. The magnetic behaviour of these free ions and
their coordination entities is similar. When more than three 3d electrons are present, like in Cr2+ and Mn3+
(d4) ; Mn2+ and Fe3+ (d5) ; Fe2+ and Co3+ (d6) ; the required two vacant orbitals for hybridisation is not
directly available (as a consequence of Hund’s rules). Thus, for d4, d5 and d6 cases, two vacant d-orbitals are
only available for hybridisation as a result of pairing of 3d electrons which leaves two, one and zero
unpaired electrons respectively.
 The magnetic data agree with maximum spin pairing in many cases, especially with coordination compounds
containing d6 ion. However, there are complications with the coordination compounds / species having d4
and d5 ions.
[Mn(CN) 6] 3– has a magnetic moment equal to two unpaired electrons while [MnCl 6] 3– has a magnetic
moment equal to four unpaired electrons.
 Similarly [Fe(CN)6]3– has magnetic moment of a single unpaired electron while [FeF6]3– has a magnetic
moment of five unpaired electrons. [CoF6]3– is paramagnetic with four unpaired electrons while [Co(C2O4)]3–
is diamagnetic.
This anomalous behaviour is explained by valence bond theory in terms of formation of inner orbitals and
outer orbitals complexes.
 [Mn(CN)6]3– , [Fe(CN)6]3– and [Co(C2O4)2]3– are inner orbital complexes involving d2sp3 hybridisation, the
former two are paramagnetic and the latter diamagnetic. [MnCl6]3–, [FeF6]3– and [CoF6]3– are outer orbital
complexes involving sp3d2 hybridisation and are paramagnetic having four, five and four electrons respectively.
9.5.3 P.No.: 257

 While the valence bond theory, to a large extent, explains the formation, structures and magnetic behaviour
of coordination compounds, it suffers from the following shortcomings :
1. A number of assumptions are involved.
2. There is no quantitative interpretation of magnetic data.
3. It has nothing to say about the spectral (colour) properties of coordination compounds.
4. It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of coordina-
tion compounds.
5. It does not make exact predictions regarding the tetrahedral and square-planar structures of 4-coordi-
nate complexes.
6. It does not distinguish between strong and weak ligands.
81. Consider the following complex ions, P, Q, and R.
06 P = [FeF6] 3–, Q = [V(H2O)6] 2+ and R = [Fe(H2O)6] 2+, the
71. The hybridization of Fe in K4[Fe(CN)6] complex is: correct order of the complex ions, according to their
spin only magnetic moment values (in B. M.) is:
(1) d 2sp 2 (2) dsp 2
2 3
(1) Q<R<P (2) R<Q<P
(3) d sp (4) sp 3
(3) R<P<Q (4) Q<P<R
72. The structure of iron pentacarbonyl is:
82. Among the following ions which one has the highest
(1) square planar
paramagnetism?
(2) triangular
(1) [Cr(H2O)6]3+ (2) [Cu(H2O)6)2+
(3) trigonal bipyramidal
(3) [Fe(H2O)6] 2+ (4) [Zn(H2O) 6] 2+
(4) none of these
83. The reaction [Fe(CNS)6]  [FeF6] 3– takes place with:
3–
3+
73. [Cr(NH3)6] ion is:
(1) decrease in magnetic moment
(1) diamagnetic (2) square planar
(2) increase in coordination number
(3) paramagnetic (4) none of these
(3) decrease in coordination number
74. In hexacyanomanganate (II) ion the d2sp2-hybrid state.
(4) increase in magnetic moment
The number of unpaired electrons in the complex is:
84. dsp2-hybridization is found in
(1) 2 (2) 3
(1) [Co(NH3)2]2+ (2) [NiCl4)] 2–
(3) 0 (4) 1
(3) [Co(NH3)6]3+ (4) [Ni(CN4)] 2–
75. Which is true in the case of [Ni(CO)4] complex?
85. The primary valency of iron in K4[Fe(CN)6] is
(1) All are correct
(1) 1 (2) 3
(2) Tetrahedral shape of the molecule
(3) 2 (4) 4
(3) Hybridization of Ni is sp3
86. The magnetic moment of K4[Fe(CN)6] is found to be 17
(4) Diamagnetic
BM. How many unpaired electron(s) is/are present per
76. Which one of the following is an inner orbital complex molecule?
as well as diamagnetic in nature?
(1) 2 (2) 3
(1) [Co(NH3)6]3+ (2) [Cr(NH3)6]3+
(3) 4 (4) 1
(3) [Ni(NH3)6]2+ (4) [Zn(NH3)6] 2+
87. Cr(H2O)6]Cl3 has a magnetic moment of 3.83 B.M. The
77. Which of the following complex exhibits the highest correct distribution of 3d electrons in the chromium of
paramagnetic behaviour? the complex is
(1) [Ti(NH3)6]3+ (1) 3dxy1, 3dyz1, 3dz2
(2) [Fe(en)(bpy)(NH 3) 2] 2+ (2) 3d1xy, 3d1yz, 3d1zx
–
(3) [Co(OX)2(OH)2] (3) 3d(x2 – y2)1, 3d1z2, 3d1xz
+
(4) [V(gly)2(OH)2(NH3)2] (4) 3dxy1, 3d1(x2 – y2), 3d1y2
78. A magnetic moment of 1.73 B.M. will be shown by one 88. Which of the following complex is an outer orbital
among the following:
(1) [Ni(NH3)6]2+ (2) [Mn(CN)6] 4–
2+ 2–
(1) [Cu(NH3)4] (2) [Ni(CN)4]
(3) [Co(NH3)6]3+ (4) [Fe(CN)6] 4–
(3) TiCl4 (4) [CoCl6]4–
89. The correct order of magnetic moments (spin values in
79. A square planar complex is followed by hybridization B.M.) among is:
of which atomic orbitals?
(1) [Fe(CN)6] 4– > [CoCl4] 2– > [MnCl4] 2–
(1) s, p x, py, dyz (2) s, px, py, dz2
(2) [CoCl4]2– > [Fe(CN)6]4– > [CoCl4] 2–
(3) s, p x, py, d x2 – y2 (4) s, px, py, dxy
(3) [Fe(CN)6] 4– > [MnCl4] 2– > [CoCl4] 2–
80. Among the following complexes (K to P),
(4) [MnCl4] 2– > [CoCl4] 2– > [Fe(CN)6] 4–
K3[Fe(CN)6](K), [Co(NH3)6]Cl3 (L),
(Atomic no. of Mn = 25, Fe = 26, Co = 27)
Na3[Co(oxalate)3] (M), [Ni(H2O)6]Cl2 (N),
90. Which one of the following has the regular tetrahedral
K2[Pt(CN)4] (O), and [Zn(H2O)6](NO3)2 (P)
structure?
The diamagnetic complexes are:
(1) [Ni(CN)4]2– (2) SF 4
(1) K, L, M, N (2) L, M, O, P –
(3) BF4 (4) XeF4
(3) K, M, O, P (4) L, M, N, O
9.5.4
 The drawbacks of VBT of coordination compounds are, to a considerable extent, removed by the Crystal
Field Theory.
 The crystal field theory (CFT) is an electrostatic model which considers the metal-ligand bond to be ionic
arising purely from electrostatic interaction between the metal ion and the ligand.
 Ligands are treated as point charges in case of anions or dipoles in case of neutral molecules. The five d
orbitals is an isolated gaseous metal atom/ion have same energy, i.e., they are degenerate.
 This degeneracy is maintained if a spherically symmetrical field of negative charges surrounds the metal
atom/ion. However, when this negative field is due to ligands (either anions or the negative ends of dipolar
molecules like NH3 and H2O) in a complex, it becomes asymmetrical and the degeneracy of the d orbitals is lost.
It results in splitting of the d orbitals. The pattern of splitting depends upon the nature of the crystals field.
CRYSTAL FIELD SPLITTING IN OCTAHEDRAL COORDINATION ENTITIES P.No.: 257
 In an octahedral coordination entity with six ligands surrounding the metal atom/ion, there will be
repulsion between the electrons in metal d orbitals and the electrons (or negative charges) of the ligands.
 Such a repulsion is more when the metal d orbital is directed towards the ligand than when it is away from
the ligand. Thus, the d x  y and d z orbitals (axial orbitals) which point towards the axis along the direction
2 2 2
of the ligand will experience more repulsion and will be raised in energy ; and the dxy, dyz and dzx orbitals
(non-axial orbitals) which are directed between the axis will be lowered in energy relative to the average
energy in the spherical crystal field.
 Thus, the degeneracy of the d orbitals has been removed due to ligand electron-metal electron repulsions in the
octahedral complex to yield three orbitals of lower energy, t2g set and two orbitals of higher energy, eg set.
 This splitting of the degenerate levels due to the presence of ligands in a definite geometry is termed as
crystal field splitting and the energy separation is denoted by 0 (the subscript o is for octahedral). Thus,
the energy of the two eg orbitals will increase by (3/5)0 and that of the three t2g will decrease by (2/5) 0.
Z
Energy Y Energy correspond
dx 2
 y2
, dz 2
eg to absorption.
3/5 0 or + 0.6 0 average
X + 6L 0 energy (Bari center)
2/5 0 or – 0.4 0
Metal Average energy level
of 'd ' orbitals in spherical t2g
d orbitals dxy, dxz , dyz
crystal field Energy corresponds to
Crystal field splitting evolution of energy.
for octahedral complex
Free metal ion
Figure showing crystal field splitting in octahedral complex.
 The crystal field splitting, 0, depends upon the fields produced by the ligand and charge on the metal ion.
Some ligands are able to produce strong fields in such a case, the splitting will be large whereas others
produce weak fields and consequently result in small splitting of d orbitals. In general, ligands can be
arranged in a series in the orders of increasing field strength as given below :
I– < Br– < S2– < Cl– < NO3– < F– < OH– < EtOH < C2O42– < H2O < NCS– < EDTA < NH3 < en < NO2– < CN–
< CO
Such a series is termed as spectrochemical series.
 It is an experimentally determined series based on the absorption of light by complexes with different
ligands. For d4 configuration, the fourth electron will singly occupy eg orbital (according to Hund’s rule) or
will undergo pairing in t2g orbital, which of these possibilities occurs, depends on the relative magnitude of
the crystal field splitting, 0 and the pairing energy, P (P represents the energy required for electron pairing
in a single orbital). The two possibilites are :
1. If 0 < P, the fourth electron enters one of the eg orbitals giving the configuration t32geg1. Ligands for
which 0 < P are known as weak field ligands and form high spin complexes.
2. If 0 > P, it becomes more energetically favourable for the fourth electron to occupy a t2g orbital with
configuration t2g4 eg0. Ligands which produce this effect are known as strong field ligands and form low
spin complexes.
CALCULATION OF CRYSTAL FIELD STABILISATION ENERGY (CGSE)
Formula : CFSE = [– 0.4 (n) t2g + 0.6 (n) eg] 0 + *nP.

where n and n are number of electron(s) in t2g and eg orbitals respectively and 0 crystal field splitting
energy for octahedral complex. *n represents the number of extra electron pairs formed because of the
ligands in comparison to normal degenerate configuration.
CRYSTAL FIELD SPLITTING IN TETRAHEDRAL COORDINATION ENTITIES P.No.: 259
 In tetrahedral coordination entity formation, the d orbital splitting is inverted and is smaller as compared to
the octahedral field splitting. For the same metal, the same ligands and metal-ligand distances, it can be
shown that t = (4/9)0. This may attributes to the following two reasons.
1. There are only four ligands instead of six, so the ligand field is only two thirds the size ; as the ligand
field spliting is also the two thirds the size and
2. The direction of the orbitals does not concide with the direction of the ligands. This reduces the
2 2 4
crystal field spliting by roughly further two third. So  t     0 .
3 3 9
Consequently, the orbital splitting energies are not sufficiently large for forcing pairing and, therefore, low
spin configurations are rarely observed.
Figure showing crystal field splitting in tetrahedral complex.

 Since t < 0 crystal field spliting favours the formation of octahedral complexes.
 sp = 1.3 0.
9.5.5 COLOUR IN COORDINATION COMPOUNDS P.No.: 259

 Coordination compounds of transition metals have fascinating colours.
 According to the crystal field theory the colour is due to the d-d transition of electron under the influence of
ligands.
 We know that the colour of a substance is due to the absorption of light at a specific wavelength in the
visible part of the electromagnetic spectrum (400 to 700 nm) and transmission or reflection of the rest of
the wavelengths.
 An object that absorbs all visible light appears black.
 The mechanism of light absorption in coordination compounds is that photons of appropriate energy can
excite the coordination entity from its ground state to an excited state.
 Consider the Ti(III) ion in solution, that is [Ti(H2O)6]3+. This is a violet colour octahedral complex, where
in the ground state of the complex a single electron is present in t2g level.
 The next higher state available for the transition is the empty eg level. If the light corresponding to the
energy of yellow-green is absorbed by the complex, it would excite the electron from t2g level to eg level.
 Consequently the complex appears violet in colour. In case of copper (II) ions in solution, for example, it
can be imagined that one of the d-electrons from the t2g set (dxy, dyz, dxz orbitals) gets excited to the eg set
(orbitals). In this case since high energy light is transmitted it means that low energy light (red region) is
absorbed. For copper (II) ions in aqueous solution, the energy gap t is relatively small. Table below gives
the relationship of the wavelength of light absorbed and the colour observed.
Relationship between the wavelength of light absorbed and the colour observed In some coordination entitles
Coordination entity Wavelength of light Colour of light Colour of coordination
absorbed (nm) absorbed entity
[CoCl(NH3)5]2+ 535 Yellow Violet
[Co(NH3)5(H2O)]3+ 500 Blue Green Red
[Co(NH3)6]3+ 475 Blue Yellow Orange
[Co(CN)6]3– 310 Ultraviolet Pale Yellow
[Cu(H2O)4]2+ 600 Red Blue
[Ti(H2O)6]3+ 498 Blue Green Purple
Note :
1. In absence of ligand, crystal field splitting does not occur and as a consequence the substance appears
colourless. For example ; (i) removal of water from violet coloured complex [Ti(H2O)6]Cl3 on heating
makes it colourless, (ii) similarly anhydrous copper sulphate (CuSO4) is white, but hydrated copper
sulphate (CuSO4.5H2O) is blue coloured.
2. The nature of the ligand and the molar ratio of metal : ligands also influence the colour of the complex.
For example ; in the pale green complex of [Ni(H2O) 6], the colour change is observed when ethyl-
enediamine is progressively added to it.
Molar ratio of en : Ni Coloured observed
1 :1 Pale blue
2 :1 Blue / Purple
3 :1 Violet
3+ 3
Note : Ruby is Al2O3 in which 0.5 – 1% Cr ions (d electron system) are randomly distributed in the
positions normally occupied by Al3+. We may consider Cr(III) species as octahedral Cr(III) complexes
incorporated into the alumina lattice ; d - d transition of electron at these centres/points give rise to the
colour (red).
Emerland is the mineral beryl (Be3Al2Si6O18) in which Cr3+ ions occupy octahedral sites, but in this
case low energy corresponding to yellow red and blue is absorbed and light corresponding to green
region is transmitted.
9.5.6 LIMITATIONS OF CRYSTAL FIELD THEORY PAGE P.No.: 261
 It considers only the metal ion d-orbitals and gives no consideration at all to other metal orbitals (such as s,
px, py and pz orbitals).
 It is unable to account satisfactorily for the relative strengths of ligands. For example it gives no explana-
tion as to why H2O is a stronger ligand than OH– in the spectrochemical series.
 According to this theory, the bond between the metal and ligands are purely ionic. It gives no account on
the partly covalent nature of the metal ligand bonds.
 The CFT cannot account for the -bonding in complexes.
07 98. Which of the following is -acid ligand?

(1) NH 3 (2) CO
91. If the crystal filed splitting energy for octahedral (3) F –
(4) ethylene diamine
complexes is 0 and for tetrahedral complexes is t, the
two are related as 99. In the complex ion MLn6 , Mn+ has five d-electrons and
L is a weak field ligand. According to crystal field theory,
4 1 the magnetic properties of the complex ion correspond
(1) t =  0 (2) t =  0
9 2 to how many unpaired electrons?
1 4 (1) 0 (2) 5
(3) 0 = t (4) 0 = t
2 9 (3) 2 (4) 3
92. Which is the strongest field ligand? 100. Increasing order of 0 of the following complex is
(1) NO 2– (2) CN – (1) Cr(NH3)63+ < Cr(H2O)63+ < Cr(NO2)63–
(3) NH 3 (4) En (2) Cr(H2O)63+ > Cr(NH3)63+ > Cr(NO2)63–
93. Considering H2O as a weak field ligand, the number of (3) Cr(H2O)63+ < Cr(NH3)63+ < Cr(NO2)63–
unpaired electrons in Mn(H 2O)62  will be: (4) Cr(NH3)63+ < Cr(NO2)63– < Cr(H2O)63+
(1) 3 (2) 2 101. The val ue of  0 for RhCl 6 3– is 243 kJ /mol what
wavelength of light will promote an electron from. The
(3) 5 (4) 4 colour of the complex is
94. Which of the following complex ions is expected to
(1) Blue (2) Green
absorb visible light?
(3) Yellow (4) Orange
(1) [Zn(NH3)6] 2+ (2) [Cr(NH3)6]3+
6 2
102. For the t e system, the value of magnetic moment
(3) [Ti(en)2NH3)2] 4+ (4) [Sc(H2O)3(NH3)3] 3+ 2g g
(µ) is:
95. Which of the following statements are correct?
(1) 2.83 B.M. (2) 1.73 B.M.
(i) In octahedral complexes, dz2, dx2 – y2 orbitals have
higher energy than d xy, dyz and d zx orbitals. (3) 3.87 B.M. (4) 4.92 B.M.
(ii) In tetrahedral complexes d xy, d yz and d zx orbitals 103. Which of the following system has maximum number
have higher energy than dz2, dx2 – y2 orbitals. of unpaired electrons?
(iii) The colours of complexes are due to electronic (1) d5 (octahedral)
transitions from one set of d–orbitals to another (2) d9 (octahedral)
set of orbitals.
(3) d7 (octahedral)
9 (4) d6 (octahedral)
(iv) tedrahedral = , octahedral
4 104. Which ion produces a small crystal field splitting (a
(1) (i), (ii) and (iii) (2) (i) and (iv) weak ligand field)?
(3) (iii) and (iv) (4) (ii), (iii) and (iv) (1) I– (2) Cl–
–
96. In crystal field splitting for a tetrahedral complex, the (3) F (4) All
number of orbitals pushed down in energy are 105. Which of the following pairs is not correctly matched?
(1) 3 (2) zero (1) Effective atomic number of Pt in [PtCl6] 2– = 84
(3) 5 (4) 2 (2) Absorption peak for [Cr III (NH 3 ) 6 ] 3+ = 21680
97. Among the ligands NH3, en, CN– and CO, the correct cm–1
order of their increasing field strength, is
(3) Crystal field stabilization energy of d 2 in weak
(1) CO < NH3 < en < CN– ligand field = (–)0.8 0
(2) NH3 < en < CN– < CO (4) Example of weak ligand field for d5 configuration
(3) CN– < NH3 < CO < en = [MnII F6] –4
(4) en < CN– < NH3 < CO
9.7 STABILITY OF COORDINATION COMPOUNDS P.No.: 261
 The stability of a coordination compound [MLn] is measured in terms of the stability constant (equilibrium
constant) given by the expression,
 n = [MLn] / [M(H2O)n][L]n
For the overall reaction :
M(H2O)n + nL   ML + nH O
n 2
By convention, the water displaced is ignored, as its concentration remains essentially constant. The above
overall reaction takes place in steps, with a stability (formation) constant, K1, K2, K3, ...... Kn for each step
as represented below :
 ML(H O) + H O ; K = [ML(H O) ] / {[M(H O) ][L]}
M(H2O)n + L  2 n–1 2 1 2 n–1 2 n
ML (H O) + L   ML + H O ; K = [ML ] / {[ML (H O)] [L]}

n–1 2 n 2 n n n–1 2
 ML n  nH 2 O
M(H 2 O) n  nL 
 n = K1 × K2 × K3 × ........ × Kn
  n, the stability constant, is related to thermodynamic stability when the system has reached equilibrium.
Most of the measurements have been made from aqueous solutions, which implies that the complex is
formed by the ligand displacing water from the aqua complex of the metal ion. Ignoring the charge and
taking L as an unidentate ligand, the stepwise formation of the complex is represented as shown above. K1,
K2, K3 ..... Kn representing the stepwise stability (or formation) constants.
 The above is thermodynamic stability criteria, there can be another kind of stability called kinetic stability,
which measures the rate of ligand replacement.
SOME IMPORTANT GENERALISATION REGARDING STABILITY CONSTANTS :

 For a given metal and ligand the stability is generally greater when the charge on the metal ion is greater.
Thus, stability of coordination entities of ions of charge 3+ is greater than the entities of 2+ ions. Further,
for the divalent ions of the first row transition elements, irrespective of the ligand involved, the stabilities
vary in the Irving-Williams order :
MnII < FeII < CoII < NiII < CuII > ZnII
 This order is according to the size of the ions, smaller the size of the ion or greater the charge density on the
metal greater is the stability of the complex.
In F¯, Cl¯, Br¯, I¯ ; F¯ forms strongest complexes due to small size & hence high charge density.
 The stability also depends on the formation of chelate rings. If L is an unidentate ligand and L – L, a
didentate ligand and if the donor atoms of L and L – L are the same element, then L – L will replace L. The
stabilisation due to chelation is called the chelate effect. It is of great importance in biological systems and
analytical chemistry.
 If a multidentate ligand happens to be cyclic and there are no unfavourable steric effects, a further increase
in stability occurs. This is termed the macrocyclic effect.
9.6 BONDING IN METAL CARBONYLS P.No.: 261
Compounds of metals with CO as a ligand are called metal carbonyls.

They are of two types.
MONOMERIC
 Those metal carbonyls which contain only one metal atom per molecule are called monomeric carbonyls.
For examples : [Ni(CO)4] (sp3, tetrahedral) ; [Fe(CO)5] (dsp3, trigonal bipyramidal);
 [Cr(CO)6] (d2 sp3, octahedral) ; [V(CO)6] (d2 sp3, octahedral, only carbonyl which is paramagnetic having
one unpaired electron ; this is least stable among all the four carbonyls)
CO CO CO
OC CO CO
Ni Fe CO Cr
OC CO OC CO CO
CO CO CO
Ni(CO)4 Fe(CO)5 Cr(CO)6
Tetrahedral Trigonal bipyramidal Octahedral
POLYMERIC
 Those metal carbonyls which contain two or more than two metal atoms per molecule and they have
metal-metal bonds are called polymeric carbonyl. For examples : Mn2 (CO)10, Co2(CO)9, etc.
CO CO CO CO
CO CO OC CO
OC Mn Mn CO Co Co
CO CO OC OC CO
CO CO CO
[Mn2(CO)10] [Co2(CO)8]
 Metal carbonyls are mostly solids at room temperature and atmospheric pressure.
 The mononuclear carbonyls are volatile and toxic. With the exception of Fe2(CO)9, carbonyls are soluble in
hydrocarbon solvents.
 Mononuclear carbonyls are either colourless or light-coloured.
 Polynuclear carbonyls are more deeply coloured. Fe3(CO)12, dodecacarbonyltriiron(o), For examples : is a
deep grass green solid.
 Metal carbonyls find use as industrial catalysts and as precursors in organic synthesis.
 The metal–carbon bond in metal carbonyls possess both  and  character.
 The M — C  bond is formed by the donation of lone pair of electrons on the carbonyl carbon (CO is a
weak base) into a vacant orbital of the metal.
 The M — C  bond is formed by the donation of a pair of electrons from a filled d orbital of metal into the
vacant antibonding * orbital of carbon monoxide.
 Thus carbon monoxide acts as  donor (OC  M) and a  acceptor (OC  M), with the two interactions
creating a synergic effect which strengthens the bond between CO and the metal as shown in figure.
p p*
M s C  O

 p
Synergic bonding
1. As M — C  bonding increases, the C — O bond becomes weaken. The greater the positive charge on
the central metal atom, the less readily the metal can donate electron density into the * orbitals of the
carbon monoxide ligands to weaken the C — O bond.
2. In contrast, in the anionic complex (i.e. carbonylate anion) the metal has a greater electron density to
be dispersed, with the result that M — C  bonding is enhanced and the C — O bond is diminished in
strength. For example ; in isoelectronic complexes the strength of metal-ligand bond increases and
strength of C — O bond in CO decreases (because bond order decreases) as the negative charge on the
complexes increases.
Thus order of CO bond strengths ;
(a) [Mn(CO)6]+ > [Cr(CO)6] > [V(CO)6]– > [Ti(CO)6]2–.
(b) [Ni(CO)4] > [Co(CO)4]– > [Fe(CO)4]2–.
Sigma () bonded organometallic compounds :

 In these complexes, the metal atom and carbon atom of the ligand Bridging groups
are joined together with a sigma bond in which ligand contrib-
utes one electron and is therefore called one electron donor. CH3 CH3 CH3
For example ;
Al Al
1. Grignard’s Reagent : R – Mg – X where R is a alkyl or aryl
group and X is halogen. CH3 CH3 CH3
2. (CH3)4 Sn, (C2H5)4 Pb, Al2 (CH3)6, Al2 (C2H5)6 etc.
Pie ()-bonded organometallic compounds :

These are the compounds of metal with alkenes, alkynes, benzene and other ring compounds.
Zeise's salt :
 In Zeise’s salt structure, the ethylene occupies the fourth coordination site of the square planar complex
with the C — C axis perpendicular to the platinum ligand plane.
 Relative to free ethylene the C — C bond is lengthened (from 133.77 H H –
pm to 137.5 pm), and the hydrogen are slightly tilted back from a C
planar arrangement. ||
 The bond between the ethylene molecule and the metal ion may be Cl C
K+
considered as a dative  bond to an available orbital on the metal.
Pt H H
 The bonding scheme is analogous to that in carbon monoxide com-
plexes in which there is a ligand metal  donation and a reciprocal Cl Cl
metal to ligand  bonding. The extent of back bonding varies depend-
ing on the metal, the substituents on ethylene, and the other ligands K [PtCl3 (2 – C2H4)]
on the metal,
Ferrocene and bis(benzene) chromium :

 Ferrocene obeys 18-electrons rule. Depending on the electron counting method adopted, the cyclopentadienyl
ligand may be viewed as either a five electron donor (neutral atom) or a six electron donor (oxidation state).
 Similarly, the benzene ligand may be viewed as a six electron donor in neutral atom as well as in the
oxidation state. Ferrocene show thermal stability and is not oxidised by air.
–1
Fe 2+ Cr
Fe (5 – C5H5)2 and Cr (6 – C6H6)2
–1
9.8 P.No.: 261
 Coordination compounds are of great importance in biological systems. Example being – chlorophyll (the
green pigment in plants); haemoglobin (the red pigment of blood, which acts as oxygen carrier) along with
myoglobin (which stores oxygen and is a regulator of respiration); Vitamin B12, cyanocobalammine, the
anti-pernicions anaemia factor. All of these, respectively, are the coordination compounds of magnesium,
iron and cobalt with the macrocyclic porphyrin and corrin ligands.
 There are many examples of the use of coordination compounds in qualitative and quantitative chemical
analysis. The familiar colour reactions given by metal ions with a number of ligands (especially the chelat-
ing ligands), as a result of formation of coordination entities, form the basis for their detection and estima-
tion by classical and instrumental methods of analysis. Familiar examples of such reagents are :
ethylenediaminetetraaceticacid (EDTA), dimethylglyoxime, a-nitroso b-naphthol, cupron, etc.
 Some important extraction processes of metals, like those of extraction of silver and gold, make use of complex
formation. Gold, for example, combines with cyanide in the presence of oxygen and water to form the coordina-
tion entity [Au(CN)2]– in aqueous solution. Gold can be precipitated from this solution by the addition of Zinc.
 Purification of metals can be achieved through formation and subsequent decomposition of their coordination
compounds. For example, impure nickel is converted to [Ni(CO)4], which is decomposed to yield pure nickel.
 EDTA is used in the treatment of lead poisoning. Some coordination compounds of platinum effectively
inhibit the growth of tumors. Examples are : cis-platin (cis-[Pt(NH3)2Cl2] and related compounds.
 Organometallic compounds are used as catalysts. These catalysts are either of the homogeneous type (soluble
in the reaction medium) or of the heterogeneous type (insoluble in the reaction medium). The catalysed
polymerisation of alkenes at atmospheric pressure and ambient temperature using Ziegler-Natta catalyst
(titanium tetrachloride plus triethylaluminium) is one of the important discoveries of organometallic
chemistry. The first effective homogeneous catalyst chloridotris(triphenylphosphine) rhodium(I),
[RhCl(PPh3)3] for hydrogenation was given by Wilkinson.
 Tetra ethyl lead (TEL) is used as antiknock compound in gasoline.
08 111. Ammonia forms the complex [Cu(NH3)4] 2+ with copper

ions in alkaline solution but not in acid solution. The
106. Chlorophyll is a coordination compound having central reason for it is:
atom of (1) in alkaline solution Cu(OH)2 is precipitated which
(1) Ca (2) K is soluble in excess of alkali
(3) Na (4) M g (2) in acidic s olution protons coord inates with
107. A reagent used for identifying nickel ion is: ammonia molecule forming NH 4+ ions and NH 3
molecules are not available.
(1) potassium ferrocyanide
(2) dimethylglyoxime (3) copper hydroxide is amphoteric
(3) phenolphthalein (4) in acidic solution hydration protects Cu2+ ions
(4) EDTA 112. Which of the following compounds is brown coloured?
108. The bond length of C – O bond in carbon mono-xide is (1) Fe[Fe(CN)4] (2) Fe4[Fe(CN)6]
1.128 A. The C – O bond in Fe(CO)5 is: (3) Fe[Fe(CN)6] (4) K2Fe[Fe(CN)6]
(1) 1.128 Å (2) 1.72 Å 113. Which one of the following statement is correct?
(3) 1.118 Å (4) 1.15 Å (1) Ferric ions give a deep green precipitate on adding
109. Backbonding involves the formation of potassium ferrocyanide solution.
(1) -bond (2) coordinate bond (2) On boiling a solution having K+, Cu2+ & HCO3– ions,
(3) -bond (4) none of these we get a precipitate of K2Ca(CO3)2
110. Composition of complex formed when the ore argentite (3) Manganese s alt give a violet bo rax test in
is treated with NaCN is reducing flame
(1) Na[Ag(CN)2] (2) Na3[Ag(CN)6] (4) From a mixed precipitate of AgCl and AgI, ammonia
(3) Na[Au(CN)6] (4) Na[Au(CN)6] solution dissolves only AgCl
114. Coordination compounds have great importance in (4) CuSO4 + 4KCN  K2[Cu(CN)4] + K2SO4
biological systems. In this context which of the 118. Which of the following observations/statements is/
following statements is incorrect: are correct?
(1) Carboxypeptidase A is an enzyme and contains (1) Anhydrous CuSO 4 becomes blue in aqueous
zinc medium due to the complex formation
(2) Haemoglobin is the red pigment of blood and (2) Ni(CN) 2 dissolves in KCN giving an orange-red
contains iron solution
(3) Cyanocobalamin in B12 and contains cobalt (3) Fe(OH)3 can be precipitated by adding NH4OH to
(4) Chlorophylls are green pigments in plants and K3[Fe(CN)6]
contain calcium (4) None of the above
115. Aqua regia reacts with Pt to yield: 119. Which one of the following statements is incorrect?
(1) Pt(NO3) 4 (2) H2PtCl6 (1) Greater the stability constant of a complex ion,
(3) PtCl4 (4) PtCl2 greater is its stability
116. Which of the following is  complex? (2) Greater the charge on the central metal ion, greater
(1) Trimethyl aluminium (2) Ferrocene is the stability of the complex
(3) Diethyl zinc (4) Nickel carbonyl (3) Greater the basic character of the ligand, the
greater is the stability of the complex
117. The equation which is balanced and represents the
correct product(s) is (4) Complexes have low stability constants.
(1) Li2O + 2KCl  2LiCl + K2O 120. In Fe(CO)5, the Fe–C bond possesses:
(2) + + 2+
[CoCl(NH3)5] + 5H  CO + 5NH4 + Cl + – (1) –character only
Excess NaOH
(2) Both  and  characters
(3) [Mg(H2O)6] 2+ + (EDTA)4   (3) Ionic character
[Mg(EDTA)2+ + 6H2O (4) –character only
9.9 Synopsis
 When solutions of two or more simple stable compounds in molecular proportions are allowed to evapo-
rate, crystals of new compounds may be formed. These compounds compounds molecular or addition
compounds. Addition compounds are of two types :
1. Double salts or lattice compounds and 2. Coordination or complex compounds.
 The addition compounds which are stable in solid state but are broken down into individual constituents
when dissolved in water are called double salts. Mohr salt, potash alum, carnallite, etc., are some examples
of double salts.
 The addition compounds which retain their identity in solid state as well as in solunon are termed
coordination or complex compounds. In these compounds at least one complex ion is present. In complex
ion, a metal atomm or ion is surrounded by a number or groups through coordination.
 Complex compounds are mainly formed by transition metals but to a small extent by other metals such as
magnesium in chlorophyll. Transition metals form complexes due to the following reasons :
(i) small size, (ii) high nuclear charge, (ii) a number of vacant orbitals of equivalent energy where the
electrons donated by ligands are accommodated.
 The neutral molecules, anions or cations which are directly linked with the central metal atom or ion in a
complex ion are called ligands. The ligand at least consists one donor atom having a lone pair of electrons
which it can donate to metal atom or ion. Ligands can be classified on the basis of number of donor atoms.
They are termed monodentate, bidentate, tridentate, etc. The ligands having two or more donor groups are
called polydentate. Polydentate ligand is known as chelating ligand if on coordination it results in the
formation of a closed or cyclic ring structure. The complexes, thus, formed are called chelates.
 The number of atoms of the ligands that are directly bound to the central metal atom or ion by coordinate
bonds is known as coordination number of the metal atom or ion. It is actually the number of chemical
bonds which the ligands form with central metal atom or ion. The most common coordination numbers are
4 or 6. 1he central metal atom or ion and the ligands that are directly attached to it are enclosed in a square
bracket. This is called coordination sphere. It behaves as a single unit. The ions present outside the coor-
dination sphere form ionisation sphere.
 4K   [Fe(CN)6 ]4 
K 4 Fe(CN)6 
 [Cu(NH3 )4 ]2   SO 24 
[Cu(NH3 )4 ] SO 4 
Charge on the complex ion = oxidation number of metal ion + charge on the ligands
Coordination [Co(NH3) 6 ] Cl3 Ionisation

sphere sphere
Central metal Coordination

ion / atom Ligands Number
 Effective Atomic Number (EAN) is defined as the resultant number of electrons with the metal atom or ion
after gaining electrons from donor atoms after ligands.
EAN = atomic number of the metal – number of electrons lost in ion formation
+ number of electrons gained from the donor atoms of the ligands
 The ollowing points are follov in naming complex compounds :
1. Cation is named first followed by anion.
2. In the coordination sphere, the ligands are named lphabetically. Anionic ligands ending with -ide are
named by replacing -ide by suffix -o or by replacing -e by -o. Ligands whose names end in -ite or -ate
become -ito or -ato, i.e., by replacing the ending -e with -o. Neutral ligands are given the same names
as the neutral molecules. However, H2O is named aqua and NH3 ammine. Positively charged ligands
have suffix -ium. If the number of a particular ligand is more than one, the number is indicated by
using di, tri, tetra, penta, etc. However, when the name of the ligand includes number, then bis, tris,
etc., are used.
3. The oxidation state of the central metal is shown by Roman numeral in bracket immediately following
its name.
4. Complex positive ions and neutral coordination compounds have no special ending but complex
negative ions always end in the suffix -ate.
 Coordination compounds exhibit structural isomerism ds well as stereoisomerism. Structural 1somerism is
displayed when different ligands are present within Oordination spheres. The coordination compounds
exhibit various types of structural isomerism.
1. Ionisation isomerism : Isomers give different ions in solution.
Examples : [Co(NH3)5Br] Cl ; [Co(NH3)5Cl]Br.
2. Hydrate isomerism : Isomers having H2O as a ligand or as water of hydration.
Examples : [Cr(H2O)6]Cl3 ; [CrCl(H2O)5] Cl2 . H2O ; [CrCl2(H2O)4] Cl . 2H2O.
3. Coordination isomerism : The ligands interchanged in both the cationic and anionic ions.
Examples : [Co(NH3)6] [Cr(CN)6] ; [Cr(NH3)6] [Co(CN)6]
4. Linkage isomerism : This type of isomerism exists when ambidentate ligand is present.
Examples : [Co(NH3)5ONO]Cl2 ; [Co(NH3)5 NO2] Cl2.
 Stereoisomerism : It arises on account of the different positions and arrangement of ligands in space
around the metal ion. It is of two types : (a) geometrical and (b) optical
Geometrical isomerism is common in coordination number 4 (square planar) and coordination number 6
compounds. This type of isomerism is termed cis-trans isomerism. When the ligands occupy adjacent
positions, the isomer is called cis-form and when opposite positions, the isomer is termed trans-isomer.
The square planar complexes having general formula Ma2b2 Ma2bc or Mabcd show cis-trans isomerism.
Square planar complexes having unsymmetrical bidentate ligands can also show geometrical isomerism.
Geometrical isomerism is not observed in complexes o coordination numbers 2 and 3. Square planar
complexes of the type Ma4, Ma3b and Mab3 do not show geometrical isomerism. Geometrical isomerism is
also not observed in tetrahedral complexes. Octahedral complexes of the type Ma4b2, Ma2b4 Ma4bc and
Ma3b3 exhibit geometrical isomerism.
 A coordination compound which can rotate the plane of polarised light is said to be optically active. The
optical isomers are pair of molecules which are non-superimposable mirror images of each other. The
isomer which rotates the plane of polarised light to right direction is termed dextro while the isomer which
rotates the plane of polarised light to left direction is termed laevo form.
Optical isomerism is very common in octahedral complexes. Octahedral compounds of general formulae
[Ma 2 b 2 c 2 ] n± [Mabcdef], [M(AA) 3] n±, [M(AA) 2 a 2 ] n± , and [M(AB) 3] n± and [M(AA) 2ab] n± where AA =
symmetrical bidentate ligands and AB = unsymmetrical bidentate ligands.
 Werner, in 1893, proposed the coordination theory to explain the properties and structures of various metal
ammines. The important postulates of the theory are :
1. Every valencies exhibits two types of valencies :
(a) Primary valency and (b) Secondary corresponds to oxidation state of metal and secondary valency
represents the coordination number of the metal. Primary valency is satisfied by negative ions and is
ionisable. The secondary valency is satisfied by neutral molecules or negative 1ons or both. This
valency is non-ionic. Metal and neutral molecules or negative ions which satisfy secondary valency
are enclosed in square bracket and termed as coordination sphere.
2. Every element tends to satisfy both its valencies. A negative ion when present in coordination sphere
shows a dual behaviour. It satisfies both primary and secondary valencies. The presence of negative
ion in the coordination sphere reduces the charge on the complex ion by the amount of charge
possessed by it and the negative ions present in the coordination sphere are not ionised.
3. The ligands in coordination sphere are directed towards fixed positions in space. The geometry of the
complex ion depends on coordination number. If the coordination number is 6, the complex is octahe-
dral. On the other hand, if the coordination number is 4, the geometry of the complex may be tetrahe-
dral or square planar.
 Valence bond theory describes the bonding in complexes in terms of two-electron, coordinate-covalent
bonds resulting from overlap of filled ligand orbitals with vacant metal hybrid orbitals that point in the
direction of the ligands :
sp (inear) ; sp3 (tetrahedral); dsp2 (square planar) and d2sp3 and sp3d2 (octahedral).
This theory explains with reasonable success the formation, magnetic behaviour and geometrical shapes of
coordination compounds. It, however, fails to provide a quantitative interpretation of magnetic behaviour
and explanation about optical properties of coordination compounds.
Examples:
(a) Octahedral complexes
1. Inner orbital (low spin) complexes involving d sp-hybridization:
[Fe(CN)6]3–, [Co(CN)6]3–, [Cr(NH3)6]3+. [Co(NH3)6]3+, etc.
2. Outer orbital (high spin) complexes involving sp3d2-hybridization :
[CoF]3–, [Fe(H2O)6]3+. [MnF6]3–, [Ni(NH3)6]2+, etc.
(b) Tetrahedral complexes involving sp3-hybridization :
[NiCl4]2–, [Cu(Cl4)]2–, Ni(CO)4, [Zn(NH3)4]2+, etc.
(c) Square planar complexes involving dsp2-hybridization :
[Ni(CN)4]2–, [Cu(NH3)4]2+, etc.
 Crystal field theory assumes that the metal-ligand bonding is entirely ionic. Because of electrostatic
repulsions between the d-electrons and the ligands, the d-orbitals are raised in energy and are diferentiated
by an energy separation called the crystal field splitting, . In octahedral complexes the d z , d x
2 2
 y2 orbitals
(e.g. set of orbitals) have higher energy than d xy, dyz and dzx orbitals (eg., set of orbitals). Tetrahedral
complexes exhibit just opposite splitting pattern.
The colours of complexes are due to electronic transitions from one set of d-orbitals to another and the
transition energies depend on the position of ligand in the spectrochemical series. Weak field ligands give
small  values and strong field ligands give small  values. Crystal field theory accounts for magnetic
properties of complexes in terms of the relative values  and the spin pairing energy. Small  values favour
hi spin complexes (maximum number of unpaired d-electrons) and large  values favour low complexes.
 In general, higher the charge density on the central ion, the greater is the stability of its complexes.
Electronegativity of the central 1on aiso intluences the stability. The higher the oxidation state of the metal,
the more stable is the complex. The more basic ligand forms the complex with greater stability.
The cyano and ammine complexes are far more stable than those formed by halide ions.
Chelating ligands form more stable complexes as compared to monodentate ligands.
 Coordination compounds are generally prepared by the application of :
1. Ligand substitution reactions :
[Cu(H 2 O)4 ]2  4NH3 
[Cu(NH3 )4 ]2  4H 2 O
2. Direct mixing of reagent :
PtCl2  2H 2 N — CH 2 — CH 2 — NH2 
[Pt(en)2 Cl2 ]
3. RedOX reaction :
K 2 Cr2 O7  7H 2 C2 O4  2K 2 C2 O4 
 2K 3 [Cr(C2 O4 )3 ]  6CO2  7H 2 O
 The complexes find applications in various fields :
1. Analytical chemistry : Cu2+, Fe3+, Ni2+, etC. tested in the form of complexes. Ca2+, Mg2+ and Zn2+ ions
are estimated volumetrically by EDTA. Mauy ions are quantitatively estimated by using a numo of
organic ligands.
2. Coordination complexes of transition metals exhibit a variety of colours. This forms the basis of colo-
rimetric estimations.
3. Complexes act as oxidation reduction indicators and sequestering reagents. Hardness of water is
estimated by use of EDTA.
4. Silver and gold are extracted by the use of complex formation.
5. Fixing of negative is done in photography by use of hypo solution. It forms soluble complex with
silver bromide.
6. During electroplating, complexes are used in electrolytue bath.
7. Cis-platin, [Pt(NH3)2Cl2], is used in the treatment of cancer.
British anti-lewisite (BAL) is used as antidote for treating poisoning by As, Hg, Au, Bi, Pb and Cd.
8. Haemoglobin is a complex of Fe, chlorophyll is complex of Mg, vitamin B12 is a complex of cobalt.
1. An aqueous solution of CoCl 2 on addition of excess 10. Assertion : [Co(NO 2 ) 3(NH 3 ) 3] does not show optical
of concentrated HCl turns blue due to formation of : isomerism.
(1) [Co(H2O)4Cl2] (2) [Co(H2O)2Cl4] 2– Reason : It has a plane of symmetry.
2–
(3) [CoCl4] (4) [Co(H2O)2Cl2] (1) If both Assertion and Reason are true and the
2. In whi ch of th e fo llo wi ng pairs, bo th th e co m- reason is the correct explanation of Assertion.
plexes show optical isomerism ? (2) If both Assertion and Reason are true but rea-
(1) cis-[Cr(C2O4)2Cl2]3–, cis-[Co(NH3)4Cl2] son is not the correct explanation of Assertion.
(2) [Co(en)3] Cl3, cis-[Co(en)2Cl2]Cl (3) If Assertion is true but Reason is false.
(3) [PtCl(dien)Cl] , [NiCl2Br2]2– (4) If both Assertion and Reason are false.
(4) [Co(NO3)3(NH3)3], cis-[Pt(en)2Cl2] 11. [Fe(NO2)3Cl3] and [Fe(O – NO)3Cl] shows :
3. The diamagnetic species is : (1) Linkage isomerism
(1) [Ni(CN)4]2– (2) [NiCl4]2– (2) Geometrical isomerism
2–
(3) [CoCl4] (4) [CoF6] 2– (3) Optical isomerism
4. The correct order for the wavelength of absorption in (4) None of the above
the visible region is : 12. Which of the following coordination entities should
(1) [Ni(NO2)6] 4– < [Ni(NH3)6] 2+ < [Ni(H2O)6] 2+ be expected to absorb light of lowest frequency?
(2) [Ni(NO2)6]4– < [Ni(H2O)6] 2+ < [Ni(NH3)6] 2+
(3) [Ni(H2O)6]2+ < [Ni(NH3)6]2+ < [Ni(NO2)6] 4+ (1) [Cr(en)3]3+ (2) [CrCl6]3–
3+
(4) [Ni(NH3)6] 2+ < [Ni(H2O)6] 2+ < [Ni(NO2)6] 4– (3) [Cr(NH3)6] (4) [Cr(CN)6]3–
5. Assertion : Potassium ferrocyanide is diamagnetic, 13. Assertion : When NO reacts with FeSO 4 , a brown
whereas potassium ferricyanide is paramagnetic. coloured complex is formed.
Reason : Crystal field splitting in ferrocyanide ion is Reason : In the complex, the coordination number
greater than that of ferricyanide ion. of Fe is 6.
(1) If both Assertion and Reason are true and the (1) Both A and R are true and R is the correct expla-
reason is the correct explanation of Assertion. nation of A.
(2) If both Assertion and Reason are true but rea- (2) Both A and R are true but R is not correct explana-
son is not the correct explanation of Assertion. tion of A
(3) If Assertion is true but Reason is false. (3) A is true but R is false
(4) If both Assertion and Reason are false. (4) A is false but R is true
6. Among the following, the species having square pla- (5) Both A and R are false
nar geometry for central atom are : 14. For the square planar complex [M(a) (b) (c) (d)] (where,
I. [XeF4] II. SF 4 M =central metal ; a, b, c and d are monodentate
III. [NiCl4] 2–
IV. [PtCl4] 2– ligands) the number of possible geometrical isomers
(1) I and IV (2) I and II are
(3) II and III (4) III and IV (1) 1 (2) 2
7. The pair in which both species have the same mag- (3) 3 (4) 4
netic moment (spin only) value is : 15. Assertion : CO and CN are referred as  acid ligands.
(1) [Cr(H2O)6]2+, [CoCl4]2– Reason : In CO and CN vacant  type orbitals are
(2) [Cr(H2O)6]2+, [Fe(H2O)6] 2+ present.
(3) [Mn(H2O)6] 2+, [Cr(H2O)6] 2+ (1) Both A and R are true and R is the correct expla-
(4) [CoCl4]2–, [Fe(H2O)6] 2+ nation of A.
8. The number of possible isomers of an octahedral com- (2) Both A and R are true but R is not correct explana-
plex [Co(C2O4)2(NH3)2] – is : tion of A
(1) 1 (2) 2 (3) A is true but R is false
(3) 3 (4) 4 (4) A is false but R is true
9. The ligands in anti-cancer drug cis-platin are : 16. Which one has the highest paramagnetism ?
(1) NH3,Cl (2) NH3H2O (1) Ni(CO)4 (2) [Co(NH3)6]Cl3
(3) Cl, H2O (4) NO, Cl (3) [Ni(NH3)6]Cl2 (4) [Cu(NH3)4]Cl2
17. Assertion : K4[Fe(CN)6] is diamagnetic and [Fe(H2O)6] (1) d4 (in strong field ligand)
Cl3 is paramagnetic. (2) d4 (in weak field ligand)
Reason : Hybridisation of central metal in [Fe(H2O)6]Cl3 (3) d3 (in weak as well as strong field ligand)
is sp3d2, while in K4[Fe(CN)6] is d2sp3. (4) d5 (in strong field ligand)
(1) Both A and R are true and R is the correct 29. Which one of the following complexes would exhibit the
explanation of A. lowest value of paramagnetic behaviour ?
(2) Both A and R are true but R is not correct
(1) [Co(CN)6]3– (2) [Fe(CN)6] 3–
explanation of A
(3) [Mn(CN)6] 3– (4) [Cr(CN)6]3–
(3) A is true but R is false
30. Nickel (Z = 28) combines with a uninegative
(4) A is false but R is true
monodentate ligand X– to form a paramagnetic complex
18. Which of the following is potassium ferricyanide? [NiX4] 2– The number of unpaired electron(s) in the nickel
(1) [K4[Fe(CN)6] (2) K3[Fe(CN)6] and geometry of this complex ion are, respectively :
(3) K3[Fe (CN)3] (4) K3[Fe(CN)4] (1) one, tetrahedral (2) two, tetrahedral
19. Which does not give a precipitate with AgNO 3 (3) one, square planar (4) two, square planar
solution?
31. The IUPAC name for the complex [Co(NO2) (NH3)5]Cl2
(1) [Co(NH3)6Cl3 (2) [Co(NH3)5Cl]Cl2 is :
(3) [Co(NH3)4Cl2]Cl (4) [Co(NH3)3Cl3] (1) Nitrito-N-pentaamminecobalt(III) chloride
20. In the complex ion [Co(NH 3 ) 6 ] 3+ , the NH 3 molecules
(2) Nitrito-N-pentaamminecobalt(II) chloride
are linked to the central metal ion by
(3) Pentaamminenitrito-N-cobalt(II) chloride
(1) ionic bonds (2) covalent bonds
(4) Pentaamminenitrito-N-cobalt(III) chloride
(3) coordinate bonds (4) hydrogen bonds
32. In Fe(CO)5, the Fe – C bond possesses :
21. A magnetic moment of 1.73 BM will be shown by one
among the following : (1) -character only
(1) [Ni(CN)4]2– (2) TiCl4 (2) both  and  characters
(3) [CoCl6]4– (4) [Cu(NH3)4]2+ (3) ionic character only
22. An excess of AgNO3 is added to 100 mL of a 0.01M (4) -character only
solution of dichlorotetraaquachromium (III) chloride. 33. How many EDTA (ethylenediaminetetraacetic acid)
The number of moles of AgCl precipitated would be : molecules are required to make an octahedral complex
(1) 0.002(2) 0.003 with a Ca2+ ion ?
(3) 0.01 (4) 0.001 (1) Six (2) Three
23. Among the following complexes the one which shows Zero (3) One (4) Two
crystal field stabilizations energy (CFSE) 34. The ‘spin only’ magnetic moment (in units of Bohr
(1) [Nn(H2O)6] 3+ (2) [Fe(H2O)6] 3+ magneton, µ B) of Ni 2+ in aqueous solution would be
(3) [Co(H2O)6] 2+
(4) [Co(H2O)6] 3+ (atomic number Ni = 28)
24. Which of the following complexes is used to be as an (1) 2.84 (2) 4.80
anticancer agent ? (3) 0 (4) 1.73
(1) mer – [Co(NH3)3Cl] (2) cis – [PtCl2(NH3)2] 35. Which one of the following has a square planar
(3) cis – K2[PtCl2Br2] (4) Na 2CoCu geometry?
25. The oxidation state of Cr in [Cr(NH3)4Cl2] + is : (1) [NiCl4]2– (2) [PtCl4] 2–
2–
(1) 0 (2) +1 (3) [CoCl4] (4) [FeCl4] 2–
(3) +2 (4) +3 (At. no. Co = 27, Ni = 28, Fe = 26, Pt = 78)
26. The IUPAC name of K3Fe(CN)6 is : 36. The coordination number and the oxidation state of
(1) Potassium hexacyanoferrate(II) the element 'E' in the complex [E(en)2(C2O4)] NO2 (when
(2) Potassium hexacyanoferrate(III) 'en' is ethylene diamine) are, respectively,
(3) Potassium hexacyanoiron(II) (1) 4 and 2 (2) 4 and 3
(4) Tripotassium hexacyanoiron(II) (3) 6 and 3 (4) 6 and 2
27. Which of the following will show optical isomerism 37. In which of the following octahedral complexes of Co (at
? no. 27), will the magnitude of 0 be the highest?
(1) [Cu(NH3)4]2+ (2) [ZnCl4] 2– (1) [Co(C2O4)3] 3– (2) [Co(H2O)6] 3+
3+
(3) [Cr(C2O4)3]3– (4) [Co(CN)6]3– (3) [Co(NH3)6] (4) [Co(CN)6]3–
28. The value of ‘spin only’ magnetic moment for one of 38. Which of the following has an optical isomer ?
the following configurations is 2.84 BM. The correct (1) [Co (en) (NH3)2] 2+ (2) [Co(H2O)4 (en)] 3+
one is : (3) [Co (en)2 (NH3)2] 3+
(4) [Co (NH3)3 Cl]+
39. Which of the following pairs represents linkage iso- (1) [Co(en)3] 3+
mers ? (2) [Co(en)2 Cl2]+
(1) [Pd(PPh 3)2 (NCS)2] and [Pd(PPh 3)2 (SCN)2] (3) [Co(NH3)3 Cl3]
(2) [Co(NH3)5 NO3] SO4 and [Co (NH3)5 (SO4)] NO3 (4) [Co(en) (NH3)2 Cl2] +
(4) [PtCl2 (NH3)4 Br2 and [Pt Br2 (NH3)4] Cl2 46. The octahedral complex of a metal ion M3+ with four
(4) [Cu (NH3)4] [Pt Cl4] and [Pt (NH3)4 [CuCl4] monodentate ligands L1, L2, L3 and L 4 absorb wave-
40. A solution containing 2.675 g of CoCl3 . 6NH3 (molar lengths in the region of red, green, yellow and blue,
mass = 267.5 g mol–1) is passed through a cation ex- respectively. The increasing order of ligand strength
changer. The chloride ions obtained in solution were of the four ligands is :
treated with excess of AgNO3 to give 4.78 g of AgCl (1) L4 < L3 < L2 < L1 (2) L1 < L3 < L2 < L4
(molar mass = 143.5 g mol–1). The formula of the com- (3) L3 < L2 < L4 < L1 (4) L1 < L2 < L4 < L3
plex is (At. mass of Ag = 108 u) 47. Potassium ferrocyanide is a
(1) [Co(NH3)6] Cl3 (2) [CoCl2 (NH3)4] Cl (1) Normal salt (2) Mixed salt
(3) [CoCl3(NH3)3] (4) [CoCl(NH3)5] Cl2 (3) Double salt (4) Complex salt
41. Which one of the following has an optical isomer ? 48. The chemical formula of diammine silver (I) chloride is
(1) [Zn(en)(NH3)2] 2+ (2) [Co(en)3] 3+ (1) [Ag(NH3)]Cl (2) [Ag(NH3)2]Cl
3+
(3) [Co(H2O) 4(en)] (4) [Zn(en)2] 2+ (3) [Ag(NH3)2]Cl (4) [Ag(NH4)2]Cl
(en = ethylenediamine) 49. A square planar complex represented as:
42. Which among the following will be named as NH2 NH2
dibromidobis (ethylene diamine) chromium (III) bro- CH2 CH2
mide?
(1) [Cr(en)3]Br3 (2) [Cr(en)2Br2]Br CH2 CH2
(3) [Cr(en)Br4]– (4) [Cr(en)Br2]Br H2N H2N
43. The magnetic moment (spin only) of [NiCl4] 2– is : (1) Geometrical isomerism
(1) 1.82 BM (2) 5.46 BM (2) Linkage isomerism
(3) 2.82 BM (4) 1.41 BM (3) Optical isomerism
44. Which of the following facts about the complex (4) None of these
[Cr(NH3)6]Cl3 is wrong ? 50. Which of the following facts about the complex
(1) The complex involves d 2sp 3 hybridisation and is [Cr(NH3)6]Cl3 is wrong:
octahedral in shape. (1) The complex involves d 2sp 3 hybridization and is
(2) The complex is paramagnetic. octahedral in shape
(3) The complex is an outer orbital complex. (2) The complex is paramagnetic
(4) The complex gives white precipitate with silver (3) The complex is an outer orbital complex
nitrate solution. (4) The complex gives white precipitate with silver
45. Which of the following complex species is not expected nitrate solution.
to exhibit optical isomerism ?
(Concept Builder)
1. Which of the following complex formed by Cu2+ ions is (1) [Cr(H2O)4Cl2]+ (2) [Pt(NH3)3 Cl]
most stable? (3) [Co(NH3)6] 3+
(4) [Co(CN)5(NC)]3–
 [Cu(NH3)4]2+, log K = 11.6
(1) Cu 2+ + 4NH3 
8. The CFSE for octahedral [COCl6] 4– is 18,000 cm–1. The
(2)  [Cu(CN)4]2–, log K = 27.3
Cu 2+ + 4CN–  CFSE for tetrahedral [COCl4] 2– will be
(3)  [Cu(en)2]2+, log K = 15.4
Cu 2+ + 2en  (1) 18,000 cm–1 (2) 16,000 cm–1
(4)  [Cu(H2O)4]2+, log K = 8.9
Cu 2+ + 4H2O  (3) 8,000 cm –1
(4) 20,000 cm–1
2. The colour of the coordination compounds depends 9. Due to the presence of ambident ate ligands
on the crystal field splitting. What will be the correct coordination compounds show isomerism. Palladium
order of absorption of wavelength of of light in the complexes of t he type [Pd(C 6 H 5 ) 2 (SCN)] 2 and
visible region, for the complexes, [Co(NH 3 ) 6 ] 3+ , [Pd(C6H5)2(NCS)2] are
[Co(CN)6] 3– , [Co(H2O)6] 3+? (1) linkage isomers
(1) 3– 3+
[Co(CN)6] > [Co(NH3)6] > [Co(H2O)6] 3+ (2) coordination isomers
(2) [Co(NH3)6] 3+ > [Co(H2O)6] 3+ > [Co(CN)6] 3– (3) ionization isomers
(3) [Co(H2O)6] 3+ > [Co(NH3)6] 3+ > [Co(CN)6] 3– (4) geometrical isomers.
10. The compoun ds [Co(SO 4 )(NH 3 ) 5 ]Br and
(4) [Co(NH3)6] 3+ > [Co(CN)6] 3– > [Co(H2O)6] 3+
[Co(SO4)(NH3)5]Cl represent
3. When 0.1 mol CoCl 3(NH 3) 5 is treated with excess of
(1) linkage isomerism
AgNO3, 0.2 mol of AgCl are obtained. The conductivity
(2) ionization isomerism
of solution will correspond to :
(3) coordination isomerism
(1) 1:3 electrolyte (2) 1:2 electrolyte
(4) no isomerism.
(3) 1:1 electrolyte (4) 3:1 electrolyte
11. A chelating agent has two or more than two donor
4. When 1 mol CrCl3.6H2O is treated with excess of AgNO3, atoms to bind to a single metal ion. Which of the
3 mol of AgCl are obtained. The formula of the complex following is not a chelating agent?
is : (1) Thiosulphate (2) Oxalato
(1) [CrCl3 (H2O)3]·3H2O (3) Glycinato (4) Ethane-1, 2-diamine
(2) [CrCl2(H2O)4]Cl·2H2O 12. Which of the following species is not expected to be a
(3) [CrCl(H2O)5]Cl2·H2O ligand?
(4) [Cr(H2O)6]Cl3 (1) NO (2) NH4+
(3) NH2CH2CH2NH 2 (4) CO
5. The correct IUPAC name of [Pt(NH3)2Cl2] is
13. What kind of isomerism exists between [Cr(H2O)6]Cl3
(1) diamminedichloridoplatinum (II)
(violet) and [Cr(H2O)5Cl)Cl2.H2O (greyish-green)?
(2) diamminedichloridoplatinum (IV)
(1) Linkage isomerism
(3) diamminedichloridoplatinum (I)
(2) Solvate isomerism
(4) dichloridodiammineplatinum (IV)
(3) Ionisation isomerism
6. The stabilization of coordination compounds due to
(4) Coordination isomerism
chelation is called the chelate effect. Which of the
14. IUPAC name of [Pt(NH3)2Cl(NO2)] is
following is the most stable complex species?
(1) platinum diaminechloronitrite
(1) [Fe(CO)5] (2) [Fe(CN)6] 3–
(2) chloronitrito-N-ammineplatinum (II)
(3) [Fe(C2O4)3] 3– (4) [Fe(H2O)6] 3+
(3) diamminechloridonitrito-N-platinum (II)
7. Indicate the complex ion which shows geometrical
(4) diamminechloronitrito-N-platinate (II).
isomerism.
• Instructions for Questions 1 to 10 8. Assertion : Potassium ferrocyanide is diamagnetic

Given below are two statements: One is labelled as Assertion where as potassium ferricyanide is paramagnetic.
(A) and the other is labelled as Reason (R).
Reason : Crystal field splitting in ferrocyanide ion is
In the light of the above statements, choose the most greater than that of ferricyanide ion.
9. Assertion : K 2 [PtCl 6 ] gives white ppt when reacts
with AgNO3.
explanation of (A)
(2) Both (A) and (R) are correct but (R) is not the correct Reason : Chloride ion in the complex is non-ionisable.
explanation of (A)
10. A s s e r t i o n : T r a n s [ C o C l 2( e n ) 2] + i s o p t i c a l l y
(3) (A) is correct the (R) is not correct inactive.
(4) (A) is not correct but (R) is correct
Reason : It has plane of symmetry.
1. Assertion : In the complex [Co(NH3)3 Cl3], chloride ions

satisfy the primary valencies as well as the secondary • Instructions for Questions 11 to 15
valencies of cobalt metal. Given below are two statements :
In the light of the above statements, choose the most appropriate
Reason : [Co(NH3)3Cl3] shows geometrical as well as
answer from the options given below :
optical isomerism.
(1) Both Statement I and Statement II are correct
2. Assertion : The complex [Cr(SCN)(NH3)5]Cl2 is linkage (2) Both Statement I and Statement II are incorrect
isomeric with [Cr(NCS)(NH3)5]Cl2.
(3) Statement I is correct but Statement II is incorrect
–
Reason : SCN is an ambident ligand in which there are (4) Statement I is incorrect but Statement II is correct
two possible coordination sites.
11. Statement I : The complex [Cr(SCN)(NH 3 ) 5]Cl 2 is
3. Assertion : [Co(NO 2) 3(NH 3) 3] does not show optical
linkage isomer with [Cr(NCS)(NH3)5]Cl2.
isomerism.
Statement II : SCN is an ambident ligand in which there
Reason : It has plane of symmetry.
are two coordination sites.
4. Assertion : In the co-ordination complex [Pt(NH3)4Cl2]
Br2, a yellow precipitate of AgBr is obtained on treat- 12. Statement I : The IUPAC name of K3[Cr(CN)6] is potas-
ing it with AgNO3 (aq). sium hexacyano chromate (III).
Reason : Bromide ions are present as counter ions in Statement II : It is an anion complex.
the ionization sphere.
13. Statement I : Charge on the complex of ferric ion with
5. Assertion : Co-ordination number of cobalt in the com- EDTA is minus one.
plex [Co(en)3] 3+ is six.
Statement II : EDTA is a hexadentate ligand.
Reason : Ethylenediamine acts as a bidentate ligand.
14. Statement I : Ti(H 2 O) 3+ is coloured ion while
6. Assertion : Charge on the complex of ferric ion with Sc(H 2 O)3+
6
is colourless.
EDTA is minus one.
Statement II : Ti3+ has 3d1 configuration whereas Sc3+
Reason : EDTA is a hexadentate ligand. has no unpaired electron and thus d-d transition is not
7. Assertion : The [Ni(en)3] Cl2 has higher stability than possible.
[Ni(NH3)6] Cl2. 15. Statement I : [Fe(H2O)5NO]SO4 is paramagnetic.
Reason : In [Ni(en)3] Cl 2, the geometry around Ni is Statement II : The Fe in [Fe(H 2O) 5NO]SO4 has three
octahedral.
unpaired electrons.
(Direct from
NCERT)
Match the List – I and List – II and choose the correct (2) (a) – (iv); (b) – (iii); (c) – (ii); (d) – (i)
combination from the options given. (3) (a) – (iii); (b) – (i); (c) – (vi); (d) – (ii)
(4) (a) – (i); (b) – (ii); (c) – (iii); (d) – (iv)
List – I List – II 4. Match List – I with List – II
(a) [Co(NCS)(NH3)5](SO3) (i) –1 List – I List – II
(b) Na[Co(CO)4] (ii) 0 (a) [Ma 3b 2c] (i) All stereoisomers are
(c) Na4[Co(S2O3)3] (iii) +1 optically inactive
(d) Co 2(CO)8 (iv) +2 (b) [Ma 3b 3] (ii) No. of geometrical
(v) +3 isomers = 2
Choose the correct answer from the options given below : (c) [Ma 3 bcd] (iii) No. of geometrical
isomer = 4
(1) (a) – (v); (b) – (i); (c) – (iv); (d) – (ii)
(d) [Ma 4 bc] (iv) Total 3 stereoisomers
(2) (a) – (iii); (b) – (i); (c) – (v); (d) – (ii)
(v) Only one enantiomeric
(3) (a) – (i); (b) – (iii); (c) – (vi); (d) – (i)
pair is possible
(4) (a) – (i); (b) – (iv); (c) – (v); (d) – (ii)
2. Match List – I with List – II (1) (a) – (iii, i); (b) – (i, ii); (c) – (i, v); (d) – (i, ii)
List – I List – II (2) (a) – (i, iv); (b) – (i, ii); (c) – (iii, v); (d) – (i, ii)
(a) Ni(CO)4 (i) sp3 (3) (a) – (i, ii); (b) – (v, i); (c) – (i, ii); (d) – (i, iv)
(b) [Ni(CN)4]2– (ii) ds p 2 (4) (a) – (i, iv); (b) – (i, ii); (c) – (i, iv); (d) – (i, ii)
(c) [Fe(CN)6] 4– (iii) sp 3 d 2 5. Match List – I with List – II
(d) [MnF6] 3– (iv) d 2 sp 3
(v) s p 2d
(a) Zeigler–Natta (i) Organomettali system
catalyst
(1) (a) – (i); (b) – (iv); (c) – (v); (d) – (ii)
(b) Wilkinson (ii) Chelating ligard
(2) (a) – (v); (b) – (i, iii); (c) – (iv); (d) – (ii)
catalyst present
(3) (a) – (i); (b) – (ii); (c) – (vi); (d) – (iii)
(c) Ethylenediaminetetra (iii) dsp 2 -hybridisation
(4) (a) – (iii); (b) – (i); (c) – (v); (d) – (ii) acetatocalcate (II) ion
3. Match List – I with List – II (d) cis-platin (iv) can show optical or
geometrical isomerism
(v) Having application
2-
(a) [Ni(CN)4] (i) tetrahedral in analytical
(b) [ZnCl4] 2- (ii) Tetragonal medicinal field
(c) [Co(en)3] 3+ (iii) Square planar Choose the correct answer from the options given below :
(d) [Cu(Cl4)]2- (iv) Square pyramid (1) (a) – (v); (b) – (i); (c) – (iv); (d) – (ii)
(v) Octahedral (2) (a) – (i); (b) – (iii); (c) – (ii); (d) – (v)
Choose the correct answer from the options given below : (3) (a) – (i); (b) – (iii); (c) – (vi); (d) – (i)
(1) (a) – (iii); (b) – (i); (c) – (v); (d) – (i) (4) (a) – (i); (b) – (iv); (c) – (v); (d) – (ii)
1. Which one of the folloiwng octahedral complexes will 7. Which of the following does not have a metal-carbon
not show geemetrical isomerism? (A and B are bond ? [AIPMT-2004]
monodentate ligands) [AIPMT-2003] (1) Al(OC2H5) 3 (2) C2H5MgBr
(1) [MA4B2] (2) [MA5B] (3) K[Pt(C2H4)Cl3] (4) Ni (CO)4
(3) [MA2B4] (4) [MA3B3] 8. CN– is strong field ligand. This is due to the fact that
2. According to IUPAC nomenclature sodium nitroprusside (1) it carries negative charge [AIPMT-2004]
is named as [AIPMT-2003]
(2) it is a pseudohalide
(1) sodium pentacyanonitrosyl ferrate (II)
(3) it can accept electrons form metal species
(2) sodium pentacyanonitrosyl ferrate (III)
(4) if forms high spin complexes with metal species
(3) sodium nitoferricyanide
9. Considering H2O as weak field ligand, the number of
(4) sodium nitroferrocyanide
unpaired electrons in [Mn(H2O)6] 2+ will be (At. no. of
3. The number of unpaired electrons in the complex ion Mn = 25) [AIPMT-2004]
[COF6] 3– is (At.no.of Co =27) [AIPMT-2003]
(1) 3 (2) 5
(1) 3 (2) 2
(3) 2 (4) 4
(3) 2 (4) 0
10. Among [Ni(CO) 4], [Ni(CN) 4] 2-, [NiCl 4] -2 species, the
4. Among the following which is not the bonded
hybridisation states of the Ni atom are, arespectively
organometallic compound ? [AIPMT-2003]
(At no.of Ni = 28) [AIPMT-2004]
(1) K[PtCl3 (- C2H4)] (2) Fe ( -C5H5)2
(1) sp3, dsp2. dsp2 (2) sp3, dsp2. sp2
(3) Cr (-C6H6)2 (4) (CH3)4 Sn
(3) sp3, sp3. dsp2 (4) dsp2, sp3. sp3
5. Which of the following coordination compounds would
11. Which one of the following is an inner orbital complex
exhibit optical isomerism ? [AIPMT-2003]
as well as diamagnetic in behaviour? (At.No. Of Zn =
(1) Pentaamminenitrocobalt (III) iodide
30, Cr =24, Co =27, Ni=28) [AIPMT-2005]
(2) Diamminedichloroplatinum (II)
(1) [Zn (NH3)6] 2+ (2) [Cr (NH3)6] 3+
(3) Trans-Dicyanobis (ethylenediamine)
(3) [Co (NH3)6] 3+ (4) [Ni (NH3)6] 2+
chromium (III) chloride
12. Which one of the following is expected to exhibit optical
(4) Tris- (ethylenediamine) cobalt (III) bromide
isomerism? (en = ethylenediamine) [AIPMT-2005]
6. Which of the following is considered to be an anticancer
(1) Cis- [Pt(NH3)2Cl2]
species? [AIPMT-2004]
(2) Trans - [Co(en)2 Cl2] +
CH2 (3) Trans- [ Pt (NH3)2 Cl2]
Cl
(4) Cis - [Co(en)2 Cl2] +
Pt CH2
(1) 13. [Co(NH3] 4 (NO2)2] Cl exhibits [AIPMT-2006]
Cl Cl (1) linkage isomerism, geometrical isomerism and
optical isomerism
(2) linkage isomerism, ionisation isomerism and optical
Cl Cl
isomerism
Pt (3) linkage isomerism, ionisation isomerism and
(2)
Cl Cl geometrical isomerism
(4) ionisation isomerism, geometrical isomerism and
optical isomerism
H3N Cl
14. [Cr (H2O)6] Cl3 (at no. of Cr = 24) has a magnetic moment
Pt of 3.83 BM. the correct distribution of 3d electrons in
(3)
H3N Cl the chromium of the complex is [AIPMT-2006]
(1) 3d 1xy ,31yz ,3d z1 2
H3N Cl (2) 3d x 2 ,3d ,3d 1yz

1
 y2 z2
Pt (3) 3d xy ,3d( x ,3d 1yz
(4) 2
y2 )
H3N Cl
(4) 3d 1xy ,3d 1yz ,3d zx1
15. The d electron configurations of Cr2+, Mn2+, Fe2+ and Ni2+ 25. The complex, [Pt(Py)(NH3)BrCl] will have how many
are 3d4, 3d 5,3d6 respectively. Which one of the following geometrical isomers [AIPMT-2011]
aqua complexes will exhibit the minimum paramagetic (1) 4 (2) 0
behaviour (At. No of Cr = 24, Mn = 25, Fe = 26, Ni = 28) (3) 2 (4) 3
[AIPMT-2007]
26. The complex [Co(NH 3) 6] [Cr(CN) 6 ] and [Cr(NH 3) 6 ]
(1) [Fe(H2O)6] 2+ (2) [Ni(H2O)6] 2+ [Co(CN)6] are the examples of which type of isomerism?
(3) [Cr(H2O)6] 2+ (4) [Mn (H2O)6] 2+ (1) Ionisation isomerism [AIPMT-2011]
16. Which of the following will give a pair of enantiomers ? (2) Coordination isomerism
(en = NH2CH2CH2NH2) [AIPMT-2007]
(3) Geometrical isomerism
(1) [Cr (NH3)6] [Co(CN)6]
(4) Linkage isomerism
(2) [Co(en)2 Cl2]Cl
27. Of the following complex ions ions which is diamagnetic
(3) [Pt (NH3)4] [PtCl6]
in nature [AIPMT-2011]
(4) [Co(NH3)4 Cl2] NO2
(1) [Ni(CN)4] 2- (2) [CuCl4] 2-
17. Which of the following complexes exhibits the highest
(3) [COF6] 3- (4) [NiCl4] 2-
paramagnetic behaviour ? Where, gly = glycine, en =
ethylendiamine and bpy = bipyridyl moities 28. Which one of the follwoing is an outer orbital complex &
exhibits paramagenetic behaviour? [AIPMT-2012]
(1) [V(gly) 2(OH)2 (NH3)2] + [AIPMT-2008]
2+
(1) [Ni (NH3)6] 2+ (2) [Zn (NH3)6] 2+
(2) [Fe (en) (py) (NH3)2]
(3) [Cr(NH3)6] 3+ (4) [Co (NH3)6] 3+
(3) [Co(ox)2 (OH)2] –
29. A magnetic moment of 1.73 BM will be shown by one
(4) [Ti(NH3)6] 3+
among the following [AIPMT-2013]
18. In which of the following coordination entities the
(1) [Cu(NH3)4] 2+ (2) [Ni (CN)4] 2-
magnitude of   (CFSE in octahedral field) will be
maximum? [AIPMT-2008] (3) TiCl4 (4) [CoCl6] 4-
(1) [Co (H2O)6] 3+
(2) [Co (NH3)6] 3+ 30. Which of the following complexes is used to be as an
3– anticancer agent [AIPMT-2014]
(3) [Co (CN)6] (4) [Co (C2O4)3] 3–
(1) Mer - [Co(NH3)3Cl3]
19. Which of the following does not show optical isomerism?
[AIPMT-2009] (2) Cis- [Ptcl2(NH3)2]
(1) [Co(en)2 Cl2] +
(2) [Co(NH3)3 Cl3] 0 (3) Cis-K2 [PtCl2 Br2]
(3) [Co)en) Cl2 (NH3)2] +
(4) [Co(en)3] 3+ (4) Na2CoCl4
20. Which of the following does not show optical isomerism 31. Among the following complexes, the one which shows
? (en= ethylenediammine) [AIPMT-2009] zero crystal field stabilasation energy (CFSE) is
(1) [Sc(H2O)3 (NH3)3] 3+ (2) [Ti(en)2 (NH3)2] 4+ [AIPMT-2014]
3+
(3) [Cr (NH3)6] 3+ (4) (Zn(NH3)3+ (1) [Mn(H2O6] (2) [Fe(H2O6] 3+
2+
21. Out of TIF6 , CoF6 , Cu2Cl2 and NiCl42– (At. no. Z of
2– 3– (3) [Co(H2O6] (4) [Co(H2O6] 3+
Ti = 22, Co = 27, Cu = 29, Ni = 28) the colourless 32. The name of complex ion [Fe(CN6)] 3– is
species are [AIPMT-2009] (1) hexacyanoiron (III) ion [AIPMT-2015]
(1) TIF62– and CoF63– (2) Cu2Cl2 and NiCl42– (2) hexacyanitoferrate (III) ion
(3) TIF22– and Cu2Cl2 (4) CoF63– and NiC42– (3) tricyanoferrate (III) ion
22. The existence of two different coloured complexes with (4) hexacyanidoferrate (III) ion
the composition of [Co(NH3)4 Cl2] + is due to 33. The sum of coordination number and oxidation number
(1) linkage isomerism [AIPMT-2010] of the metal M in the complex [M(en)2 (C2O4)Cl (Where,
(2) geometrical isomerism en is ethylendediamine) is [AIPMT-2015]
(3) coordination isomerism (1) 9 (2) 6
(4) ionisation isomerism (3) 7 (4) 8
23. Crystel field stabilisation energey for high spin d 4 34. The hybridisation involved incomplex [Ni(CN) 4] 2- is
octahedral comple is [AIPMT-2010] (Atomic number of Ni = 28) [AIPMT-2015]
(1) –1.80 (2) –1.60 + P (1) dsp2 (2) sp3
(3) –1.20 (4) – 0.60 (3) d2sp2 (4) d2sp3
24. Which of the following comlex ions is not expected to 35. Number of possible isomers for the complex [Co(en)2 Cl
absorb visible light? [AIPMT-2010] will be (en ethylendiamine) [AIPMT-2015]
(1) [Ni (CN)4] 2- (2) [Cr (NH3)6] 3- (1) 2 (2) 1
(3) [Fe (H2O6)4] 2+ (4) [Ni (H2O6)4] 2+ (3) 3 (4) 4
36. Which of these statements about [Co(CN)6] 3– is ture ? 45. An example of a sigma bonded organometallic compound
(1) [Co(CN)6] 3- has no unpaired electrons and will be is [NEET-2017]
in a low-spin configuration. [AIPMT-2015] (1) ruthenocene
(2) [Co(CN)6] 3- has four unpaired electrons and willbe (2) Gignard’s reagent
ina low-spin configuration. (3) ferrocence
(3) [Co(CN)6] 3- has four unpaired electrons and will be (4) cobaltocene
in a low -spin configuration
46. The type of isomerism shown by the complex CoCl2 (en)2]
(D) [Co(CN)6] 3- has no unpaired electrons and will be is [NEET-2018]
in high -spin configuration.
(1) Ionization isomerism
37. Cobalt (III) chloride forms several octahedral complexes
(2) Coordination isomerism
with ammonia. Which of the following will not give test
for chloride ions with silver nitrate at 250C ? (3) Geometrical isomerism
[AIPMT-2015] (4) Linkage isomerism
(1) CoCl3. 3NH3 (2) CoCl3. 4NH3 47. The geometry and magnetic behaviour of the complex
(3) CoCl3.5NH3 (4) CoCl3. 6NH3 [Ni(CO)4 ] are [NEET-2018]
38. Jahn-Teller effectg is not observed in high spin complexes (1) square planar geometry and paramagnetic
of [NEET-2016] (2) tetrahedral geometry and diamagnetic
(1) d 7 (2) d8 (3) square planar geometry and diamagnetic
(3) 8 4 (4) d9 (4) tetrahedral geometry and paramagnetic
39. The correct increasin order of trans-effect of the following 48. Iron carbonyl, Fe(CO)5 is [NEET-2018]
species is [NEET-2016] (1) trinuclear (2) mononuclear
(1) NH3 > CN = > Br– > C6H5– (3) tetranuclear (4) dinuclear
(2) CN– > C6H5- > Br– NH3
49. What is the correct electronic configuration of the cen-
(3) Br– > CN– > NH3 > C6H5– tral atom in K4[Fe(CN)6] based on CFT [NEET-2019]
(4) CN– > Br- > C6H5 > NH3 4
(1) t2 g eg
2 6
(2) t2 g eg
0
40. Which of the follwing pairs of d-orbitals will have (3) e t23 3
(4) e t24 2
electrondensity along the axis ? [NEET-2016]
50. Which of the following is the correct order of increasing
(1) d z 2 , d xz (2) dxz, d yz
field strength of ligands to form coordination com-
(3) d 2, d (4) d xy , d x  y
2 2
pounds? [NEET-2020]
41. Which of the following has longest C — O bond length? – –
(1) SCN < F < CN < C2O4 – 2–
(Free C — O bond length in CO is 1.128A.)
(2) F– < SCN– < C2O42– < CN–
[NEET-2016]
– (3) CN– < C2O42– < SCN– < F–
(1) [Co(CO)4] (2) [Fe (CO)4] 2–
(3) [Mn(CO)6] +
(4) Ni (CO)4 (4) SCN– < F– < C2O42– < CN–
42. Pick out the correct statement with respect to [Mn(CN)6]3– 51. Match the coordination number and type of hybridisation
[NEET-2017] with distribution of hybrid orbitals in space based on
Valence bond theory.
(1) It is sp 3d2 hybridised and octahedral
Coordination No. Distribution of hybrid
(2) It is sp 3 d2 hybridised and tetrahedral
& type of hybri. orbitals in space
(3) It is d 2sp3 hybridised and octahedral
(a) 4, sp3 (i) trigonal
(4) It is dsp 2 hybridised and square planar
bipyramidal
43. Correct increasing order for the wavelengths of absorption
(b) 4, dsp2 (ii) octahedral
in the visible region for the complexes of CO3+ is
[NEET-2017] (c) 5, sp3d (iii) tetrahedral
(1) [Co(en)3] 3+ ,[Co(NH3)6] 3+ [Co(H2O6)] 3+ (d) 6, d2sp3 (iv) square planar
(2) [Co(H2O)6] 3+ ,[CO(en3)] ]3+, [Co(NH3)6] 3+ Select the correct option : [NEET-2020]
(3) [Co(H2O6)3] 3+ ,[Co(NH3)3+], [Co(NH3)6] 3+ (1) (a)-(ii) (b)-(iii) (c)-(iv) (d)-(i)
(4) [Co(NH3)6] 3+ ,[Co(en3)3+], [Co(H2O)6] 3+ (2) (a)-(iii) (b)-(iv) (c)-(i) (d)-(ii)
44. The correct order of the stoichiometrics of AgCl formed (3) (a)-(iv) (b)-(i) (c)-(ii) (d)-(iii)
when AgNO3 in excess is treated with the complexes : (4) (a)-(iii) (b)-(i) (c)-(iv) (d)-(ii)
CoCl3 6NH3 , CoCl3. 5NH3 . 4NH3 respectively is 52. Tritium, a radioactive isotope of hydrogen, emits which
(1) 1 AgCl, 3AgCl, 2AgCl [NEET-2017] of the following particles ? [NEET-2021]
(2) 3 AgCl, 1AgCl, 2AgCl (1) Beta ( –) (2) Alpha ()
(3) 3 AgCl, 2Agcl, 1AgCl (3) Gamma () (4) Neutron (n)
(4) 2 AgCl, 3AgCl, 1AgCl
53. Ethylene diaminetetraacetate (EDTA) ion is : 56. Given below are two statements : one is labelled as As-
(1) Hexadentate ligand with four "O" and two "N" sertion (A) and the other is labelled as Reason (R).
donor atoms [NEET-2021] [NEET-2022]
(2) Unidentate ligand Assertion (A): The metal carbon bond in metal carbonyls
(3) Bidentate ligand with two "N" donor atoms possesses both  and  character..
(4) Tridentate ligand with three "N" donor atoms Reason (R): The ligand to metal bond is a  bond and
54. Match List-I with List-II [NEET-2021] metal to ligand bond is a  bond.
List-I List-II In the light of the above statements, choose the most ap-
propriate answer from the options given below:
(a) [Fe(CN)6] 3– (i) 5.92 BM
(b) [Fe(H2O)6] 3+ (ii) 0 BM
explanation of (A)
(c) [Fe(CN)6] 4– (iii) 4.90 BM
2+
(2) Both (A) and (R) are correct but (R) is not the
(d) [Fe(H2O)6] (iv) 1.73 BM correct explanation of (A)
Choose the correct answer from the options given below: (3) (A) is correct but (R) is not correct.
(1) a–iv, b–ii, c–i, d–iii (2) a–ii, b–iv, c–iii, d–i (4) (A) is not correct but (R) is correct.
(3) a–i, b–iii, c–iv, d–ii (4) a–iv, b–i, c–ii, d–iii 57. The IUPAC name of the complex
55. Match List-I with List-II [NEET-2022] [Ag(H2O)2][Ag(CN)2] is: [NEET-2022]
List-I List-II (1) dicyanidosilver(I) diaquaargentate(I)
(Complexes) (Types) (2) diaquasilver(I) dicyanidoargentate(I)
(a) [Co(NH3) 5NO2]Cl2 (i) Ionisation (3) dicyanidosilver(II) diaquaargentate(II)
& [Co(NH3)5ONO]Cl2 isomerism (4) diaquasilver(II) dicyanidoargentate(II)
(b) [Cr(NH3)6] [Co(CN)6] (ii) Coordination 58. The order of energy absorbed which is responsible for
& [Cr(CN)6] [Co(NH3)6] isomerism the color of complexes [NEET-2022]
(c) [Co(NH3)5(SO4)]Br (iii) linkage (i) [Ni(H2O)2(en)2] 2+
& [Co(NH3)5Br]SO4 isomerism (ii) [Ni(H2O)4(en)] 2+ and
(d) [Cr(H2O)6]Cl3 & (iv) solvate (ii) [Ni(en)3] 2+ is
[Cr(H2O)5Cl]Cl2.H2O isomerism (1) (iii) > (i) > (ii)
Choose the correct answer from the options given below: (2) (ii) > (i) > (iii)
(1) a–iii, b–i, c–ii, d–iv (2) a–ii, b–iii, c–iv, d–i (3) (i) > (ii) > (iii)
(3) a–iii, b–ii, c–i, d–iv (4) a–iv, b–iii, c–ii, d–i (4) (iii) > (ii) > (i)
9.15
DAILY PRACTICE PROBLEM (DPP) – 01 MISCELLANEOUS QUESTIONS FROM NCERT
1. (1) 2. (3) 3. (2) 4. (4) 5. (4) 1. (2) 2. (2) 3. (4) 4. (1) 5. (3)
6. (3) 7. (2) 8. (3) 9. (4) 10. (3) 6. (1) 7. (2) 8. (3) 9. (1) 10. (1)
11. (1) 12. (2) 13. (2) 14. (1) 15. (1)
16. (3) 17. (3) 18. (2) 19. (4) 20. (2)
11. (2) 12. (1) 13. (1) 14. (2) 15. (2) 21. (4) 22. (4) 23. (2) 24. (2) 25. (4)
16. (2) 17. (3) 18. (3) 19. (1) 20. (4) 26. (2) 27. (3) 28. (1) 29. (1) 30. (2)
21. (3) 22. (4) 23. (4) 24. (3) 25. (3) 31. (4) 32. (2) 33. (3) 34. (1) 35. (2)
36. (3) 37. (4) 38. (3) 39. (1) 40. (1)
41. (2) 42. (3) 43. (3) 44. (2) 45. (3)
26. (2) 27. (4) 28. (2) 29. (4) 30. (2) 46. (2) 47. (4) 48. (2) 49. (4) 50. (3)
31. (2) 32. (1) 33. (1) 34. (3) 35. (4)
1. (2) 2. (3) 3. (2) 4. (4) 5. (1)
6. (3) 7. (1) 8. (3) 9. (1) 10. (4)
41. (4) 42. (2) 43. (4) 44. (1) 45. (1) 11. (1) 12. (2) 13. (2) 14. (3)
46. (4) 47. (2) 48. (3) 49. (4) 50. (2)
51. (1) 52. (3) 53. (2) 54. (2) 55. (1) ASSERTION–REASON & STATEMENT QUESTIONS
1. (3) 2. (1) 3. (1) 4. (1) 5. (1)
6. (2) 7. (2) 8. (3) 9. (4) 10. (1)
56. (4) 57. (2) 58. (3) 59. (2) 60. (2) 11. (1) 12. (2) 13. (2) 14. (1) 15. (1)
61. (3) 62. (1) 63. (1) 64. (2) 65. (1)
66. (2) 67. (3) 68. (3) 69. (2) 70. (2) MATRIX TYPE QUESTIONS
DAILY PRACTICE PROBLEM (DPP) – 06 1. (1) 2 (3) 3. (1) 4. (2) 5. (2)
71. (3) 72. (3) 73. (3) 74. (4) 75. (1) ARCHIVE QUESTIONS
76. (1) 77. (1) 78. (1) 79. (3) 80. (2)
81. (1) 82. (3) 83. (4) 84. (4) 85. (3) 1. (2) 2. (2) 3. (3) 4. (4) 5. (4)
86. (4) 87. (2) 88. (1) 89. (4) 90. (3) 6. (3) 7. (1) 8. (2) 9. (2) 10. (2)
11. (3) 12. (4) 13. (3) 14. (4) 15. (2)
21. (3) 22. (2) 23. (4) 24. (1) 25. (2)
91. (1) 92. (2) 93. (3) 94. (2) 95. (1)
96. (4) 97. (2) 98. (4) 99. (2) 100. (3) 26. (1) 27. (1) 28. (1) 29. (1) 30. (2)
101. (4) 102. (1) 103. (4) 104. (4) 105. (1) 31. (2) 32. (4) 33. (2) 34. (1) 35. (3)
36. (1) 37. (1) 38. (2) 39. (2) 40. (3)
46. (3) 47. (2) 48. (2) 49. (2) 50. (4)
106. (4) 107. (2) 108. (4) 109. (2) 110. (1)
51. (2) 52. (1) 53. (1) 54. (4) 55. (3)
111. (2) 112. (3) 113. (4) 114. (4) 115. (2)
116. (2) 117. (2) 118. (1) 119. (4) 120. (2) 56. (3) 57. (2) 58. (1)

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CHEMISTRY

Percentage of Questions in Last 34 Years' in NEET / AIPMT from this Chapter

A. Order of Reaction 45%

WHAT DO YOU WANT TO KNOW? 4.4 TEMPERATURE DEPENDENCE OF THE RATE OF

Explained by Order Integrated Rate constant

Temperature Concentration Catalyst Heterogenous

Single Complex - many Decides rate

4.0 INTRODUCTION P.No.: 95

4.1 RATE OF A CHEMICAL REACTION P.No.: 96

 The change in concentration of either reactant or product per unit time.

AVERAGE RATE OF REACTION P.No.: 97

(–) Change in the concentration of reactants Product

Unit of concentration gram mole

INSTANTANEOUS RATE OF THE REACTION P.No.: 98

in terms of the concentrations of N2, H2 and NH3 can be expressed as :

4.2 FACTORS AFFECTING THE RATE OF REACTION P.No.: 100

NCERT LIKE PROBLEM NCERT P.No.-98

NCERT LIKE PROBLEM NCERT P.No.-98

(a) Rate of disappearance of A = Rate of disappearance of B

2. In a catalytic conversion of N 2 to NH 3 by Haber’s

4.2.1 P.No.: 100

4.2.2 P.No.: 100

4.2.3 P.No.: 102

ELEMENTARY REACTION P.No.: 102

COMPLEX REACTIONS P.No.: 102

NCERT LIKE PROBLEM NCERT P.No.-102

NCERT LIKE PROBLEM NCERT P.No.-102

Rate mol L–1s 1 s 1

NCERT LIKE PROBLEM NCERT P.No.-102

4.2.4 P.No.: 102

NCERT LIKE PROBLEM NCERT P.No.-103

(C) r = k [A]n ...(i) ; 2r = k [4A]n ...(ii)

NCERT LIKE PROBLEM NCERT P.No.-103

NCERT LIKE PROBLEM NCERT P.No.-103

(D) r = k [X2]1/2 [Y2]1

NCERT LIKE PROBLEM NCERT P.No.-103

Rate = k [Reactant]n = 4a ; rate = 2r1

02 14. For a reactions A + B  product, it was found that rate

4.3 INTEGRATED RATE EQUATIONS P.No.: 105

4.3.1 P.No.: 105

4.3.2 P.No.: 106

 Reactions in which the rate of reaction is directly proportional to concentration of reactant.

 Unit of rate constant : [k = time–1]

4.3.3 P.No.: 110

The time in which half of the initial amount of reactant is consumed.

NCERT LIKE PROBLEM NCERT P.No.-106

NCERT LIKE PROBLEM NCERT P.No.-106

NCERT LIKE PROBLEM NCERT P.No.-106

For first order reaction

NCERT LIKE PROBLEM NCERT P.No.-106

2.303 C 2.303 C t log 4 2log 2

SECOND ORDER REACTIONS (NOT IN NCERT)

NCERT LIKE PROBLEM NCERT P.No.-106

NCERT LIKE PROBLEM NCERT P.No.-106

NCERT LIKE PROBLEM NCERT P.No.-106

0.693 0.693 0.693

HALF-LIFE METHOD P.No.: 110