Chemistry Booklet No 4 Engineering

CHEMISTRY
for
Joint Entrance Examination (JEE)
Mains & Advanced
Maharashtra - Common Entrance Test
(MHT-CET)
1. CHEMICAL KINETICS
2. SOLID STATE
3. IUPAC NOMENCLATURE & STRUCTURAL
ISOMERISM
4. STEREOISOMERISM
Chaitanya's aCademy
Study Material
CHEMICAL KINETICS
CONTENTS
TOPIC PAGE NO.
KEY CONCEPTS 1-12
TEST YOUR UNDERSTANDING & MSPs 13-34
BOARD LEVEL EXERCISE 35-36
EXERCISE # 1 37-52
EXERCISE # 2 53-62
EXERCISE # 3 62-70
HINTS AND SOLUTIONS 71-90
ADVANCED LEVEL PROBLEMS 91-104
SOLID STATE
CONTENTS
TOPIC PAGE NO.
KEY CONCEPTS 105-120
EXERCISE # 1 130-136
IUPAC NOMENCLATURE &

STRUCTURAL ISOMERISM
CONTENTS
TOPIC PAGE NO.
KEY CONCEPTS-IUPAC NOMENCLATURE 189-215
KEY CONCEPTS-STRUCTURAL ISOMERISM 216-224
STEREOISOMERISM
CONTENTS
TOPIC PAGE NO.
KEY CONCEPTS-IUPAC NOMENCLATURE 297-316
CHEMICAL KINETICS
1 CHEMICAL KINETICS Chemistry
KEY CONCEPTS (b) C + O2 Room

 temperatur
  e  CO2
1. Introduction (c) CO + 2H2 Room

 temperatur
  e  CH3OH
The branch of physical chemistry which deals

(d) Rusting of iron
with the rate, mechanism of a chemical reaction
and influence of various factors such as 2.3 Moderate reactions :
concentration, temperature, pressure, catalyst (i) These are the reactions which takes place at
on the rate of chemical reaction is called moderate and measurable rates at room
Chemical Kinetics. temperature and only these reactions are
studied in chemical kinetics.
2. Types of Reactions
(ii) Most of these reactions are molecular in
On the basis of their rates, the chemical reactions nature.
have been classified into the following three eg. (a) 2H2O2  2H2O + O2
types. (b) 2N2O5  2N2O4 + O2
2.1 Very fast or Instantaneous reaction : (c) CH3COOC2H5 + NaOH CH3COONa
(i) These reaction are so fast, they occur as soon + C2H5OH
as the reactants are brought together. (d) C12H22O11 + H2O C6H12O6 + C6H12O6
(ii) These are mostly ionic reaction and do not (e) NO2 + CO  NO + CO2
involve any type of bond fission and
(f) 2FeCl3 (aq) + SnCl2  2FeCl2 (aq)
formation between atoms.
+ SnCl4 (aq)
Reason :
(g) decolorization of acidified potassium
(i) The ionic reactants are already present in permanganate with sodium oxalate.
ionic state in their aqueous solution and thus
this type of reactions occur very fast or 3. Rate of reaction
instantaneously due to columbic forces
among ions. Rate of the reaction defined as the ratio of
change in concentration of reactant or product to
(ii) The rate of such type of reactions are very
the time required to produce that change i.e.
fast. So, it is very difficult to determine the
rate of these reactions. Rate of reaction
eg. (a) Ag+(aq)+NO3–(aq)+H+(aq)+Cl–(aq)  change in concentration of reactant
   AgCl(s) + H+(aq) + NO3–(aq) c or product(in mol L–1 )
= =
(b) Na+(aq) + OH–(aq) + H+(aq) + Cl–(aq)  t time (in second)
H2O() + Na+(aq) + Cl–(aq) Consider following reaction
2.2 Very Slow reaction : A  Products
(i) These reactions are extremely slow and take t=0 a mol L–1
months together to show any measurable t = t sec (a – x) mol L–1 × mol L–1
change at room temperature.
x
(ii) The rate of such type of reactions are very average rate of reaction =
t
slow. So, it is also very difficult to determine
Note :
the rate of these reactions.
(i) Normally, the rate of reaction changes with
eg.
time and hence it should be expressed as
(a) 2H2 + O2 Room
 temperatur
 e  2H2O dx
instantaneous rate as, r =
t
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(ii) Graphically rate of reaction can be Rate measured for a definite time interval is
determined by curve between concentration called average rate of reaction.
and time
c 2 – c1
rate(avg) = where c2 & c1 are
t 2 – t1
t concentration at time t2 & t1 respectively

(ii) Instantaneous rate of reaction :
Concentration Rate measured for an infinitesimilly small
of reactant time interval is called instantaneous rate of
x
reaction.
 c 
r(inst.) = lim  
t  0
 t 
time
dc
The slope of the above curve gives rate of =
dt
reaction.
3.2 Reaction life time : It is defined as the time
x
i.e. tan = = rate of reaction taken by the reaction to proceed almost
t
completely.
(iii) Unit for rate of reaction is mole L–1 sec–1.
3.3 Half life time : It is defined as the time taken
(iv) The change is concentration of different
reaction components, in the same time, may by reaction to proceed to 50% completion
differ according to the balanced chemical i.e. concentration of reactant decreases to
reaction and hence the rate is normaly half of its initial value. It is denoted by t1/2 or
expressed as change in concentration per t50.
unit time per mol of that substance. 3.4 Generation time : In biological processes
Consider a general reaction. time taken by certain virus or bacteria to
m1A + m2B  n1P + n2Q double its population or colony is called
generation time.
1 d[ A ] 1 d[B]
rate of reaction = – =–
m 1 dt m 2 dt 4. Rate Law & Rate Constant
1 d [P] 1 d [Q ]
= = At a given temperature, the rate of a reaction at
n 1 dt n 2 dt
a particular instant is proportional to the product
e.g. N2 + 3H2  2NH3 of the active masses of the reactants raised to
–d [N 2 ] 1 d [H 2 ] 1 d [ NH3 ] the exerimentally determined powers.Consider a
rate = = – =
dt 3 dt 2 dt general reaction
Note : Here, –ve sign represent the aA + bB  products
decrease in concetration with time and +ve rate [A]x [B]y ; rate = k [A]x [B]y
sign, increase in concetration with time. Here k is velocity constant or rate constant or
3.1 Classification of rate of reaction : specific rate of reaction & x and y are
Rate of reaction can be classified into two experimently determined values.
categories If [A] = [B] = 1 or rate = k
(i) Average rate of reaction :

So rate constant is defined as rate of reaction 4.2 Units of rate constant :

when concentration of all reactants is taken
Unit of rate constant
unity.
n –1
 1 
4.1 Factors affecting rate constant : =  × time–1
 unit of conc. 
Value of rate constant depends on following
n –1
factors  litre 
=  × second–1
(i) Temperature  mole 
(ii) Catalyst where n is the order of reaction .
Note :– Above factors will be discussed after

collision theory.
4.3 Difference between rate of reaction and rate

constant :
Rate of reaction Reaction rate constant
1. Rate of reaction is called as the change in 1. Rate constant is the proportionality constant in
the concentration of the reactant or rate law equation. When molar concentration of
product per unit time. reactants is taken as unity, its value is equal to
rate of reaction.
2. Rate of reaction varies with concentration of 2. Since it is proportionality constant for a particular
the reactant reaction, it is independent of the concentration of
the reactant.
3. The units of rate of reaction is mole litre–1 3. The units of reaction rate constant depends upon
time–1 irrespective to the order of reaction. the order of reaction i.e. its unit differs
according to order of reaction.

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aA + bB + cC  Product
5. Molecularity of Reaction
Let rate of reaction depends on the product
of concentrations of A, B and C raised to the
(i) For elementary or single step reactions power ,  and  respectively. So we can
the molecularity is defined as the write rate law for above reaction.
number of molecules of reactants
rate = k[A] [B] [C] (k is rate constant)
involved in the balanced stoichiometric
equation. Here sum of power of concentration terms
involved in rate law expression is called
Eg. PCl5  PCl3 + Cl2
order of reaction or overall order of
(Unimolecular)
reaction.
2HI  H2 + I2
 = order (n)
(Bimolecular)
 are order of reaction w.r.t. A, B &
2SO2 + O2  2SO3
C respectively.
(Trimolecular)
Note :
(ii) But for multi step reactions the
molecularity is defined as the minimum (i) If  = a,  = b &  = c then order of
number of reacting particles reaction
(molecules, atoms or ions) taking part in = molecularity of reaction. Such
slowest step or rate determining step reaction will be definitely single step
(RDS) of chemical reaction. reaction.
(a) eg. (ii) Order is an experimently determined
H2O2  H2O + O (Slow) quantity.
(iii) It may be zero, positive, negative,
O + O  O2 (Fast) fractional and greater than three.
(iv) Infinite and imaginary values are not
2H2O2  2H2O + O2
possible.
(Unimolecular)
(b) eg. (v)  ,  and  are not stoichiometric
coefficients as used in law of mass
NO2 + F2  NO2F + F (Slow)
action. Actually, law of mass action
NO2 + F  NO2F (Fast) applicable only on elementary chemical
2NO2 + F2  2NO2F reactions, for which order and
(Bimolecular) molecularity are same.
Note : e.g.
(i) Molecularity is theoretical concept. (a) N2O5  N2O4 + 1/2 O2
(ii) Molecularity can not be zero, rate = k [N2O5] (from experiment)
negative or fractional. order is unity or first
(iii) Molecularity can not be more than (b) 2NO2 + F2  2NO2F
3.
rate = k [NO2] [F2] (from
experiment)
6. Order of Reaction
order is two or second
:
Consider a general reaction

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6.1 Pseudo unimolecular reactions : 1  1 1 

or k  – 
In second order reaction, when one n –1
t (n – 1)  [ A] t [A] 0n –1 
reactant is present in large excess, the ...(2)
second order reaction confirms to the first Case 2 :
order and is known as Pseudo unimolecular
when n = 1, on integration of
reaction.
equation (1)
e.g.
–loge (a – x) = kt + C
H
CH3COOC2H5+H2O  at t = 0 ; x = 0  c = – logea
CH3COOH+C2H5OH
or logea – loge (a–x) = kt
molecularity = 2 ; order = 1 (H2O in excess)
2.303  a 
k= log 
7. Integrated Rate Laws t a –x
...(3)
another form of above equation is
Differential equation (rate laws) obtained
from experimental data or mechanism of 2.303 [A ]0
k log
reaction can be integrated for certain time t [A ]t
period to get the concentrations of reaction
or [A]t  [A]0 e –kt
components.
...(4)
7.1 Kinetics of nth order : (it is known as wilhelmy eq.)
Consider the reaction A  product ; From above equation we conclude
which is nth order reaction so 1
(a) t 1  n –1
and
dx c
= k (a – x)n 2
dt
dx 1
or, = kdt (b) graph between versus t is
(a – x ) n (a – x ) n –1
integrating both side. linear.
dx
7.2 Zero order reactions :
 (a – x ) n
=  kdt
Reactions whose rate is not affected by
.....(1) concentration of reactants or rate of
Case 1 : reaction is proportional to the zeroth
power of concentration of the
when n  1, on integration of reactants.
equation (1) Consider a reaction
1 1 A  Product
. = k. t + C
(n – 1) ( n – 1) n –1 dx
= k [A]º = k
dt
at t = 0 x=0
7.2.1 Some photochemical reactions,
1 1 hetrogeneous reactions and
C= . n –1 enzyme catalyzed reactions are
(n – 1) (a ) zero order reactions.
h
1 1  1 1  e.g. (i) H2+Cl2  2HCl [photo
so k =  n –1
– n –1  chemical]
t (n – 1)  (a – x ) a 

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(ii) 2HI gold

 H2 + I2 7.3 First order reactions :
surface
[hetrogeneous A reaction is called first order if its rate is

adsorption] determined by the change of one
(iii) 2NH3 Mo
 N2 + 3H2 concentration term only i.e. rate is
[hetrogeneous proportional to unity power of
adsorption] concentration term.
pt
(iv) N2O  N2 + ½O2 7.3.1 Example of first order reactions :

(v) Enzyme catalyzed reactions (i) H2O2  H2O + ½O2

eg. substrate enzyme

 Product (ii) NH4NO2  N2 + 2H2O
rate = k [enzyme]1 [substrate]0 (iii) C6H5N2Cl + H2O C6H5OH + N2 +
7.2.2 Integrated rate law : HCl
Putting the value n = 0 in (iv) (CH3)3COOC(CH3)32CH3COCH3+ C2H6
equation (2), we get
di–tertbutyl peroxide
[A]t = [A]0 – kt
(v) N2O5  2NO2 + ½O2
7.2.3 Half life (t½) :
(vi) (CH3)2CHN2CH(CH3)2  N2 +
a
At t = t½ x = C6H14
2
from eq (1) Azoiso propane
a (vii) SO2Cl2  SO2 + Cl2
t½ = or t½  a
2k (viii) Radio active decay, virus or
so half life is directely bacteria generation or
proportional to the initial
inactivation.
concentration of the reactant.
7.2.4 Graphical representation & unit 7.3.2 Integrated rate law :
of rate constant from equation (3) and (4)
(a) 2.303 [A]0
k= log
t [ A ]t
or [A]t = [A]0e–kt
dx 7.3.3 Half life (t½) :

(rate)
dt Zero order a
at t = t½ x =
2
2.303  2a 
from eq (1) k = log 
(a – x) t1 / 2  2 
concentration
0.693
k=
t1 / 2
(b) Unit of rate constant
n –1
i.e. t½ does not depend on initial
 L  –1 concentration of reactant.
unit of k =   × time ,
 mole 
7.3.4 Graphical representation & unit
n=0
of rate constant
so unit of k = mol L–1sec–1 i.e. unit
of rate of reaction.

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(a) (a) 2A 

product
t=0 a or [A]0 x/2
log of conc.
 t=t a–x or [A]t
1 x
from equation (2) k =
t a (a – x )
time
2.303 1 1 1 
slope = tan = or k=  – 
k t  [ A]t [ A]0 
2.303 a (b) Consider another reaction
t= log
k a–x A + B 
y = mx + C product
2.303 t=0 a b
here slope = m =
k t=t a–x b–x x
n –1
 L  dx
(b) Unit of rate constant =   × = k(a – x) (b – x)
 mol  dt
time–1 on integrating
n=1 2.303 b (a – x )
–1
k= log10
so unit of k = sec t (a – b) a (a – x )
7.4 Second order reaction (Only for REE Note :
aspirants.) : (i) In above equation (a > b)
A reaction is called second order (ii) Type (b) reactions i.e.
reaction if it is depend on two A + B  product, can be
concentration terms. converted into first order reaction
7.4.1 Example : if one reactant is in excess.
(i) CH3 COO C2H5 +NaOH  i.e. if a >>> b
CH3COONa then (a – x) a and (a – b)a
+ 2.303 ba
k= log10
C2H5OH ta a (b – x )
2.33  b 
(Saponification) or ka = k´ = log 
t b–x
(ii) 2 NO2  2 NO + O2
(iii) 2 O3  3O2 (First order kinetics)
(iv) 2 Cl2O  2 Cl2 + O2 7.4.3 Graphical representation & unit
(v) 2CH3CHO  2CH4 + 2CO of rate constant
(vi) S2O82- + 2I  2SO42- + I2
(Persulphate ion)
7.4.2 Second order kinetics can be
applied on two types of reactions
viz.
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7.6 First order growth reaction :

For bacteria multiplication or virus
1
growth use following concept
(a – x )
consider a growth reaction
Second order
Time Population (or
time colony)
n –1 0 a
 L 
Unit of k =    time –1 dt (a + x)
 mol 
dx dx
n = 2 So unit of k = L mol–1 sec–1 = k(a+x) or = kdt
dt (a  x )
7.4.4 Half life (t½) :
on integration
For second order reactions of
loge (a+x) = kt + C
type
(a) 2A  product. at t = 0; x = 0  C = logea
a a
kt = –loge or k
at t = t½ x= ax
2
1
2.303  a 
= – log10   or
 t½ = t ax
ka
t½ is inversely proportional to the 2.303 ax
k= log10  
initial concentration of the t  a 
reactant 7.6.1 Generation time :
For second order reaction of type
At t = generation time, x = a
(b), the half life of reaction is
given as the half life of limiting 0.693
t =
reagent. K
7.7 First order kinetics in terms of volume,
7.5 Pseudo first order reactions :
pressure and rotation :
When one of the reactant is present in (a) If volume of reagent or product is
large excess, the second order reaction given then use following relation.
confirms to the first order and known as consider A  product
pseudo unimolecular reaction. [see 8.1 at t = 0 v0 (used)
article] e.g. at t = t vt (used)

(i) CH3COOC2H5+H2O H CH3COOH + at t =  v (used) (i.e. reaction is
C2H5OH (excess) almost complete)
(Bimolecular) 2.303  V – V0 
k= log 

rate = k [CH3COOC2H5] st
(1 order) t  V – Vt 

(ii) C12H22O11 + H2O H C6H12O6 + C6H12O6 Note :
(i) If v0 is not given then left v0 term in
formula.
(excess)
(ii) If v is not given then left v term in
(Bimolecular) formula.
rate = k [C12H22O11] (1st
order)
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(iii) If v0, vt or v is not given directly rt = angle of rotation at t = 't'

use stoichiometric equation to get
then. 8. Method of Determination of Order
(b) If pressure is given in gaseous of Reaction
reactions then use following
formula.
2.303  P  8.1 Method of integration (Hit & Trial) :
k= log10  0 
t  P0 – x  In this method we put given data in
various order's integrated laws to get
P0 = Initial pressure of reagent rate constant. It should be constant
P0–x = pressure of reactant at time throughout the given set of data.
't'. i.e.
Note : 2.303 a
(i) k = log10 for 1st order
t a–x
(i) If P0 and (P0–x) is not given directly
use stoichiometric realtion to set 1 1 1
them. (ii) k =  –  for 2nd order
t  (a – x ) a 
(ii) If the presence of mixture is given
then use following concept. (iii) [A]t = [A]o – kt for zero order
consider reaction
8.2 Graphical method :
A(g) B(g) + 2C(g) +
D(liq.) for a reaction of nth order a graph of
1
at t = 0 P0 – – versus time must be a
– (a – x ) n – 1
straight line.
at t = t P0 – P´ P´ 2P´
–
at t =  – P0 2P0 1
– (a – x ) n –1
so total press. of mixture after 't' time
Ptotal = P0 – P´ + P´ + 2P´ time

8.3 Half life method :
and Ptotal after long period or t = 
General expression for half life is t½ 
Ptotal = P0 + 2P0
1
n –1
(iii) If vapour pressure of liquid is given a
then it will remain constant where a = initial concentration and n =
throughout the reaction.
order of reaction
(c) If rotation of optically active species
n –1
is given then use following formula ( t ½ )1 a 
so =  2 
2.303  r – r0  ( t½ )2  a1 
k= log 

t  r – rt 
taking log both side
r = angle of rotation at t = 
log10 ( t ½ )1 – log10 ( t ½ ) 2
n=1+
r0 = angle of rotation at t = 0 log10 (a 2 ) – log10 (a1 )

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8.4 Vant Hoff's differential method : collision. For a collision to be effective

the following two barriers are to be
Consider two reaction having C1 & C2 as
cleared.
initial concentration with nth order.
9.2 Energy barrier :
dC dC 2
– 1 = kC1n and –  kC n2 The minimum amount of energy which
dt dt
the colliding molecules must posses as
taking log both side to make the chemical reaction to occur
is known as threshold energy.
 dC 
log 1  = log k + n log C1 ...(1)
 dt 
Threshold
 dC  energy Ea Activation Energy
log 2  = log k + n log C2 ..(2) Energy
 dt  Product
Avg. Energy
from (1) & (2) or reactant Reactant
Progress of reaction
From the given diagram we can

 dC   dC 2 
log  – 1  – log  –  conclude that “ The minimum amount
n=  dt   dt  where of energy required by reactant
log C1 – log C 2 molecules to participate in a reaction is
called activation energy (Ea) ".
dC1 dC
– & – 2 are rate of reaction
dt dt
w.r.t. reactants. 9.3 Orientation barrier :
Energy alone does not determine the
9. Collision Theory effectiveness of the collision. The
reacting molecules must collide in
proper direction to make collision
9.1 Assumptions :
effective. Following diagrams can
(i) A chemical reaction takes place due to explain importance of suitable direction
the collision among reactant molecules. for collision.
The number of collisions taking place
per second per unit volume of the
reaction mixture is known as collision
frequency (Z).
Fraction of molecules
E = Threshold energy
Fraction of molecules capable
or bringing effective collision
Energy
(ii) Every collision does not bring a chemical
change. The collision that actually
produce the products are effective
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(b) Physical size of reactants – As we

decrease the particle size rate of
reaction increases, since surface area
increases.
(c) Chemical nature of reactants – Number
of bonds to be broken and bond
strength of reacting molecules also
affect the rate of reaction.
(i) If more bonds are to be broken, the
A A
A A rate of reaction will be slow.
B B A A (ii) Similarly bond strength is more, rate
Reactants B B
of reaction will be slow.
Transition B B
state Product 10.2 Concentration of Reactants :
Reactants
Conc.
No time
reaction
We know from law of mass action that "
Reactants Rate is proportional to concentration of
So one can conclude that the colliding reactants." So rate of reaction
molecules must be in the direction of decreases with passage of time, since
maximum overlapping. concentration of reactants decreases.
The curve show decrease in the slope
Hence, rate of reaction may be given by
with time and slope is the measure of
Rate = collision frequency x fraction of rate.
effective collision R = Z × f
10.3 Effect of temperature :
10. Factor Affecting Rate of Reaction (i) Rate of reaction increases with increase
in temperature. In general for every
10ºC rise in temperature rate of
10.1 Nature of Reactants :
reaction increases 2 to 3 times.
(a) Physical state of reactants - This has (ii) The temperature coefficient (µ) of a
considerable effect over rate of chemical reaction is defined as the ratio
reaction. We have following relation of the specific rates of a reaction at two
between state of reactant & rate of temperature differing by 10ºC (25°C to
reaction. 35°C).
k ( t  10) k T2
Gaseous state  Liquid state  Solid state µ = = 2 to 3 or =
k(t) k T1
Decreasing order of rate of reaction
( T2  T1 )

 10
Because collisions in homogeneous
system are more effective than
heterogenous system.
`
Arrhenious suggested an equation k1

fractional yield of B =
which describes k as a function of k1  k 2
temperature. k2
fractional yield of C =
k  Ae  E a / RT k1  k 2
where 11.2 Successive reactions :
Ea = activation energy Consider A converted into B according

to first order kinetics and
A = Frequency factor or pre exponential simultaneously B converted into C
factor k1
following first order kinetics A 
Taking log log (k) = log (A) – k2
B  C where [A]0 is the
Ea t½ (A) t½ (B) initial conc.
2.303RT of A
E [A]0
Slope = tan  =
2.303R
Let after time 't' concentration of A & B
Intercept = log A are [A]t and [B]t respectively.
If T2 > T1 and corresponding rate [A]t = [A]0 e – k1t
constant are k2 and k1 then
k1[A ]0
[B]t = [e – k 1 t – e – k 2 t ]
k  Ea  T2  T1  ( k 2 – k1 )
log  2 
 2.303 = 
 TT 

 k1   1 2  from the above equation following
10.4 Presence of catalyst : cases of equilibrium may be considered.
(a) Presence of positive catalyst lower down

the activation energy hence increases (i) Transient equilibrium
the rate of reaction. when (t½)A > (t½)B or k1 < k2
(b) Presence of negative catalyst increases
activation energy hence decreases the
[ A ]t k 2 – k 1
rate of reaction. 
[ B ]t k1
11. Kinetics of Simultaneous Reactions (ii) Secular equilibrium
: if (t½)A >> (t½)B or k1 << k2
11.1 Parallel reactions : [A ]t k 2

Consider following first order reaction [B]t k1
proceeding through two parallel paths (iii) Disequilibrium
one leading to product B and other
leading to product C. if (t½)A < (t½)B or k1 > k2
then calculation is beyond our
k1
B scope.
A
(iv) Maximum concentration of B can
k2 C
be achieved in time (t) which can be
where k1 and k2 are respective rate calculated as
constants. 2.303 (log k1 – log k 2 )
so overall rate constant t=
k1 – k 2
k = k 1 + k2

13 CHEMICAL EQUILIBRIUM Chemistry
TEST YOUR UNDERSTANDING
CHEMICAL KINETICS
Ex-1. From the concentrations of R at different times given below, calculate the average rate of
the reaction: R  P during different intervals of time.
t/s 0 5 10 20 30
103 × [R]/mol L–1 160 80 40 10 2.5
Sol. 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  t1 ]
160 80 5 0 16
80 40 10 5 8
40 10 20 10 3
10 2.5 30 20 0.75
Ex.2 The rate of a certain reaction depends on concentration according to the equation :
 dC K1C
 .
dt 1 K 2C
W hat will be the order of reaction, when concentration (C) is :
(a) very-ver y high, (b) very-very low.
Sol.
 dC K1C K1
(a) = =
dt 1 K 2C 1  K
2
C
if C is very-ver y high then1/C being small may be neglected.
 dC K1
 = constant, i.e., zero order reaction.
dt K2
(b)If C is very-very low 1 + K 2 C  K


 dC K1C  K1 
 =  × concentration
dt K  K 
i.e.,  order reaction.

t 0.75
Ex.3 Calculate for a 1st order reaction:
t0.50
2.303 C 2.303 C t log 4 2 log 2
Sol. K= log 0 = log 0  3/ 4 = = =2
t3 / 4 1 t1/ 2 C0 t1 / 2 log 2 log 2
C0
4 2
Ex.4 At least how many half-lives should elapse for a 1 st order reaction A products so that
the reaction is at least 95% completed ? (log 2 = 0.3)
(A) 4 (B) 5 (C) 6 (D) 7
100 t
1/ 2
50 t
1/ 2
25 t
1/ 2
12.5 t
1/ 2
6.25 t
1/ 2 3.125
Sol. (B)
0% 50% 75% 87.5% 93.75% 96.875%
Ex.5 Hydrolysis of methyl acetate in aqueous solution has been studied by titrating the
liberated acetic acid against sodium hydroxide. The concentration of the ester at
different times is given below :
t/min 0 30 60 90
c/M 0.8500 0.8004 0.7538 0.7096.
Show that it follows a pseudo first order reaction as the concentration of H 2 O
remains nearly constant (51.2 M) during the course of the reaction. W hat is the value
of k in the equation?
rate = k [CH 3 COOCH 3 ] [H 2 O]
Sol. For pseudo first order reaction, the reaction should be first order with respect to the
ester when [H 2 O] = constant. From the above data we note
ln (c0 / c)
t c k{H 2 O] = min – 1
t
0 0.8500 –
30 0.8004 2.004 × 10 – 3
60 0.7538 2.002 × 10 – 3
90 0.7096 2.005 × 10 – 3
It can be seen that k [H 2 O] is constant and equal to 2.004 × 10 – 3 min – 1 and hence it is
pseudo first order reaction. W e can now determine k from
k [H 2 O] = 2.004 × 10 – 3 min – 1
It can be seen that k [H 2 O] is constant and equal to 2.004 × 10 – 3 min – 1 and hence it is
pseudo first order reaction. W e can now determine k from
k [H 2 O] = 2.004 × 10 – 3 min – 1
k [51.2 M] = 2.004 × 10 – 3 min – 1
k = 3.914 × 10 – 5 M – 1 min – 1
It has the units of a second order reaction.
Ex.6 The rate of decomposition of N2O5 in CCl4 solution has been studied at 318 K and the following
results have been obtained :
t/min 0 135 342 683 1693
c/M 2.08 1.91 1.67 1.35 0.57
Find the order of the reaction and calculate its rate constant. What is the half-life period?
Sol. It can be shown that these data will not satisfy the integrated rate law of zero order. We now try
ln (c0 / c)
integrated first order equation i.e., k=
t

ln (c0 / c)
t/min c/M k= min–1
t
0 2.08 6.32 × 10–4
135 1.91 6.30 × 10–4
342 1.67 6.32 × 10–4
683 1.35 6.32 × 10–4
1693 0.57 6.31 × 10–4
It can be seen that the value of k is almost constant for all the experimental results and hence it is
first order reaction with k = 6.31 × 10–4 min–1 .
0.69
t1/2 = 4 1
= 1.094 × 103 min–1
6.3110 min
Graphical method : Alternatively, if we draw a graph between ln c against t, we obtain a
straight line with slope = – k.
Ex.7 In the reduction of nitric gas with hydrogen, the reaction was found to be 50%
complete in 210 seconds when the initial pressure of the mixture was 200 mm. In a
second experiment the time of half reaction was 140 seconds when the initial
pressure was 300 mm. Calculate the total order of the reaction.
1
Sol. For a nth order reaction (n  1), t 1 / 2 
c0n 1
n 1
210  300 
=  n =2
140  200 
Ex.8 The reaction : CH3COF + H2O CH3COOH + HF

has been studied under the following initial conditions :
Case I Case II
cH0 2O = 1.00 M cH0 2O = 0.02 M
0 0
cCH 3COF
= 0.01 M cCH 3COF
= 0.80 M
Concentration were monitored as a function of time and are given below :
Case I Case II
t/min cCH 3COF / M t/min c H 2O /M
0 0.01000 0 0.0200
10 0.00857 10 0.0176
20 0.00735 20 0.0156
40 0.00540 40 0.0122
Determine the order of the reaction and the rate constant for the reaction.
Sol. Let rate = k (cCH 3COF ) a (cH 2O )b

We shall use here Ostwald isolation method, as in one set of experimental conditions,
cH0 2O  cCH
0
3COF
and in the second case, cH 2O  cCH 3COF . In the first case we determine the
0 0
order of the reaction with respect to CH3COF. We note that the reaction is not of zero order as rate
of reaction changes with time. We now, apply first order equation and find,
 cH0 2O 
ln  
k (cCH 3COF )b  cH O 
t/min cCH 3COF / M =
 2 
1
min t

0 0.01000 –
10 0.00857 0.0154
20 0.00735 0.0154
40 0.00540 0.0154
Therefore, k (cH 2O ) = 0.0154 min–1
and we know that the order of reaction with respect to CH3COF is 1. Now we determine the order of
reaction with respect to water. Again we try for first order equation.
 cH0 2O 
ln  
k (cCH 3COF )b  cH O 
t/min cH 2O / M =
 2 
1
min t
0 0.0200 –
10 0.0176 0.0128
20 0.0156 0.0124
40 0.0122 0.0124
average = 0.0125 min–1
The reaction is first order in H2O and we have k (cCH 3COF ) = 0.0125 min–1
0.0154 min 1
Now in case , k = = 0.0.154 M–1 min–1
1.00
0.0125
and in case  = = 0.0156 M–1 min–1.
0.800
Ex.9 Find the expression for K in terms of P0 , Pt and n
Sol. Let there is a 1st order reaction
A(g)   nB(g)
Let initial pressure at time t P0 0 t=0
PA = (P0 – x) nx
 Pt (Total pressure at time ‘t’) = P0 – x + nx = P0 + (n – 1) x
Pt  P0
 x=
n 1
P  P0 P n  Pt
 PA = P0 – t = 0
n 1 n 1
nP0  Pt
 a  p0 & a – x  PA =
n 1
2.303 P (n  1)
 k= log 0
t nP0  Pt
Final total pressure after infinite time = Pf = nP0
 Formula is not applicable when n = 1, the value of n can be fractional also.
 Do not remember the formula but derive it for each question.
Ex.10 Study of a reaction whose progress is monitored by measuring the volume of a escaping
gas.

NH4NO2 (s)   2H2O () + N2 (g)
Sol. Let, Vt be the volume of N2 collected at time ‘t’
V = be the volume of N2, collected at the end of the reaction.

a V and x Vt

(a – x)  V – Vt
2.303 V
 k= log
t V  Vt
Ex.11 From the following data show that the decomposition of hydrogen peroxide in
aqueous solution is a first - order reaction. W hat is the value of the rate constant?
Time in minutes 0 10 20 30 40
Volume V in ml 25.0 20.0 15.7 12.5 9.6
where V is the number of ml of potassium permagnate required to react with a

definite volume of hydrogen peroxide solution.

Sol. The equation for a f irst order reaction is 2H 2 O 2 
 2H2O () + O2 (g)
the volume of KMnO 4 used, evidently corresponds to the undecomposed hydrogen
peroxide
.
Hence the volume of KMnO 4 used, at zero time corresponds to the initial
concentration a and the volume used after time t, corresponds to (a – x) at that time.
Inserting these values in the above equation, we get
2.303 25
W hen t = 10 min. k 1 = log = 0.022318 min – 1 = 0.000372 s – 1
10 20.0
2.303 25
when t = 20 min. k 1 = log = 0.023265 min – 1 = 0.000387 s – 1
20 15.7
2.303 25
30 12.5
2.303 25
40 9.6
The constancy of k, shows that the decomposition of H 2 O 2 in aqueous solution is a
first order reaction. The average value of the rate constant is 0.0003879 s – 1 .
Ex.12 Conversion of N–chloro acetanilide into p–chloroacetanilide
HCl

The above reaction is first order reaction and its progress is monitored by iodometric titration in
which liberated iodine is titrated against a standard solution of Hypo using starch as indicator.
Given that in this reaction KI does not react with the product (p–chloro acetanilide).
Calculate the rate constant of the reaction. Given that volume of hypo consumed at t = 0 is V0 and
at time ‘t’, Vt
Sol. Let, V0 = volume of hypo consumed at t = 0
Similarly Vt = volume of hypo consumed at t = ‘t’
 a  V0 { K reacts with the reactant only}
a – x  Vt

2.303 V
k= log 0
t Vt
Ex.13 Study of acid hydrolysis of an ester.

H
CH3COOCH3 + H2O (excess)  CH3COOH + CH3OH
( HCl )
The progress of this reaction is monitored or determined by titrating the reaction mixture at different
time intervals against a standard solution of NaOH using phenolphthalein as indicator. Find out rate
constant of the reaction in terms of volume of NaOH consumed at t = 0, V0 , at t = , V & at time t,
Vt .
Sol. Let, V0 = vol. of NaOH used at t = 0 [this is exclusively for HCl.]
Vt = vol. of NaOH used at ‘t’
V = vol. of NaOH used at t = 
a  V – V0
a – x  V – Vt
x  Vt – V0
2.303 V  V0
a  V – V0 ; k= log 
t V  Vt
Ex.14 Study of hydrolysis of sucrose progress of this reaction is monitored with the help of polarimeter
because a solution of sucrose is dextrorotatory and on hydrolysis, the mixture of glucose as
fructose obtained becomes laevorotatory. That’s why this reaction is also known as inversion of
cane sugar.
H
C12H22O11 + H2O  C6H12O6 + C6H12O6
excess glucose fructose
Sp. rotation +66.5º +52.7º –92.4º
Let the readings in the polarimeter are
t = 0 , 0 ; t = ‘t’, t and at t =  
Then calculate rate constant ‘k’ in terms of these readings.
Sol. The principle of the experiment is that change in the rotation is directly proportional to the amount
of sugar hydrolysed.
 a  0 –  ; a – x  t – 
2.303     
k= log  0 
t  t   
k 40 ºC
Ex.15 For a reaction T.C. = 2, Calculate for this reaction.
k 25 º C
15 3
t
k2
 (T .C.) 10  (2)  ( 2)  8
10 2
Sol.
k1
 But the method of temperature coefficient was not exact and to explain the effect of temperature on
reaction rate new theory was evolved
Ex.16 Two st order rxns. are initially having equal rate at a particular temprature. Temprature of both the
reaction is increased by same amount. Calculate rate of which reaction will increase by greater
amount ( reaction with low Ea or high Ea)
 k 2  Ea  1 1 
Sol. n   =    .....(i)
k
 1 R T1 T2 

 k 2 '  Ea ' 1 1 
n   =    .....(ii)
 k1  R  T1 T2 ' 
Equation (i) – (ii).
 k2  T
n   = ( Ea – Ea,)
 k2 '  R
if Ea > Ea, k2 > k2
 Ea / RT
or k = Ae
dk  EaA   1  e Ea / RT
=  2 A
dT RT T 
1 dk Ea
temprature coeff. of rate constant =
K dT RT 2
k
= fractional change / unit temp. rise
k . T
Ex.17 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.
 K eq1  H  1 1 
n  =   
 K eq  R T1 T2 
 2 
Sol. H = Eaf – Eab > 0 (for endothermic)

Eaf > Eab
on increasing temp. kf more than kb
equilibrium will shift in forward direction.
Ex.18 For the reaction CO(g) + Cl 2 (g)  COCl 2 (g) under the same concentration
conditions of the reactants, the rate of the reaction at 250°C is 1500 times as fast as
the same reaction at 150°C. Calculate the activation energy of the reaction. If the
frequency factor is 2.0 × 10 1 0 M – 1 sec – 1 , calculate the rate constant of the reaction at
150°C.
k2 E  T2  T1 
Sol. log =  
k1 2.303 R  T1 T2 
E 100
log 1500 = 
2.303  2 523  423
3.1761 2.303  2  523  423

E = = 32.36 kcal mol – 1
100
E 32360
log k = log A – = log (2.0 × 10 1 0 ) – = 10.301 – 16.609 = – 6.308
2.303 RT 2.303  2  423
k = 4.92 × 10 – 7 litres mol – 1 sec – 1

Ex.19 The pyrolysis of an organic ester follows a first order process and its rate constant
can be expressed as
42075
ln k = 78.09 –
T
where k is given in the min – 1 . Calculate the time required for 25 percent reaction to
complete at 227°C
42075
Sol. ln k = 78.09 – = – 6.06
500
6.06
log k = – = – 2.63 ; k = 2.344 × 10–3 min – 1
2.303
2.303 a
when x = 0.25 ; k = log
t1/ 4 0.75 a
2.303
t1/4 = log 1.333 = 123.06 min
2.344 10 3
1
Ex.20 The slope of the plot of log k vs for a certain reaction was found to be – 5.4 × 10 3 .
T
Calculate the energy of activation of the reaction. If the rate constant of the reaction
is 1.155 × 10 – 2 sec – 1 at 373 K, what is its frequency factor ?
E
Sol. (a) slope = = – 5.4 × 10 3
2.303 R
E = 5.4 × 10 3 × 2.303 × 1.987 = 24.624 cal mol – 1

24.624
(b) E = Ae – E/RT
; log 1.155 × 10 – 2 = log A –
2.303 1.987  373
or A = 1.764 × 10 3 sec – 1
Ex.21 Calculate order and rate law of reaction
2NO2 + F2 2NO2F with help of mechanism
 NO2 + F2 
K1
NO2F + F (slow )
molecularity = 2 for both
NO2 + F 
K
 : 2
NO2F (fast )
According to RDS
Rate = k1 [NO2] [F2]
Ex.22 Calculate rate law

3ClO– ClO3– + 2Cl–
2ClO– K1
ClO2– + Cl– (slow)
ClO2– + ClO– 
K2
ClO3– + Cl– (fast )
Rate = k1[ClO ] – 2
Ex-23 2O3  3O2

k1
O3 k2 O2 + O (fast eq. step)
(intermediate)

O + O3 
k
3
2O2 (slow)
From R.D.S., rate = k3 [O3] [ O]
According to equilibrium step.
k1 [O2 ][O ]
Keq. = =
k2 [O3 ]
 k1 [O3 ] 
[O] =  
 k 2 [O2 ] 
 k1 [O3 ] 
Rate = k3 [O3] [O] = k3 [O3] .  
 k 2 [O2 ] 
k1 k 3 [O3 ]2
Rate =
k 2 [O2 ]
Br –
Ex-24 H+ + HNO2 + C6H5NH2  C6H5N2+ + 2H2O
Intermediate
k1
H + HNO2
+
k2 H2 NO2+ (fast) equilibrium step
Intermediate
H2NO2+ + Br –
k3
NOBr + H2O (slow)
NOBr– + C6H5NH2 
k 4
C6H5N2+ + Br – + H2O (fast)
Sol. r = k3 [Br–] [H2NO2+]


k1 [ H 2 NO2 ]
Keq = =
k 2 [ H  ][ HNO2 ]
 k1  +
[H2NO2+] =   [H ] [HNO2]
 k2 
k k
r = 1 3 [H+] [HNO2] [Br–].
k2
Ex-25 2O3  3O2

k
O3  O2 + O
1
k2
O2 + O 
 O3
k
O3 + O 

3
2O2
 1 d [O3 ] 1 d [O2 ]
Sol. rate = =
2 dt 3 dt
d [O3 ]
= – k1 [O3] + k2 [O2][O] – k3 [O3] [O]
dt

d [O2 ]
= k1 [O3] – k2 [O2] [O] + k3 [O3] [O]
dt
d [O]
At steady state =0
dt
d [O]
= k1 [O3] – k2 [O2] [O] – k3[O3] [O] = 0
dt
k1[O3 ]
[O] =
k 2 [O2 ]  k3 [O3 ]
d [O3 ]
= – k1 [O3] +
k 2 [O2 ] k1[O3 ]
–
k1 k3[O3 ]2
dt k 2 [O2 ]  k3 [O3 ] k 2 [O2 ]  k3 [O3 ]
k1k 2 [O2 ][O3 ] – k1k3[O3 ]2

= – k1 [O3] +
k 2 [O2 ]  k3 [O3 ]
k1k 2 [O2 ][O3 ] – k1k3[O3 ]2  k1k 2 [O2 ][O3 ] – k1k3 [O3 ]2
=
k 2 [O2 ]  k3[O3 ]
– 2k1 k3 [O3 ]2
=
k 2 [O2 ]  k3 [O3 ]
 –1 d  k1 k3 [O3 ]2
[O ] =
 2 dt 3  k [O ]  k [O ]
  2 2 3 3
1 d
Rate = – [O3]
2 dt
k1 k3[O3 ]2
So, Rate (r) =
k 2 [O2 ]  k3 [O3 ]
if 3rd step is RDS then k1>> k3
k2 >> k3
k1 k3[O3 ]2
r=
k 2 [O2 ]  k3 [O3 ]
Ex-26 H+ + HNO2 + C6H5NH2 

Br
C6H5N2+ + 2H2O
H+ + HNO2  k1
H2NO2+
H2NO2+ 
k2
H+ + HNO2
HNO2+ + Br– 
k3
NOBr + H2O.
NOBr + C6H5NH2  C6H5N2+ + H2 O + Br–
k4

d [ H 2 NO2 ]
Sol. = k1 [H+][HNO2] – k2 [H2NO2+] – k3 [H2 NO2+] [Br–] = 0
dt

[ H  ]]HNO2 ]
[H2NO2 ] = k1
+
k 2  k3[ Br – ]
d d
rate = [C6 H 5 NH 2 ] = [ HNO2 ]
dt dt
d
[C6 H 5 NH 2 ] = k4 [ONBr ] [C6H5NH2]
dt
d
[NOBr ] = – k4 [C6H5NH2][NOBr ] + k3 [Br–] [H2NO2+] = 0
dt

k [ Br – ][ H 2 NO2 ]
[NOBr] = 3
k 4 [C6 H 5 NH 2 ]

k 4 k3 [ Br – ][ H 2 NO2 ]
r = [C6 H 5 NH 2 ] 
k 4 [C6 H 5 NH 2 ]
k1 k3[ Br – ][ H  ][ HNO2 ]
  r=
k 2  k3[ Br – ]
dN
Ex.27 Starting from the equation for radioactive decay i.e. – = N, derive the
dt
1
expression, mean life = .

dN
Sol. (i) – = N . This on integration gives (with N = N 0 , at t = 0) ; N = N 0 e –  t
dt
   
dN

  tdN t  0 dt t  0 (N 0 )e t dt 1
 t
 t dt
 t 0  = 1
Mean life = =  = .  Mean life =
   
dN  
  dN   dt  (N 0 )e  t dt
 t  0  t  0 dt t 0
k1 k2
Ex.28 In the case of first order consecutive reactions A  B  C (Product), one
may show that the concentration of B is given by
k1C A0
CB =
(k 2  k1 )
k
 k

e  1t  e  2t .
The usual assumptions are C A = C A 0 at t = 0 while C B = C C = 0 at t = 0. Show that C B
 2.303  k 
has its maximum value at time t =   log  2 
 k 2  k1   k1 
k1C A
Sol.
dC B
dt
=
(k 2  k1 )

k 2e  k2t  k1e  k1t 
equating this zero k 2 e  k2 t  k1 e  k1 t

k2 k2  2.303  k
t =   log 2
( k k ) t
  = e 2 1 n = (k 2 – k 1 ) t 
k1 k1  k 2  k1  k1
MISCELLANEOUS SOLVED PROBLEMS (MSPS)
Ex.1 For each reaction below, express the rates of change of [product] and [reactant]
in the correct relationship to each other.
(a) 2O 3 (g)  3O 2 (g) (b) 2HOF(g)  2HF(g) + O 2 (g)
1 d [O3 ] 1 d [O2 ] 1 d [ HOF ] 1 d [ HF ] d [O2 ]
Sol. (a) – =+ (b) – =+ =+
2 dt 3 dt 2 dt 2 dt dt
 d [O3 ] 2 d  d [ HOF ] d [ HF ] 2d [O2 ]
= [O2] =+ =+
dt 3 dt dt dt dt
Ex.2 In a catalytic experiment involving the Haber's process, N 2 + 3H 2  2NH 3 , the

rate of reaction was measured as rate = = 2 x 10  4 M.s  1 . If there were no side
reactions, express the rate of reaction in terms of (a) N 2 (b) H 2 ?
d[ N2 ]  1 d[H 2 ] 1 d [ NH 3 ]
Sol. Rate of Reaction = – = =+
dt 3 dt 2 dt
d [ N 2 ]
(a) 2 × 10–4 = –
dt
d[H 2 ]
(b) 2 × 10-4 × 3 = – = 6 × 10-4 MS-1.
dt
Ex.3 W rite the units of the rate constants for a (i) Zeroth order, (ii) half order, (iii)
first order, (iv) 3/2 order, (v) second order, (vi) 5/2 order, (vii) third order
reactions.
Sol. Unit of Rate Constant = (Mole)1-n (Litre)n-1 Sec-1 Where n is the order of Reaction
(i) For Zeroth order = Mole(1-0) (Litre)(0-1) Sec-1
Unit of K
n=o Mole Litre(-1) Sec-1
Similarly For others
Ex.4 The reaction CO(g) + NO 2 (g)  CO 2 + NO is second order in NO 2 and zero order
in CO at temperatures less than 500K.
(a) W rite the rate expression for the reaction.
(b) How will the reaction rate change if the NO 2 concentration is halved?
d d
Sol. (a) [CO] = (NO2) = K [NO2]2 Order is zero w.r.t. CO but Conc will Still change
dt dt
(b) Rate of Rxn = K[NO2 ]2 of Conc of NO2 Half The Rate becomes One fourth
Ex.5 For a reaction A + 3B  Product, Rate = {– d[A] / dt} = k [A] 2 [B] , the
expression for the rate of reaction in terms of change in the concentration of B;
{– d[B] / dt} will be :
(A) k[A] 2 [B] (B) k [A] 2 [3B] (C) 3k [A 2 ] [B] (D) (1/3) k [A 2 ]
[B]
Sol. (C) For the given reaction
 d [ A] 1  d [ B]
= = K[A]2[B]
dt 3 dt

 d [ B]
Then = 3K[A]2[B]
dt
Ex.6 Gaseous cyclobutane isomerizes to butadiene in a first order process which
has k = 3.3 x 10  4 s  1 at 153 0 C . How many minutes would it take for the
isomerization to proceed 40 % to completion at this temperature .
Sol. For the First order Rxn
2.303 a 2.303  100 
t= log t= 4
log  
K (a  x) 3.3 10  60 
t = 1.54 × 10+3 Second. = 25.80 Minute
t 0. 5
Ex.7 Calculate for a 1st order reaction
t0.25
2.303 a
log
K a
(a  )
Sol.
t 0. 5
= 2 = log 2
t0.25 2.303 a 4
log (log )
K a 3
(a  )
4
Ex.8 For the reaction A + B  products

the following date were obtained :
initial rate (mole/liter.sec) 0.030 0.059 0.060 0.090

0.089
[A] (mole/liter) 0.10 0.20 0.20 0.30

0.30
[B] (mole/liter) 0.20 0.20 0.30 0.30

0.50
W rite the rate equation for this reaction. Be sure to evaluate k.

Sol. Rate = K[A]x [B]y
From data I. 0.030 = K [0.10]x [0.20]y (1)
From data II. 0.059 = K [0.20]x [0.20]y (2)
From III. 0.060 = K [0.20]x [0.30]y (3)
divide 1 equation by (2)
0.030 K [0.10] x [0.20] y
=
0.059 K [0.20] x [0.30] y
 x = 1
Then divide (2) eguation by (3)
0.059 K [0.20] x [0.20] y
=
0.060 K [0.20] x [0.30] y
y=0
Put the value of x and y in (1) equation
0.030 = K[0.10]1 [0.20]0
0.030
K= = 0.3 Sec-1
0.10

Ex.9 The following data is for the decomposition of ammonium nitrite in aqueous solution.
Volume of N2 in cc. Time (minutes)
6.25 10
9.00 15
11.40 20
13.65 25
35.05 infinity
The order of the reaction is

Sol. NH4NO2(s)  N2(q) + 2H2O(l)
Let Vt be the volume of N2 Collected at time ‘t’
V = be the volume of N2 Collected at the end of the Reaction
a  v
 (a - x)  V - Vt
Then from the given data We assume the Rxn is first order Then
2.303 a 2.303 V
K= log = log
t (a  x) t V – Vt
2.303 35.05
From Ist data K= log = 1.96 × 10–2 sec–1
10 (35.05  6.25)
2.303 35.05
IInd data K= log = 1.96 × 10–2 sec–1
15 (35.05  9)
2.303 35.05
IIIrd data K= log = 1.96 × 10–2 sec–1
20 (35.05  11.40)
From these relation the value of K are same the Rxm will be First order
Ex.10 Decomposition of H2O2.

H2O2  H2O () + O2 (g)
The progress of this reaction is measured by titrating the reaction mixture with KMnO4 at
different time intervals. Calculate rate constant of the reaction in terms of volume of KMnO4
consumed at time t = 0, V0 and at time t, Vt.
Sol. Assume the decomposition of H2O2 is a first order reaction
H2O2  H2O (l) + O2(g)
KMnO4 React Only with the H2O2 them
2.303 a
For Ist order reaction K= log
t (a  x)
Then aVo
and (a -x)  Vt
2.303 V 
Then K = log  0 
t  Vt 
D
Ex.11 A  B + C
Time 0 t 
Volume of reagent V1 V2 V3
The reagent reacts with only B, C and D. Find k.

D
Sol. A B+C
at t = o a o o
t=t (a - x) x x
t =   o a a
at t = 0 only D. React
after t = 0 reagent react with B.C.D.
2a  (V3 - V1)
(V3  V1 )
a
2
2x  (V2 - V1)
2(a - x)  (V3 - V1 - V2 + V1)
(V3  V2 )
(a - x) 
2
1 (V  V1 )
Then K = ln 3
t (V3  V2 )
Ex.12 A  B + C
Time 0 t
Volume of reagent V1 V2
The reagent reacts with A, B and C. Find k.

Sol. A  B + C
t=0 a 0 0
t=t (a -x) x x
a V1
(a - x) + x + x  V2
(a + x)  V2
1 [ A]o 1 V1
(a -x)  (2V1 - V2) ; K= ln = ln
t [ A]t t (2V1  V2 )
Ex.13 A  B + C
Time T 
Volume of reagent V2 V3
Reagent reacts with all A, B and C and have ‘n’ factors in the ratio of 1 : 2 : 3
with the reagent. Find k.
Sol. A B+C
t=0 a 0 0
t=t (a-x) x x
t= 0 a a
Reagent React with all A, B, C. and have ‘n’ factor in the Ratio 1 : 2 : 3
2a + 3a  V3
V3
a 
5
(a-x) × 1 + 2x + 3x V2
(a + 4x)  V2

V3
+ 4x  V2
5
1 V 
x  V2  3 
4 5
V 1 V 
(a-x)  3 - V2  3 
5 4 5
5(v3  v2 )
(a-x) 
20
1 4V3
K = ln
t 5(v3  v2 )
Ex.14 Now, let us assume that A, B and C are optically active compounds, which rotate the plane
polarized light in the clockwise or anticlockwise direction.
A(soln.) 
 B(soln.) + C(soln.)
Time 0 t 
Total rotation in degrees r0 rt r
Calculate the expression of rate constant.

Sol. The principle of the experiment is that change in the rotation is directly proportional to
concentration.
a  (ro - r)
(a - x)  (rt - r)
Then Expression For rate constant
2.303 r  r
K= log o
t rt  r
Ex.15 The hydrolysis of cane sugar was studied using an optical polarimeter and the
following readings were taken :
time (min.) : 0 84 min 
observed rotation : 50 20 –10
(degrees)
W hen will the mixture optically inactive? (log 2 = 0.3, log 3 = 0.48)
Sol. From the hydrolysis
K=
2.303
log
ro  r  = 2.303 log 50  10
t rt  r 84 20  10
2.303
K= × 0.3010 = 8.252 × 10–3
84
The time taken when sample are optically Inactive is t
2.303  0.3010 2.303 50  10
K= = log
84 t 20  10
t = 217.14 minute
Ex.16 The optical rotation of sucrose in 0.5 HCl at 35 0 C at various time intervals are
given below. Show that the reaction is first order.
Time (minutes) 0 10 20 30 40 
Rotation (degrees) +32.4 +28.8 +25.5 +22.4 +19.6 –11.1
Sol. If reaction first order the value of K same in First-Order Expression

K=
2.303
log
ro  r 
t rt  r
2.303 32.4  11.1 0.03751 2.303
K= log = = 8.63 × 10-3
10 28.8  11.1 10
2.303 32.4  11.1
K= log = 8.63 × 10-3
20 25.5  11.1
2.303 32.4  11.1
K= log = 8.63 × 10-3
30 22.4  11.1
2.303 32.4  11.1
K= log = 8.63 × 10-3
40 19.6  11.1
The reaction show Ist order kinetics
Ex.17 Temperature coefficient of the rate of a reaction is 3. How man y times the rate
of reaction would increase if temperature is raised by 30 K :
(A) 3 (B) 9 (C) 27 (D) 81
30
R K
Sol. (C) For same concentration 2  2  310  27.
R1 K1
Ex.18 The reaction

A + B  products
is first order with respect to both A and B has a rate constant of 6.0 mol – 1 sec – 1 .
at 27°C. Calculate the initial rate of the reaction at 47°C when equal volumes of A and B of
concentration 0.02 moles litre–1 in each are mixed. The activation energy of the
energy of the reaction is 42 kJ mol – 1 .
Sol. Reaction A + B Product
 K2  E  1 1 
We know log   =   
 K1  2.303R  T1 T2 
K  E  T2  T1 
log  2  =  
 K1  2.303R  T1T2 
K  42 103[320  300] 840
log  2  = =
 6  2.303  8.3  300  320 1835.03
K2
log = .4577
6
K2
= anti log (.4577)
6
K2 = 2.863 × 6 = 17.178
Rate at 47oC will be
The Rate2 = 17.178 × [0.01] × [0.01]
Rate2 = 17.178 × 10-4 = 1.7178 × 10-3
Ex.19 For a gaseous reaction A  products, the half-life of the first order
decomposition at 400 K is 150 minutes and the energy of activation is 65.0 kJ
mole – 1 . W hat fraction of molecules of A at 400 K have sufficient energy to give
the products ?
K
Sol. = e–Ea/RT = 3.13 × 10-6. = Fraction of Molecule Having Sufficient Energy
A

Ex.20 An exothermic reaction A  B has an activation energy of 17 KJ per mole of A.

The heat of reaction is – 40 KJ/mole. The activation energy for the reverse
reaction B  A is :
(A) 75 KJ per mole (B) 67 KJ per mole (C) 57 KJ per mole (D) 17 KJ per
mole
Sol. (C)H = EA – EB
–40 = 17 – EB
EB = 57
Ex.21 The rate of decomposition for methyl nitrite and ethyl nitrite can be given in
terms of rate constant (in sec – 1 ) K 1 and K 2 respectively. The energy of
activations for the two reactions are 152.30 kJ mol – 1 and 157.7 kJ mol – 1 as well
as frequency factors are 10 1 3 and 10 1 4 respectively for the decomposition of
methyl and ethyl nitrite. Calculate the temperature at which rate constant will be
same for the two reactions.
Sol. Rate constant will be same.
K1 = K2
 Ea1  Ea2
A1e = A2e
RT RT
Ea2  Ea1
T=
A 
2.303 log 2   R
 A1 
157.7  152.3
T= T = 282K
 10 4 
2.303  8  log 3 
 10 
Ex.22 Use the diagram below to answer the following questions.

(a) Is the reaction exothermic or endothermic?
(b) W hat is the approximate value of  E for the forward reaction?
(c) W hat is activation energy in each direction?
(d) A catalyst is found that lowers the activation
energy of the reaction by about 10 kJ/mol. How will
this catalyst affect the rate of the reverse reaction?
Sol.
(a) Forward Rxn are endothermic

(b) E = (Ea – Ea1) = (50 – 30) = 20 KJ / Mole.

(c) Eaf = 50 KJ/Mole Eab = 30 KJ/Mole
(d) Increases
Ex.23 At some temperature, the rate constant for the decomposition of HI on a gold surface is .1M.s-
1
2H  H2(g) + 2(g)

What is the order of the reaction? How long will it take for the concentration of HI to drop from
2M to 0.5M
Sol. From the unit of k given, the reaction is of zero order. As this reaction is of the type 2A 
Products, we apply
x a  (a  x)
k0 = where n = 2 or k0 = or 0.1 =
nt nt
2  0.5
2t
t = 7.5 sec
.
Ex.24 The rate of a first order reaction is 0.05 mole/L/s at 10 minutes and 0.04 mole/L/s at 30
minutes after initiation. Find the half-life of the reaction
Sol. Let the concentrations of the reactant after 10 min and 30 min be C1 and C2 respectively.
Rate after 10 min = KC1 = 0.05 × 60 and
Rate after 30 min = KC2 = 0.04 × 60
c1 5
 =.
c2 4
Supposing the reaction starting after 10 minutes
2.303 c 2.303 5
k= log 1 = log = 0.011159
20 c2 20 4
0.6932 0.6932
 t1/2 = = = 62.12 min.
k .011159
Ex.25 For a chemical reaction A+B  Product, the order is 1 with respect to each of A and B Find x
and y from the given data.
Rate (moles/L/s) [A] [B]
0.10 0.1 M 0.1M
0.80 xM 0.1M
0.40 0.2 M yM
Sol. The rate law may be written as
rate = k [A] [B]
Substituting the first set of data in the rate law, we get,
0.10 = k × 0.1 × 0.1
k = 10
Now substituting the second and third sets of data, we get,
0.8 = 10 × x × 0.1
x = 0.80 M
And, 0.4 = 10 × 0.2 × y
y = 0.20 M.
Ex.26 In the decomposition of H2O2 at 300 K, the energy of activation was found to be 16 kcal/ mole,
while it decreased to 10 kcal/ mole when the decomposition was carried out in the presence
of a catalyst at 300 K, How many times is the catalysed reaction faster than the uncatalysed
one?
Sol. Suppose E1 and E2 are the energies of activation when the reaction is carried out in the
absence and presence of a catalyst respectively.

Thus, k1 = Ae E1 / RT k2 = Ae
 E2 / RT
E1
Taking log, In k1 = In A -
RT
E2
In k2 = In A -
RT
E2 E1
 In k2 - In k1 = - +
RT RT
k2 1 6
or In = (16 –10) =
k1 0.002  300 0.002  300
k
2.303 log 2 = 10
k1
k 10
log 2 = = 4.342
k1 2.303
k
Taking antilog 2 = 2.190 × 10
k1
Ex.27 In Arrhenius`s equation for a certain Reaction, the value of A and E (activation energy) are 6
× 1013 s-1 and 98.6 kJ mol-1 respectively. If the reaction is of first order, at what temperature
will its half-life period be 20 minutes ?
Sol. k = Ae-E/RT
E
In k = In A –
RT
E
2.303 log k = 2.303 log A –
RT
E
or log k = log A – .....(1)
2.303RT
Given that A = 6 × 1013 s -1, E = 98.6 kJ mol-1
t1/2 = 20 × 60 s.
0.6932 0.6932 -1
For first-order reaction k = = s
t1/ 2 1200
Thus (1) becomes,
0.6932 98.6
log = log (6 × 1013) - [R = 8.314 × 10-3 kJ/K/mol]
1200 2.303  8.314 103  T
T = 302.26 K.
Ex.28 The decomposition of N2O5 according to the equation

2N2O5(g)  4NO2(g) + O2(g)
is a first-order reaction. After 30 minutes from the start of the decomposition in a closed
vessel, the total pressure developed is found to be 284.5 mm of Hg and on complete
decomposition the total pressure is 584.5 mm of Hg. Calculate the rate constant of the
reaction.
Sol. 2N2O5  4NO2 + O2
at t = 0 a
After 30 min: a–x 2x x/2
x
 (a – x) + 2x + = 284.5
2
5a
or = 584.5 ....(2)
2
From (1) and (2), we get,
a = 233.5, x = 34
Thus, for a first-order reaction of the type 2A  products
1 a
k= log
2t ax
2.303 233.5
k= log = 2.625 × 10-3 min-1
2  30 233.5  34
Ex.29 The complexation of Fe2+ with the chelating agent dipyridyl has been studied kinetically in
both forward and reverse directions.
Fe2+ + 3 dipy Fe(dipy)32+
Rate (forward) = (1.80 × 1013) [Fe2+] [dipy]3
and rate (reverse) = (1.20 × 10-4) [Fe (dipy)32+]
Find the stability constant for the complex.
Sol. At dynamic equilibrium,
rate of formation of complex = rate of its decomposition
(1.8 × 1013) [Fe2+] [dipy]3 = (1.20 × 10-4) [Fe(dipy)32+]
2
[ Fe(dipy) 3 ] 1.8 1013
Ks = . = = 1.5 × 1017
[ Fe 2 ][dipy]3 12 104
Ex.30 The approach to the following equilibrium was observed kinetically from both directions.
PtCI42- + H2O Pt(H2O)CI-3 + CI- at 25oC It was found that
d [ PtCI ]2 4
– = (4.8 × 10-5) [PtCI2-4] – (2.4 × 10-3) [Pt(H2O)CI-3] [CI-]
dt
Calculate the equilibrium constant for the complexation of CI– with Pt(II).
d [ PtCl4 ]2
Sol. At equilibrium, =0
dt
Hence, 4.8 × 10-5 [PtCI2-4] = 2.4 × 10-3 [Pt(H2O)CI-3] [CI-]
[ PtCl4 ]2 2.4 103
or K= = = 50.
[ Pt ( H 2O)Ci  3 ][CI  ] 4.8 105
Ex.31 Some PH3(g) is introduced into a flask at 600oC containing an inert gas PH3 proceeds to
decompose into P4(g) and H2(g) and the reaction goes to completion. The total pressure is
given below as a function of time. Find the order of the reaction and calculate the rate
constant for the reaction:
Time (s) : 0 60 120
p mm (Hg) 262.40 272.90 275.51 276.40
4PH3  P4 + 6H2
Sol. Let the initial Partial pressures of PH3 and the inert gas be p and pi mm respectively and p’
mm of PH3 decomposes at different time intervals.
Initial partial pressure. P
4PH3  P4 + 6H2
Partial pressure at different times: p – p p/4 6p/4
As given, at t = 60 seconds.
p + p = 262.40 ...(1)

p' 6 p '
and, p - p + + + p = 272.90 ...(2)
4 4
p' 6 p '
At t = : + + p = 276.40. ...(3)
4 4
Solving, equations (1), (2) and (3), we get,
p = 18.67 and p = 14.
Similarly, at t = 120 seconds
p' 6 p '
p - p + + + p = 275.51. ...(4)
4 4
Solving, equations (1), (4) and (3), we get
p = 18.67 and p’ = 17.48.
As the given reaction is of the type nA  products, where n = 4, we have the following equation for
first-order kinetics
2.303 a 2.303 p
k1 = log = log .
4t ax 4t p  p'
2.303 18.67
Thus, at t = 60s; k1 = log = 5.8 × 10-3 s-1
4  60 18.67  14
2.303 18.67
t = 120s; k1 = log = 5.8 × 10-3 s -1.
4 120 18.67  17.48
As the values of k1 are constant, the given reaction following the first order kinetics.

Type (I) : Very Short Answer type Question : (1 Mark)

1. What is the order of Radio active decay ?
2. The half life of reaction is 50 minutes. What will be the order of the reaction if reaction goes to completion in
100 minutes ?
3. What is the effect of catalyst on the rate of reaction ?

4. Define threshold energy of a reaction.
1
5. What is the shape of graph between log K. v/s ? What is the relationship between its slope and activation
T
energy (Ea) ?
6. Define activation energy of a reaction.
Type (II) : Short Answer type Question : (2 Marks)

7. What is meant by order and molecularity of a reaction ? Distinguish between order and molecularity.
8. What is temperature coefficient of a reaction ?
9. Derive an expression for first order reaction.
10. Time required for a particular reaction to be half completed is 693 seconds. Calculate the time required for
90% completion of this reaction.
2000 1000
 
11. The rate constants K1 and K2 for two different reaction are 1016 e T and 1015 e T respectively. Calculate
the temperature at which K1 = K2
12. Calculate the half-life of a first order reaction from their rate constants given below :
(i) 200 s–1 (ii) 2 min– 1
Type (III) : Long Answer type Question : (3 Marks)
13. The reaction 2NO2 + F2  2NO2F involves the following steps :
NO2 + NO2 N2O4 (fast)
N2 O 4 + F 2 2NO2F (slow)
Write the rate law. Calculate the overall order of the reaction and what is the rate determing step ?
14. A first order reaction is 25% completed in 30 minutes.

Calculate : (a) Specific reaction rate ‘K’ (b) t 1/2
15. A first order reaction has a rate constant 1.15 × 10–3 s–1 . How long will 5 g of this reactant take to
reduce to 3 g ?
16. A reaction is first order in A and second order in B.

(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three times?
(iii) How is the rate affected when the concentrations of both A and B are doubled?
17. In a reaction between A and B, the initial rate of reaction (r 0) was measured for different initial
concentrations of A and B as given below:
A / moL–1 0.2 0.2 0.4

B / moL–1 0.3 0.1 0.05
r0 / moL–1S –1 5.07  10 – 4 5.07  10 – 3 1.43  10 – 4
What is the order of the reaction with respect to A and B?
CHAITANYA'S ACADEMY www.chaitanyasacademy.com

Type (IV) : Very Long Answer type Question : (5 Marks)
18. Mention the factors that affect the rate of a chemical reaction.
19. For the decomposition of azoisopropane to hexane and nitrogen at 543K, the following data are obtained.
t (sec) P(mm of Hg)
Calculate the rate constant.

20. (a) Given one example of a reaction in which order and molecularity are
(i) same (ii) different
(b) At constant temperature and volume
X decomposes as
2 X(g)  3Y(g) + 2Z (g)
PX is partial pressure of X
Observation Time in min PX (mm of Hg)

1 0 800
2 100 400
3 200 200
(i) what is order of reaction with respect of X?

(ii) Calculate time for 25% completion of reaction?
(iii) Find the total pressure when pressure of ‘X’ is 600 mm.
21. (a) Observe the graph shown and answer the following questions?
(i) What is order of reaction?
(ii) What are units of ‘K’
(b) For a zero order reaction starting with initial concentration [R0] how much time it will take for completion?
(c) Rate constant K of a reaction varies with temperature according to the equation
Ea 1
log10 K = log10A – ×
2.303 R T
1
when Ea is activation energy of the reaction draw the shape of graph between log10 K verses . If the slope
T
of this line is – 6670K. Calculate the energy of activation for this reaction [R = 9.314 JK mole ].
–1 –1

PART - I : SUBJECTIVE QUESTIONS
Section (A) : Rate of chemical reaction and Dependence of Rate : Basic

A-1. The oxidation of iodide ion by peroxy disulphate ion is described by the equation :
3– (aq) + S2O82– (aq)  3– (aq) + 2SO42– (aq)
[S2O82 ] [  ]
(a) If – =1.5 × 10–3 Ms–1 for a particular time interval, what is the value of – for the same time
t t
interval ?
(b) What is the average rate of formation of SO42– during that time interval ?
A-2. In the following reaction 2H2O2 (aq)  2H2O (l) + O2 (g) rate of formation of O2 is 36 g min–1 ,
(a) What is rate of formation of H2O. (b) What is rate of disappearance of H2O2.
A-3. Hydrogenation of vegetable ghee at 25 °C reduces the pressure of H2 from 2 atm to 1.2 atm in 50 minute.
Calculate the rate of reaction in terms of change :
(a) In pressure per minute. (b) In molarity per second.
A-4. The stoichiometric equation for the oxidation of bromide ions by hydrogen peroxide in acid solution is
2Br (aq) + H2O2 (aq) + 2H+ (aq)  Br2 (l) +2H2O (l)
Since the reaction does not occur in one stage, the rate equation does not correspond to this stoichiometric
equation but is
rate = k[H2O2] [H+] [Br  ]
(a) If the concentration of H2O2 is increased by a factor of 3, by what factor is the rate of consumption of
Br  ions increased.
(b) If, under certain conditions, the rate of consumption of Br  ions is 7.2 x 10mole dms, what is the
rate of consumption of hydrogen peroxide. What is the rate of production of bromine.
(c) What is the effect on the rate constant k of increasing the concentration of bromide ions.
(d) If by the addition of water to the reaction mixture the total volume were doubled, what would be the effect
on the rate of change of the concentration of Br. What would be the effect on the rate constant k.
Section (B) : Integrated rate law : Zero and First Order Reaction
B-1. For the zero order reaction A  2B, the rate constant is 2 × 10–6 M min–1. The reaction is started with 10
M of A (i) What will be the concentration of a after 2 days? (ii) What is the initial half-life of the reaction ? (iii)
In what time, the reaction will complete?
B-2. Substance A reacts according to a first order rate law with k = 5 x 105 s1.
(a) If the initial concentration of A is 1.0 M, what is initial rate .
(b) What is the rate after 1.0 hour. (Given e–0.18 = 0.84)
B-3. A and B are two different chemical species undergoing 1st order decomposition with half lives equal to 5 sec.
CA t
and 7.5 sec. respectively. If the initial concentration of A and B are in the ratio 3 : 2. Calculate C after three
Bt
half lives of A. Report your answer after multiplying it with 100.
B-4. In the biological processes, the time taken by certain virus or bacteria to double its population, is called
generation time. In milk, at 37ºC, lactobacillus acidophilus has a generation time of about 75 min. Calculate
the population relative to the initial value at 60 min.
Section (C) : Integrated Rate law : Second Order & Pseudo first order reaction
C-1. The rate constant for a certain second order reaction is 8  10 5 M 1 min 1 . How long will it take a 1 M
solution to be reduced to 0.5 M in reactant ? How long will it take from that point until the solution is
0.25 M in reactant.


C-2. The reaction CH3CH2NO2 + OH  CH3 CH NO2 + H2O obeys the rate law for pseudo first order
kinetics in the presence of a large excess of hydroxide ion. If 1% of nitro ethane undergoes reaction in half
a minute when the reactant concentration is 0.002 M. What is the pseudo first order rate constant ?
(log 99 = 1.996)
d [A ]
C-3. For the reaction A  B, the rate law expression is – = K[A]1/2. If initial concentration of A is A0.
dt
Calculate
(a) integrated form of the rate law expression (b) nature of plot of [A]1/2 vs. time. (c) half life period.
Section (D) : Experimental Method to calculate order and rate law of reaction and Methods
to Monitor the progress of Reaction
D-1. The following data are for the reaction A + B  products:
conc. A conc. B Initial Rate
(M) (M) (mol L1 s1)
0.1 0.1 4.0 x 104
0.2 0.2 1.6 x 103
0.5 0.1 2.0 x 103
0.5 0.5 1.0 x 102
(i) What is the order with respect to A and B for the reaction?
(ii) Calculate the rate constant.
(iii) Determine the reaction rate when the concentrations of A and B are 0.20 M and 0.35 M, respectively.
D-2. (a) The half life period and initial concentration for a reaction are as follows. What is order of reaction?
Initial concentration 350 540 158
t1/2 425 275 941
(b) The half-life period for the thermal decomposition of PH3 at three different pressures are given below
Initial pressure (mm Hg) 707 79 37.5
Half--life (seconds) 84 84 83
What is the order of the reaction ?
D-3. For the reaction A  products, the following data is given for a particular run.
time (min.) : 0 5 15 35
1
(M–1) : 1 2 4 8
[A]
Determine the order of the reaction.
D-4. (a) Let there be as first-order reaction of the type, A  B + C. Let us assume that all three species are
gases. We are required to calculate the value of rate constant based on the following data.
Time 0 T 
Partial pressure of A P0 Pt –
(b) Let there be a first order reaction, A  B + C. Let us assume all three are gases. We are required to
calculate the value of rate constant based on the following data
Time 0 t 
Total pressure P0 Pt –
(c) A(g)  B(g) + C(g)
Time 0 t 
Total pressure of B + C – Pt P

(d) A(g)  B(g) + C(s)
Time 0 t 
Total pressure of B – Pt P
D-5. The decomposition of Cl2O7 at 400 K in gaseous phase to Cl2 and O2 is of  order reaction. After 55 sec at 400
K, the pressure of reaction mixture increases from 0.62 to 1.88 atm. Calculate the rate constant of given
reaction, also calculate the pressure of reaction mixture after 100 second.
31 7
[Given : ln = 0.869, e1.58 = 4.858] CI2O7(g) 
 CI2 (g) + O (g)
13 2 2
Section (E) : Method to monitor the progress of Reaction

E-1. The kinetic of hydrolysis of methyl acetate in excess dilute HCl at 25°C were followed by withdrawing 2 mL
of the reaction mixture at intervals of (t), adding 50 mL water and titrating with baryta water. Determine the
velocity constant of hydrolysis.
t (in minute) 0 75 119 259 
Titre value (in mL) 19.24 24.20 26.60 32.23 42.03
22.79 22.79 22.79
[ln = 0.2454, ln = 0.39, ln = 0.8439]
17.83 15.43 9. 8
E-2. The decomposition of hydrogen peroxide in an aqueous solution is a first order reaction. It can be studied by
titrating quickly 10 ml. portions of reactions mixture at various times form the t = 0 of reaction against a
standard solution of KMnO4. Volume of KMnO4 solution used in each case is proportional to the remaining
concentration of H2O2.
From the following data calculate the rate constant of the reaction,
Time (seconds) 0 600 1200
KMnO4 solution used (ml) 22.8 13.8 8.2
E-3. For a first order reaction A  2B + C. It was found that at the end of 10 minutes from the start, the total
optical rotation of the system was 60° and when the reaction is complete, it was 180°. The B and C are only
optically active and intially only A was taken.
(i) What is the rate constant of the above reaction in (hour)–1 ?
(ii) At what time (in minute) from the start, total optical rotation will be 90º.
(Take log2 = 0.3, log3 = 0.48, log7 = 0.85, ln10 = 2.3)
Section (F) : Complication in 1st Order Reaction

F-1. For a first order reaction
Percentage of B in the product is 30%.Calculate the value of k1 and k2. ((t1/2)over all = 100 hr))
F-2. An organic compound dissociates into n parallel first order reactions simultaneously and produces n different
products P1, P2, P3, ......., Pn having rate constants k, 2k, 3k, ......, nk and activation energies E, 2E, 3E
..............., nE respectively. Calculate the overall energy of activation of the compound P.
F-3. For a first order reversible reaction A B , the initial concentration of A and B are [A]0 and zero
respectively. If concentrations at equilibrium are [A]eq. and [B]eq. derive an expression for the time taken by B
to attain concentration equal to [B]eq/2 .

k1 k2
F-4. For a consecutive first order reaction A 
 B  C, the values of k1 and k2 are 45 hr–1 and 15 hr–1
respectively. If the reaction is carried out with pure A at a concentration of 1.0 mol dm–3,
(a) How much time will be required for the concentration of B to reach a maximum.
(b) What will be the maximum concentration of B.
(c) What will be the composition of the reacting system after a time interval of 10 minute.
Section (G) : Temperature dependence of rate

G-1. From the following data for the reaction between A and B.
–3 –1
[A] [B] Initial rate (mole dm min )
–3 –3
(mole dm ) (mole dm )
300 k 320 k
–3
(i) 2.5 × 10
–4
3.0 × 10
–5
5.0 × 10
–4 2.0 × 10
–4 –5 –3
(ii) 5.0 × 10 6.0 × 10 4.0 × 10
–3 –5 –2
(iii) 1.0 × 10 6.0 × 10 1.6 × 10
Calculate the following

(i) The order w.r.t. A and w.r.t. B (ii) The rate constant at 300 K
(iii) The energy of activation (iv) The pre-exponential factor
[e–22.18 = 2.3283 × 10–10 , ln2 = 0.693]
G-2. Find out the percentage of the reactant molecules crossing over the activation energy barrier at 325 K, given
that H325 = 0.12 kcal, Ea(b) = + 0.02 kcal.
G-3. Consider the following figure for the reaction :

A + B  M + N
Answer the following :
(A) Energy level of (A + B)
(B) Energy lelvel of (M + N)
(C) Threshold energy level for the reaction
(D) Energy of activation for the forward reaction.
(E) Energy of activation for the backward reaction.
(F) H or heat of reaction.
Section (H) : Catalyst dependence of rate and type of Reaction and Determination of rate
law and order with the help of given mechanism
H-1. On introducing a catalyst at 500 K, the rate of a first order increase to 1.718 times. The activation energy in
the presence of a catalyst is 6.05 KJ/mole. The slope of the plot of lnk (sec–1) against 1/T in the absence of
catalyst is :
H-2. The thermal decomposition of N2O5 occurs in the following steps.

slow
Step -  N2O5   NO2 + NO3

fast
Step -  N2O5 + NO3   3NO2 + O2
2N2O5 
 4NO2 + O2
suggest the rate expression.

H-3. The reaction 2NO (g) + Br2 (g)  2NOBr (g), obeys the following mechanism.
(i) NO(g) + Br2(g) NOBr2(g)

Slow
(ii) NOBr2(g) + NO(g)   2NOBr(g)
Suggest the rate expression.
H-4. Given the following steps in the mechanism for a chemical reaction :
A + B   C (fast)
B + C   D + E slow)
D + F   A + E fast)
At any time [C] is directly proportional to [A].
(a) What is the stoichiometric equation for the reaction ?
(b) Which species, if any, are catalysts in this reaction ?
(c) Which species, if any, are intermediates in this reaction?
(d) Write the rate law for the rate-determining step.
(e) Write the rate law for this reaction.
(f) What is overall order of the reaction ?
Section (I) : Radio Activity

I-1. The activity of a radio-isotope falls to 12.5% in 90 days. Compute the half life and decay constant of the radio-
isotope.
I-2. Radioactive decay is a first order process. Radioactive carbon in wood sample decays with a half life of 5770
years. What is the rate constant (in years –1) for the decay? What fraction would remain after 11540 years.
I-3. 1 gram of 79Au198 (t1/2 = 65 hrs) decays by beta emission and produces stable mercury. How much mercury
will be present after 260 hours.
I-4. A sample of U238 (half life = 4.5 × 109 year) ore is found to contain 23.8 g of U238 and 20.6 g of Pb206. Calculate
the age of the ore.
PART - II : OBJECTIVE QUESTIONS
Section (A) : Rate of chemical reaction and Dependence of Rate : Basic
A-1 Rate of formation of product at t = 20 seconds is
(A) 0.5 MS–1 (B) 1 M S-1 (C) 1.5 M S–1 (D) 2MS–1
A-2 In the following reaction : xA  yB

 d[ A ]   d[B] 
log  dt  = log  dt  + 0.3
   
where –ve sign indicates rate of disappearance of the reactant. Thus, x : y is :
(A) 1 : 2 (B) 2 : 1 (C) 3 : 1 (D) 3 : 10

A-3 Rate of formation of SO3 in the following reaction 2SO2 + O2  2SO3 is 100 g min–1. Hence rate of
disappearance of O2 is :
(A) 50 g min-1 (B) 40 g min–1 (C) 200 g min–1 (D) 20 g min–1
A-4* Which of the following are true about rate of a reaction?

(A) Rate of a reaction cannot be negative
(B) Rate of a reaction is change in concentration of the reactant per unit time per mol
(C) Average rate and instantaneous rate can never be equal.
(D) Rate depends upon surface area of the reactants.
A-5 aA + bB  Product, dx/dt = k [A]a [B]b . If concentration of A is doubled, rate is four times. If concentration
of B is made four times, rate is doubled. What is relation between rate of disappearance of A and that of B ?
(A) – {d [A] / dt} = – {d [B] / dt} (B) – {d [A] / dt} = – {4 d [B] / dt}
(C) – {4 d [A] / dt} = – {d [B]/ dt} (D) None of these
A-6 For the reaction, 2NO(g) + 2H2(g)  N2(g) + 2H2O(g) the rate expression can be written in the following
ways:
{d [N2] / dt} = k1 [NO][H2] ; {d[H2O] / dt} = k[NO][H2] ; {– d[NO] / dt} = k1 [NO] [H2] ; {–d[H2] / dt} = k1 [NO][H2]
The relationship between k, k1 , k1 and k1. is :
(A) k = k1 = k1 = k1 (B) k = 2k1 = k1 = k1
(C) k = 2k1 = k1 = k1 (D) k = k1 = k1 = 2 k1
A-7 For a reaction pA + qB  products, the rate law expression is r = k[A]1 [B]m , then :
(A) (p+1) < (1+ m) (B) (p + q) > (1 + m)
(C) (p + q) may or may not be equal to (1+ m) (D) (p + q) = (1 + m)
A-8* Which of the following statement is/are correct ?

(A) A second order reaction must be a bimolecular elementary reaction
(B) A bimolecular elementary reaction must be a second order reaction
(C) Zero order reaction must be a complex reaction
(D) First order reaction may be complex or elementary reaction
A-9 For the irreversible process, A + B  products, the rate is first–order w.r.t. A and second–order w.r.t. B.
If 1.0 mol each of A and B introduced into a 1.0 L vessel, and the initial rate was 1.0 × 10–2 mol L–1 s–1 , rate
when half reactants have been turned into products is :
(A) 1.25 × 10–3 mol L–1 s–1 (B) 1.0 × 10–2 mol L–1 s–1
–3
(C) 2.50 × 10 mol L s –1 –1 (D) 2.0 × 10–2 mol L–1 s–1
A-10 If rate constant is numerically the same for the three reactions of first, second and third order respectively.
Assume all the reactions of the kind A  products. Which of the following is correct :
(A) if [A] = 1 then r1 = r2 = r3 (B) if [A] < 1 then r1 > r2 > r3
(C) if [A] > 1 then r3 > r2 > r1 (D) All
Section (B) : Integrated rate law : Zero and First Order Reaction
B-1 The rate constant of the reaction A  2B is 1.0 × 10–3 mol lit–1 min–1, if the initial concentration of A is 1.0
mole lit–1 what would be the concentration of B after 100 minutes.
(A) 0.1 mol lit–1 (B) 0.2 mol lit–1 (C) 0.9 mol lit–1 (D) 1.8 mol lit–1
B-2 A drop of solution (volume 0.05 mL) contains 3.0 × 10–6 moles of H+. If the rate constant of disappearance of
H+ is 1.0 × 107 mole litre–1 sec–1. How long would it take for H+ in drop to disappear :
(A) 6 × 10–8 sec (B) 6 × 10–7 sec (C) 6 × 10–9 sec (D) 6 × 10–10 sec
B-3 Graph between concentration of the product and time of the reaction A  B is of the type Hence
graph between – d[A]/dt and time will be of the type :

(–d[A]/dt)
(A) (B) (C) (D)
Time

B-4 What will be the order of reaction and rate constant for a chemical change having log t50% vs log concentration
of (A) curves as :
(A) 0, 1/2 (B) 1, 1 (C) 2, 2 (D) 3, 1
d[ A ] 1
B-5 For a reaction 2A + B  product, rate law is – = k[A]. At a time when t = , concentration of the
dt k
reactant is : (C0 = initial concentration)
C0 C0 1
(A) (B) C0e (C) 2 (D) C
e e 0
B-6 Two substances A (t1/2 = 5 min) and B (t1/2 = 15 min) are taken in such a way that initially [A] = 4[B]. The
time after which both the concentration will be equal is : (Assume that reaction is first order)
(A) 5 min (B) 15 min
(C) 20 min (D) concentration can never be equal
B-7 A reaction follows the given concentration (M)–time graph. The rate for this reaction at 20 seconds will be :
0.5
0.4
0.3
0.2
0.1
0 20 40 60 80 100
Time/second
(A) 4 × 10–3 M s–1 (B) 8 × 10–2 M s–1 (C) 2 × 10–2 M s–1 (D) 7 × 10–3 M s–1
B-8 In a first order reaction the reacting substance has half-life period of ten minutes. What fraction of the
substance will be left after an hour the reaction has occurred ? :
(A) 1/6 of initial concentration (B) 1/64 of initial concentration
(C) 1/12 of initial concentration (D) 1/32 of initial concentration
d [C ]
B-9* For the reaction 2A + B  C with the rate law = k [A]1 [B]–1 and started with A and B in
dt
stoichiometric proportion. Which is/are true?
(A) unit of k is Ms –1
(B) [A], [B] and [C] all will be linear functions of time
(C) [C] = 2kt
(D) [C] = kt
Section (C) : Integrated Rate law : Second Order & Pseudo first order reaction
C-1 A reaction, which is second order, has a rate constant of 0.002 L mol–1 s–1. If the initial conc. of the reactant
is 0.2 M. how long will it take for the concentration to become 0.0400 M ?
(A) 1000 s (B) 400 s (C) 200 s (D) 10, 000 s
C-2 Which is not true for a second order reaction ?

(A) It can have rate constant 1 × 10–2 L mol–1 s–1
(B) Its half-life is inversely proportional to its initial concentration
(C) Time to complete 75% reaction is twice of half-life
1
(D) T50 = K  Initial conc.

1
C-3* For a second order reaction plots are made for [ A ] vs time for the reaction, 2A  Product. Pick up the
correct sentences.
(A) the graph will show straight line with slope K
(B) the graph will show straight line with intercept [A]0
(C) the graph will show straight line with slope [A]0
1
(D) the graph will show straight line with intercept [ A ]
0
C-4 A certain reaction A + B C, the first order with respect to each reactant k = 10–3. Determine the final
concentration of A after 100 s, if the initial concentration of A was 0.1 M and that of B was 0.2 M.
(A) 0.098 M (B) 0.088 M (C) 0.078 M (D) 0.068 M
C-5 For the reaction 2NO2  N2O2 + O2, rate expression is as follows
d [NO 2 ]
– =K [NO2]n , where K = 3 × 10–3 mol–1 L sec–1. If the rate of formation of oxygen is 1.5 × 10–4 mol L–1
dt
sec–1, then the molar concentration of NO2 in mole L–1 is
(A) 1.5 × 10–4 (B) 0.0151 (C) 0.214 (D) 0.316
C-6 At the point of intersection of the two curves shown, the conc. of B is given by.......for, A  nB :
nA 0 A0 nA 0  n – 1
(A) (B) (C) (D)   A0
2 n–1 n 1  n  1
C-7 A graph between log t 1/ 2 and log a (abscissa) a being the initial concentration of A in the reaction
For reaction A  Product, is the rate law is :
log t 1/2 Slope = – 1
log a
– d[A ] – d[A ] – d[A ] – d[A ]

(A) =K (B) = K [A] (C) = K [A]2 (D) = K [A]3
dt dt dt dt
C-8 Which of the following are example of Pseudo uni molecular reaction?
H 
(A) CH3 – C – OC2H5 + H2O  CH3COOH + C2H5OH
||
O
H 
(B) C12H22O11 + H2O  C6H12O6 (glucose) + C6H12O6 (fructose)
OH –
(C) CH3 – C – OC2H5 + H2O   CH3 – C – OH
|| ||
O O
(D) CH3 – C – Cl + H2O  CH3COOH + HCl

||
O

t3 / 4
C-9 Statement-1 : The ratio of for third order reaction is equal to 5 : 1
t1 / 2
Statement-2 : t1/2 & t3/4 of a reaction depends only on order, not on the concentration of reactant.
(A) Statement 1 and statement 2 are correct and statement 2 is the correct explanation of statement 1.
(B) Statement 1 and statement 2 are correct but the statement 2 is not correct explanation of statement 1.
(C) statement 1 is correct but statement 2 is false.
(D) statement 1 is false but statement 2 is correct.
Section (D) : Experimental Method to calculate order and rate law of reaction
D-1 The data for the reaction A + B  C is
Exp. [A]0 [B]0 initial rate
1 0.012 0.035 0.10
2 0.024 0.035 0.80
3 0.012 0.070 0.10
4 0.024 0.070 0.80
(A) r = k [B]3 (B) r = k [A]3 (C) r = k [A] [B]4 (D) r = k [A]2 [B]2 .
D-2 Match the graphical study with the order of the reactions :
I : Rate II : Half life III : (a – x)–1
I II III I II III
(A) A B C (B) B C A
(C) C B A (D) C A B
D-3 In three different reactions, involving a single reactant in each case, a plot of rate of the reaction on the y
axis, versus concentration of the reactant on the xaxis, yields three different curves shown below.
(i) (ii) (iii)
What are the possible orders of the reactions (i), (ii), (iii).
(A) 1, 2, 3 (B) 2, 1, 1/2 (C) 0, 1, 2 (D) 0, 1, 1/2
Section (E) : Methods to Monitor the progress of Reaction

E-1 At 373 K, a gaseous reaction A  2B + C is found to be of first order. Starting with pure A, the total pressure
at the end of 10 min. was 176 mm and after a long time when A was completely dissociated, it was 270 mm.
The pressure of A at the end of 10 minutes was :
(A) 94 mm (B) 47 mm (C) 43 mm (D) 90 mm
E-2 The reaction A(s)  2 B(g) + C(g) is first order. The pressure after 20 min. and after very long time are 150
mm Hg and 225 mm Hg. The value of rate constant and pressure after 40 min. are :
(A) 0.05 In 1.5 min–1 ,200 mm (B) 0.5 ln 2 min–1 ,300 mm
–1
(C) 0.05 In 3 min , 300 mm (D) 0.05 In 3 min–1 , 200 mm

E-3* In the following gaseous phase first order reaction
A(g)  2B(g) + C(g)
initial pressure was found to be 400 mm and it changed to 1000 mm after 20 min. Then :
(A) Half life for A is 10 min (B) Rate constant is 0.0693 min–1
(C) Partial pressure of C at 30 min is 350 mm (D) Total pressure after 30 min is 1100 mm
E-4 Which integrated equation is correct for the following Ist order reaction started with only A(g) in a closed rigid
vessel.
A (g)  B (g) + C (g) + D (g)
Pi = initial pressure ; Pt = total pressure at time t
2.303  Pi  2.303  Pt 
(A) K = log10  P  (B) K = log10  P 
t  t t  i
2.303  2Pi  2.303  3Pi 

(C) K = log10  3P – P  (D) K = log10  2P – 3P 
t  i t t  i t
E-5 The decompostion NH3 gas on a heated tungsten surface gave the following results :
Initial pressure (mm) 65 105 y 185
Half-life (sec) 290 x 670 820
Calculate approximately the values of x and y.
(A) x = 410 sec (B) x = 467 sec (C) x = 490 sec (D) x = 430 sec
y = 115 mm y = 150 mm y = 120 mm y = 105 mm
E-6 In the reaction NH4NO2 (aq.)  N2 (g) + 2 H2O (l) the volume of N2 after 20 min and after a long time is 40 ml
and 70 ml respectively. The value of rate constant is :
(A) (1/20) In (7/4) min–1 (B) (2.303 /1200) log (7/3) sec–1
(C) (1/20) log (7/3) min–1 (D) (2.303 / 20) log (11/7) min–1
E-7 If no catalyst (H+) is present in acid hydrolysis of ester (in above question) then rate constant K is :
2.303 V0 2.303 V
(A) log (B) log
t ( Vt  V ) t ( V  Vt )
2 .303 V 2.303 V
(C) log 0 (D) log
t Vt t ( Vt  V )
Section (F) : Method to monitor the progress of Reactions (Titration Method and Optical
Activity Method)
F-1 For a reaction A  B+ C, it was found that at the end of 10 minutes from the start the total optical rotation
of the system was 50° and when the reaction is complete, it was 100°. Assuming that only B and C are
optically active and dextrorotatory. calculate the rate constant of this first order reaction.
(A) 0.693 min–1 (B) 0.0693 sec–1 (C) 0.0693 min–1 (D) 0.00693 sec–1
F-2 In the above question solution is optically inactive when :
(A) rt = a (B) rt = 0 (C) rt = x (D) rt = (a + x)
F-3 The following data were obtained in an experiment on inversion of cane sugar (a first order kinetics)
Time (min) 0 10 After a long time
Total angle of rotation (degree) +40 +15 – 10
The rate constant (in second–1) is [ln 2 = 0.693]
(A) 0.0693 (B) 1.15  10–3 (C) 0.693 (D) 1.15  10–2
1
F-4 Half life of reaction : H2O2(aq)  H2O(l) + O (g) is independent of initial concentration of H2O2 volume
2 2
of O2 gas after 20 minute is 5L at 1 atm and 27°C and after completion of reaction 50L. The rate constant is
1 2.303 2.303 50 2.303 45
(A) log 10 min 1 (B) log 10 min 1 (C) log min 1 (D) log min 1
20 20 20 45 20 50

F-5 The decomposition of N2O5 in chloroform was followed by measuring the volume of O2 gas evolved : 2N2O5
(CCI4)  2N2O4 (CCI4) + O2 (g). The maximum volume of O2 gas obtained was 100 cm3. In 500 minutes,
90 cm3 of O2 were evolved. The first order rate constant (in min–1) for the disappearance of N2O5 is :
2.303 2.303 100 2.303 90 100
(A) (B) log (C) log (D)
500 500 90 500 100 10  500
Section (G) : Parallel reaction in 1st Order Reactions

G-1 The substance undergoes first order decomposition. The decomposition follows two parallel first order reactions
as :
K1 = 1.26 × 10–4 sec–1 and K2 = 3.8 × 10–5 sec–1
The percentage distribution of B and C

(A) 80% B and 20% C (B) 76.83% B and 23.17%C
(C) 90% B and 10% C (D) 60% B and 40% C
G-2 The rate constant for two parallel reactions were found to be 1.0 × 10–2dm3 mol-1 s–1 and 3.0 × 10–2 dm3
mol–1s–1. If the corresponding energies of activation of the parallel reactions are 60.0 kJ mol–1 and 70.0 kJ
mol–1 respectively, what is the apparent overall energy of activation ?
(A) 130.0 kJ mol–1 (B) 67.5 kJ mol–1 (C) 100.0 kJ mol–1 (D) 65.0 kJ mol–1
G-3 For the follwing parallel chain reaction if the sum of the concentration of B and C at
any time is 2M then what will be [B] t and [C] t respectively?
11 13 3 5 4 6 8 18
(A) M M (B) M, M (C) M, M (D) M, M
12 12 4 4 5 5 13 13
Section (H) : Reversible first order reactions and Sequential first order reactions
H-1 At a given temperature, k1 = k2 for the reaction
A+B C+D
 dx 
If  dt  = k1 [A] [B] – k2[C] [D] in which set of the concentration reaction ceases?
 
[A] [B] [C] [D] [A] [B] [C] [D]
(A) 0.1 M 0.2 M 0.3 M 0.4 M (B) 0.4 M 0.25 M 0.2 M 0.5 M
(C) 0.2 M 0.2 M 0.3 M 0.2 M (D) 0.2 M 0.2 M 0.4 M 0.2 M
k1
H-2 Following reaction can take place in both direction A B,
k2
Graph is given for the forward reaction :
–1
and for the backward reaction following data are given Rate (M s )
[B] Rate
0.01 M 1 × 10–2 Ms–1
0.02 M 2 × 10–2 Ms–1
[A],M
Hence, net reaction rate of B is :
(A) = k1 [A] – k2 [B] (B) = k1 – k2 [B]
(C) = k1 [A] – k2 (D) = k1 – k2

H-3 For the complex Ag+ + 2NH3 [Ag(NH3)2+]
 dx 
  = 2 × 107 L2 mol–2 s–1 [Ag+] [NH ]2 – 1 × 10–2 s–1 [Ag(NH ) +]
 dt  3 3 2
Hence, ratio of rate constants of the forward and backward reactions is :

(A) 2 × 107 L2 mol–2 (B) 2 × 109 L2 mol–2
(C) 1 × 10 L mol
–2 2 –2
(D) 0.5 × 10–9 L2 mol–2
k1 k2
H-4 For the system A B,A C which was started with only A the equilibrium concentration [A]eq
k–1 k–2
is correctly related to [B]eq and [C]eq as :
k 1 [B]eq  k 2 [C] eq k 1 [B]eq  k  2 [C] eq
(A) (B)
(k 1  k 2 ) (k 1  k 2 )
k 1 [B]eq  k 2 [C] eq k 1 [B]eq  k  2 [C] eq

(C) (D)
(k 1  k 2 ) (k 1  k 2 )
k ( time 1) k ( time1)

H-5* For the consecutive reaction A 1    B 2   C following curves were obtained depending
upon the relative values of k1 & k2
Now which of the following is the correct match

(A) figure 1 – (k1 < k2 ) (B) figure 2 – (k1 < k2)
(C) figure 2 – (k1 >> k2) (D) figure 1 – (k1 >> k2)
H-6 Consider the elementary reaction sequence shown in figure. Which of the following equations are correct?
d[A] d [ C]
(A) = k1[A] + k4[D] (B) = k2[B]  k3[C]
dt dt
d [D]
(C) = k4[D] + k3[D] (D) Nothing can be said about order of reactions in this problem
dt
Section (I) : Temperature dependence of rate

I-1 The rate constant, the activation energy and the frequency factor of a chemical reaction at 25°C are
3.0 × 10–4 s–1, 104.4 KJ mol–1 and 6.0 × 1014 s–1 respectively. The value of the rate constant as T   is :
(A) 2.0 × 1018 s–1 (B) 6.0 × 1014 s–1 (C) infinite (D) 3.6 × 1030 s–1
I-2* A large increase in the rate of a reaction for a rise in temperature is due to
(A) increase in the number of collisions (B) the increase in the number of activated molecules
(C) The shortening of mean free path (D) the lowering of activation energy

I-3 Following are the values of Ea and H for three reactions carried out at the same temperature :
I : Ea = 20 kJ mol–1 , H = – 60 kJ mol–1
II : Ea = 10 kJ mol–1 , H = – 20 kJ mol–1
III: Ea = 40 kJ mol–1 , H = + 15 kJ mol–1
If all the three reaction have same frequency factor then fastest and slowest reactions are :
Fastest Slowest
(A) I II
(B) II III
(C) I III
(D) can’t be predicted.
I-4 The rate constant K1 of a reaction is found to be double that of rate constant K2 of another reaction. The
relationship between corresponding activation energies of the two reactions at same temperature (E1 and E2)
can be represented as :
(A) E1 > E2 (B) E1 < E2 (C) E1 = E2 (D) None of these
I-5 When a graph between log K and 1/T is drawn a straight line is obtained. The point at which line cuts y -axis
and x -axis respectively correspond to the temp :
(A) 0, Ea / 2.303 R log A (B) , Ea / (R ln A)
(C) 0, log A (D) None of these.
I-6 How much faster would a reaction proceed at 25°C than at 0°C if the activation energy is 65 kJ?
(A) 2 times (B) 5 times (C) 11 times (D) 16 times
I-7 For a reaction A  B, Ea = 10 kJ mol–1 , H = 5 kJ mol–1 . Thus, potential energy profile for this reaction is :
(A) (B)
(C) (D)
I-8 For a certain reaction the variation of the rate constant with temperature is given by the equation
 ln 3 
ln kt = ln k0 +   t (t  0°C)
 10 
The value of the temperature coefficient of the reaction rate is therefore
(A) 4 (B) 3 (C) 10 (D) 2
I-9* Which of the following statements about the arrhenius equation are correct ?
(A) The pre exponential factor become equal to the rate constant of the reaction at temperature T  
(B) When the activation energy of the reaction  zero, the rate becomes independent of temperature.
(C) The term e–Ea/RT represents the fractions of the molecules having energy is excess of the threshold value.
(D) On raising temperature , rate constant of the reaction of greater activation energy increases less rapidly
than that of the reaction of smaller activation energy.

Section (J) : Catalyst dependence of rate
J-1 The Ea of a reaction in presence of a catalyst is 4.15 kJ mol–1 and in absence of a catalyst is 8.3 kJ mol–1.
1
What is slope of the plot of lnk vs in the absence of catalyst
T
(A) + 1 (B) –1 (C) + 1000 (D) –1000
J-2 For the decomposition of H the following logarithmic plot is shown : [R = 1.98 cal/mol-K]
The activation energy of the reaction is about
1
(A) 45600 cal
0
(B) 13500 cal logk
–1
(C) 24600 cal –2
(D) 32300 cal –3
1.2 1.3 1.4 1.5 1.6
103/T
Section (K) : Type of Reaction and Determination of rate law and order with the help of
given mechanism
K-1 For the reaction H2 (g) + Br2 (g)  2HBr (g) the experiment data suggested that r = k[H2][Br2]1/2
The molecularity and order of the reaction are respectively :
(A) 2, 3/ 2 (B) 3/2 , 3/2 (C) Not defined, 3/2 (D) 1,1/2
K-2 The reaction of NO2 (g) and O3 (g) is first-order in NO2 (g) and O3 (g)
2 NO2 (g) + O3 (g)  N2O5 (g) + O2 (g)
The reaction can take place by mechanism :
slow
I : NO2 + O3  NO3 + O2
fast
NO3 + NO2    N 2 O 5
ka fast
II : O3 O2 + [O]
kb
slow
NO2 + O   NO3
fast
NO3 + NO2   N2O5
Select correct mechanism.
(A) I only (B) II only (C) both I and II (D) None of I and II
K-3 A hypothetical reaction X2 + Y2  2XY follows the mechanism given below..
X2 X + X [Fast]
X + Y2  XY + Y [Slow]
X + Y  XY [Fast]
The order of overall reaction is
(A) 2 (B) 1 (C) 1.5 (D) Zero
K-4 The reaction of hydrogen, and iodine monochloride is represented by the equation :
H2(g) + 2Cl(g)  2HCl(g) + 2(g)
This reaction is first–order in H2(g) and also first–order in Cl(g). Which of these proposed mechanism
can be consistent with the given information about this reaction ?
Mechanism  : H2(g) + 2Cl(g)  2HCl(g) + 2(g)
Mechanism  : H2(g) + Cl(g)   HCl(g) + H(g)

Slow
HI(g) + Cl(g)   HCl(g) + I2(g)

fast
(A)  only (B)  only (C) both  and  (D) neither  nor 

K-5 Reaction A + B  D + E take place as
K1
A + B  K2
 2C ; C + B  2D
C + A  K3
 2E
The rate of disapperance of C is given by
d [ C] d [ C]
(A) – = K2 [B][C] + K3[A][C] – 2K1[A][B] (B) – = K2[B][C] + K3 [E] – K1[C]
dt dt
d [ C] d
(C) – = K2[D]O + K3[E] – K1[C] (D) – [C] = 2K1[A][B] – K2 [B][C] – K3[A][C]
dt dt
K-6 The steady state concentration of the activated molecule [A] in the following sequence of steps is given by:
K K2
A + A 1  A + A* ; A* + A 
 2A
K 2 [A] K 1[ A ] K 1K 2
(A) K1 (B) K2 (C) K1K2[A] (D)
[A]
K-7* Select the correct statements :

(A) the molecularity of an elementary reaction indicates how many reactant molecules take part in the step.
(B) the rate law of an elementary reaction can be predicted by simply seeing the stoichiometry of reaction.
(C) the slowest elementary step in sequence of the reactions governs the overall rate of formation of product.
(D) a rate law is often derived from a proposed mechanism by imposing the steady state approximation or
assuming that there is a pre-equilibrium.
Section (L) : Radio Activity

L-1 Radioactivity is affected by :
(A) temperature (B) Pressure
(C) electric and magnetic field (D) none of these
L-2 Half life period of 10 gm radioactive element is 20 days. Then half life period of 100 gm of this element is :
(A) 20 days (B) 200 days (C) 100 days (D) 10 days
L-3 Determine the average life of U238 having t0.5 = 138.5 day.
(A) 138.5 day (B) 199.86 day (C) 238 day (D) None of these
L-4 A radioactive element has a half life of one day. After three days the amount of the element left will be :
(A) 1/2 of the original amount (B) 1/4 of the original amount
(C) 1/8 of the original amount (D) 1/16 of the original amount
L-5 The activity per ml of a solution of radioactive substance is x. How much water be added to 200 ml of this
solution so that the acitivity falls to x/20 per ml after 4 half-lives ?
(A) 100 ml (B) 150 ml (C) 80 ml (D) 50 ml.
L-6 The  activity in 1g sample of 226Ra (t1/2 = 1600 years) is equal to :

(A) 2.19 × 1012 dpm (B) 2.19 × 1014 dpm (C) 2.19 × 1016 dpm (D) 4.96 × 1012 dpm
L-7 A sample of rock from moon contains equal number of atom s of uranium and lead
(t1/2 for U = 4.5 × 109 years). The age of the rock would be :
(A) 9.0 × 109 years (B) 4.5 × 109 years (C) 13.5 ×109 years (D) 2.25 × 109 years
L-8 The half-life of 99Tc is 6.0 h. The total residual activity in a patient after receiving an injection containing 99Tc
must not be more than 0.01 Ci , after 36.0 hours. What is the maximum activity (in Ci) that the sample
injected can have ?
(A) 0.06 (B) 0.16 (C) 0.32 (D) 0.64

L-9 The radioactive decay is first order reaction. Its rate, on increasing 10ºC temperature
(A) increases 2-3 times (B) decreases 2-3 times
(C) does not change (D) increases 10 times
L-10 The half  life of a radioactive isotope is 3 hours . If the initial mass of the isotope were 256 gm , the
mass of it remaining undecayed after 18 hours would be :
(A) 4 gm (B) 8 gm (C) 12 gm (D) 16 gm
L-11 A radioactive isotope X with half - life of 6.93 × 109 years decay to Y which is stable. A sample of rock from
the moon was found to contain both the element X and Y in the mole ratio 1 : 7.What is the age of the rock?
(A) 2.079 × 1010 years (B) 1.94 × 1010 years (C) 1.33 × 109 years (D) 1010 years
PART - III : ASSERTION / REASON

Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
1. Statement-1 : For A + 2B  C (rate= K[A]1[B]0), the half life time of reaction is only defined when conc.
of A and B are in stoichiometric ratio
Statement-2 : For above given order half life of reaction is directly proportional to conc. of A and not to conc.
of B due to its zero order.
2. Statement-1 : Many reactions occurring on solid surface are zero order reactions.
Au
Statement-2 : N2 O(g) 
 N2 (g)  1/ 2O 2 ; rate = k[N2O]0 = k = constant is a zero order reaction.
3. Statement-1 : Half life of a certain radioactive element is 100 days. After 200 days, fraction left undecaye
will be 25%.
n
Ct  1 
Statement-2 :    , where symbols have standard meaning.
C0  2 
4. Statement-1 : If the activation energy of reaction is zero temperature will have no effect on the rate constant
Statement-2 : Lower the activation energy faster is the reaction
k1 k2
5. Statement-1 : In A  B  C
If half life of A is very less as compared to B, so the net reaction is A  C with rate constant
(k1 × k2)
Statement-2 : Slowest step is the rate determining step so B  C is rate determining step.


1. Decomposition of ammonia on platinum surface follow the change,
2NH3 (g)  N2 (g) + 3H2 (g)
d [NH3 ] d [N2 ] d [H2 ]
(a) What does denote ? (b) What does and denote?
dt dt dt
(c) If the decomposition is zero order then what are the rate of production of N2 and H2 if k = 2.5 × 10–4 Ms–1?
d [NH3 ] k1 [NH3 ]
(d) If the rate obeys – = 1  k [NH ] , what will be the order for decomposition of NH3 if (i) [NH3] is very
dt 2 3
very less and (ii) [NH3] is very very high K1 and K2 are constant.
2. A 1mL sample of a bacterial culture at 370C is taken, and diluted to 10 L. A 1mL sample of the diluted culture
is spread on a culture plate. Ten minutes later, another 1mL sample taken from the original culture diluted
and spread in the same way. The two plates are incubated for 24 hours. The first sample exhibits 48 colonies
of bacteria, the second 72 colonies. If we assume that each colony originates with a single bacterium, what
is the generation time (time required for doubling the population).
3. The acid catalysed hydrolysis of an organic compound A at 300C has a time for half change of 100 minutes,
when carried out in a buffer solution at pH 5 and of 10 minutes, when carried out at pH 4. Both times of half
d[ A ]
change are independent of the initial concentration of A. If the rate of reaction is given by = k[A]a[H+]b,
dt
what are the values of a and b?
4. Decomposition of H2O2 is a first order reaction. A solution of H2O2 labelled as 20 volumes was left open. Due
to this, some H2O2 decomposed. To determine the new volume strength after 6 hours, 10 mL of this solution
was diluted to 100 mL. 10 mL of this diluted solution was titrated against 25 mL of 0.025M KMnO4 solution
20
under acidic conditions. Calculate the rate constant for decomposition of H2O2. [ln = 0.1335]
17 .5
5. A quantity of ethyl acetate is mixed with an excess of sodium hydroxide at 25ºC. 100 c.c. of the mixture is
immediately titrated against 0.05 N Hydrochloric acid, of which 75 c.c. were required for neutralisation. After
30 minutes, 50 c.c. of the mixture required, similarly, 25 c.c. of the acid. When the original reaction of ester
was complete 25 c.c. of the mixture required 6.25 c.c. of the acid. Calculate the second order velocity
constant (at time = 0) of the reaction, using concentration in moles per litre and time in minutes. Reaction is
first order each w.r.t. NaOH & ester. Indicator chosen for above titration is such that, it gives end point when
hydrochloric acid reacts with NaOH only. (log2 = 0.30, log3 = 0.48, ln10 = 2.3)
6. A certain reactant Bn+ is getting converted to B(n+4)+ in solution. The rate constant of this reaction is measured
by titrating a volume of the solution with a reducing reagent which only reacts with Bn+ and B(n+4)+. In this
process, it converts Bn+ to B(n2)+ and B(n+4)+ to B(n1)+. At t=0, the volume of the reagent consumed is 25 ml
and at t = 10 min, the volume used up is 32 ml. Calculate the rate constant of the conversion of Bn+ to B(n+4)+
assuming it to be a first order reaction.
7. An organic compound A decomposes by following two parallel first order mechanisms:
k1 1 –5 –1
k 2 = 9 and k1 = 1.3 × 10 sec .
Calculate the concentration ratio of C to A, if an experiment is allowed to start with only A for one hour.
8. The formation in water of dpotassium chromooxalate from its lform is reversible reaction which is first
order in both directions, the racemate being the equilibrium product. A polarimeter experiment at 220C
showed that, after 506 sec, 12 mole % of the lisomer was converted to the dform. Find the rate constant
for the forward and the reverse reactions.

9. For an isomerisation reaction A B in gaseous phase, the equilibrium constant at 60°C is 3.60.
Both forward and backward reactions are of first order. Starting with an initial pressure of P atm, of A, the
pressure became 0.25 P atm in 40 minutes. Find the values of individual rate constants for the forward and
backward reactions.
10. Mole percentage of A as a function of time in the following reversible first order reaction A B are :
Time (hr) 0 1 Infinity
Mole % of A 100 75 30
Determine mole percentage of A after four hour from the beginning.
11. The mean life of a first order reaction at 610 K is 127 hours. What fraction of the initial concentration will
decompose in 42 hours at 600 K, given that the activation energy is 30 Kcal mol–1 ?
12. Two reaction (i) A  products (ii) B  products, follow first order kinetics. The rate of the reaction (i) is
doubled when the temperature is raised from 300 K to 310K. The half life for this reaction at 310K is 30
minutes. At temperature 310 K, B decomposes twice as fast as A. If the energy of activation for the reaction
(ii) is half that of reaction (i), calculate the rate constant of the reaction (ii) at 300K.
13. Experiment shows that the equilibrium constant of the reaction :
C2H5OH + CH3COOH CH3COOC2H5 + H2O
is 2.8 at room temperature, and the velocity constant of the forward reaction is 0.002. When a catalyst is
added this velocity constant is increased to 0.0045. What is now the velocity constant of the backward
reaction?
14. A 1st order chemical reaction was carried out for 1.0 hour in absence of a catalyst and 20% reaction was
complete. A catalyst was then added and reaction was allowed to continue for next 30 min when 60%
reaction was complete. A second catalyst was then added at this time and reaction was allowed to continue
for further 10 min. when 90% reaction was complete. If activation energy of the original path was 80 kJ,
determine activation energies of catalyzed pathways. Assume constant temperature throughout to be 300 K.
15. Derive an expression for the velocity of reaction :
2N2O5(g)  4NO2(g) + O2(g)
With the help of following mechanism
Ka K a
N2O5 
 NO2 + NO3 ; NO3 + NO2   N2O5
Kb Kc
NO2 + NO3 
 NO2 + O2 + NO ; NO + NO3 
 2NO2
16. Derive an expression for the velocity of reaction :

H2 (g) + Br2 (g)  2HBr (g)
With the help of following mechanism
k k
Br2 

1
2Br ; Br + H2 
2
 HBr + H
k k k
H + Br2 
3
 HBr + Br ; H + HBr 
4
 H2 + Br ; Br + Br 
5
 Br2
210
17. 84Po decays with alpha to 82Pb206 with half life of 138.4 days. If 1.0 gram of Po210 is placed in a sealed
tube, how much helium will accumulate in 69.2 days? Express the answer in cm3 at S.T.P.

Single choice type
1. For a chemical reaction A  products, the rate of disappearance of A is given by :
– dC A K 1C A
= 1  K C At low CA the reaction is of the ..... order with rate constant.....(Assume K1, K2 are
dt 2 A
lesser than 1)
K1 K1
(A) , K (B) I, K1 (C) II, K1/K2 (D) II, K  K
2 1 2

2. The reaction A(g) + 2B(g)  C(g) is an elementary reaction. In an experiment involving this reaction, the
initial partial pressures of A and B are PA = 0.40 atm and PB = 1.0 atm respectively. When pressure of
C becomes 0.3 atm in the reaction the rate of the reaction relative to the initial rate is :
1 1 1
(A) (B) (C) (D) none of these
12 50 25
3. The rate law for the dimerisation of NO2 is

d [NO 2 ]
– = k [NO2]2
dt
which of the following changes will change the value of the specific rate constant , k :
(A) Doubling the total pressure on the system
(B) Doubling the temperature
(C) Both of (A) and (B)
(D) None of the above
4. If for a reaction in which A(g) converts to B(g) the reaction carried out at const.
V & T results into the following graph.
(A) then the reaction must be A(g)  3B(g) and is a first order reaction.
(B) then the reaction must be A(g)  3B(g) and is a second order reaction.
(C) then the reaction must be A(g)  3B(g) and is a zero order reaction.
(D) then the reaction must be A(g)  3B(g) and is a first order reaction.
5. A graph plotted between log t50% vs. log concentration is a straight line. What conclusion can you draw from
this graph.
(A) n = 1 ; t1/2  a (B) n = 2, t1/2  1/a

(C) n = 1 ; t1/2 = (0.693 / k) (D) None of these
1 1
6. Concentration of the reactant in first-order is reduced to 2 after : (Natural life = )
e K
(A) one natural life-time (B) two-natural life-time
(C) three natural life-time (D) four natural life-time
7. In a reaction involving one single reactant, the fraction of the reactant consumed may be defined as f =
 C 
1  
 C  where C0 and C are the concentrations of the reactant at the start and after time, t. For a first order
 0
reaction
df df df df
(A) = k(1  f) (B)  = kf (C)  = k(1  f) (D) = kf
dt dt dt dt
 dx   dx 
8. A  Product and  dt  = k[A]2 . If log  dt  is plotted against log [A], then graph is of the type :
   
(A) (B) (C) (D)

9. For a first order reaction, nA B whose concentration vs time curve is as shown in the figure. If half life for
the reaction is 24 minutes . Find out the value of n.
(A) 1 (B) 2 (C) 3 (D) 4
10. The inversion of cane sugar proceeds with half life of 50 minute at pH = 5 for any concentration of sugar.
However if pH = 6, the half life changes to 500 minute of any concentration of sugar. The rate law expression
for the inversion of cane sugar is written as : r = K [sugar]1 [H+]y. Determine the value of y.
(A) r = K [sugar]1 [H+]-1 (B) r = K [sugar]1 [H+]2
1
(C) r = K [sugar] [H ]+ 1 (D) r = K [sugar]1 [H+]0.
11. The following data is for the decomposition of ammonium nitrite in aqeous solution.
Volume of N2 in cc. Time (minutes)

6.25 10
9.00 15
11.40 20
13.65 25
35.05 infinity
The order of the reaction is

(A) zero (B) one (C) minus one (D) minus two
12. Formation of NO2F from NO2 and F2 as per the reaction 2NO2(g) + F2(g)  2NO2F(g) is a second order
reaction, first order with respect to NO2 and first order with respect to F2. If NO2 and F2 are present in a
closed vessel in ratio 2 :1 maintained at a constant temperature with an initial total pressure of 3 atm, what
will be the total pressure in the vessel after the reaction is complete?
(A) 1atm (B) 2 atm (C) 2.5 atm (D) 3 atm
13. Acid catalysed hydrolysis of ester is first-order reaction and rate constant is given by
2.303 V  V0
k= log V  V
t  t
where V0, Vt and V are the volume of standard NaOH required to neutralise acid present at a given time ; if
ester is 50% hydrolysed then :
(A) V = Vt (B) V = (Vt – V0) (C) V = 2Vt – V0 (D) V = 2Vt + V0
14. In a hypothetical reaction, A(aq) 2B(aq) + C(aq) (1st order decomposition)

'A' is optically active (dextro-rototory) while 'B' and 'C' are optically inactive but 'B' takes part in a titration
reaction (fast reaction) with H2O2. Hence, the progress of reaction can be monitored by measuring rotation of
plane polarised light or by measuring volume of H2O2 consumed in titration.
In an experiment the optical rotation was found to be  = 40° at t = 20 min and  = 10° at t = 50 min. from start
of the reaction. If the progress would have been monitored by titration method, volume of H2O2 consumed at
t = 15 min. (from start) is 40 ml then volume of H2O2 consumed at t = 60 min will be:
(A) 60 ml (B) 75 ml (C) 52.5 ml (D) 90 ml

15. Inversion of sucrose (C12H22O11) is first-order reaction and is studied by measuring angle of rotation at different
instant of time
+
H
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose Glucose Fructose
d d l
If (r – r0)  a and (r – rt)  (a – x) (where r, rt and r are the angle of rotation at the start, at the time t and at
the end of the reaction respectively, then there is 50% inversion when :
(A) r0 = 2rt – r (B) r0 = rt – r (C) r0 = rt – 2r (D) r0 = rt + r
16. For a first order reaction A B + 2C + 3D (A is optically inactive and B, C and D are dextrorotary), the optical
rotation at time t and  are rt and r respectively, the expression for rate constant is
1 rt 1 r 1 r  rt
(A) K = ln (B) k = ln (C) k = ln (D) none of these
t r  rt t r  rt t rt
17. For the decomposition of H2O 2(aq) it was found that VO2 (t = 15 min.) was 100 mL (at 0ºC and 1 atm)
while VO2 (maximum) was 200 mL (at 0ºC and 2 atm). If the same reaction had been followed by the
( c M) ( c M)
titration method and if VKMnO 4 (t = 0) had been 40 mL, what would VKMnO 4 (t = 15 min) have been ?
(A) 30 mL (B) 25 mL (C) 20 mL (D) 15 mL
18. A (aq)  B (aq) + C (aq) is a first order reaction.
Time t 
moles of reagent n1 n2
Reaction progress is measure with the help of titration of reagent ‘R’.If all A, B and C reacted with reagent and
 mol. wt 
have ‘n’ factors n factors; eq.wt. 
n 
in the ratio of 1 : 2 : 3 with the reagent.The k in terms of t, n1 and

n2 is :
1  n2  1  2n 2  1  4n 2  1  4n 2 
(A) k  t ln  n  n  (B) k  t ln  n  n  (C) k  t ln  n  n  (D) k  t ln  5(n  n ) 
 2 1  2 1  2 1  2 1 
19. For the following parallel chain reaction
 [B] t 16 
what will be that value of overall half-life of A in minutes? Given that [C]  9 
 t 
(A) 3.3 (B) 6.3 (C) 3.6 (D) None
20. For the follwing parallel chain reaction the overall half life of A is 12 hours If rate
of formation of C is 60% of a rate of decomposition of A then what will be half life of A while it is converting into
B?
(A) 40 hours (B) 60 hours (C) 50 hours (D) 30 hours
21. At what time will B be present in greatest concentration ?

k1 1 k1 1 k1
(A) K  K (B) K  K ln k (C) K  K ln k (D) None of these
2 1 1 2 2 2 1 2

5 1 6 1 3 1
K  210 s K  810 s K  310 s
22. A    B      C    D
The rate determing step of the reaction is :
(A) A  B (B) C D (C) B  C (D) A D
23. The Arrhenius relationship of two different reactions is shown below. Which reaction is faster at a lower
temperature and which is more sensitive to changes of temperature ?
(A) B faster, A more sensitive (B) B in both cases
(C) A in both cases (D) A faster, B more sensitive
24. Consider the following reactions at 300 K.

A  B (uncatalysed reaction)
A   B (catalyst reaction)
catalyst
The activation energy is lowered by 8.314 KJ mol–1 for the catalysed reaction. How many times the rate of
this catalysed reaction greater than that of uncatalysed reaction ? (Given e3.33 = 28)
25. For the same mechanism as Problem refer to the given Fig. and choose the correct set of identifications.
E + S ES
(enzyme) (reactant) (intermediate-1)
ES EP
(intermediate-1) (intermediate-2)
EP E + P
(intermediate-2) (enzyme) (product)
(1) (2) (3) (4)
(A) E for Ea for Eoverall Ea for
E + S  ES ES  EP for S  P EP  E + P
(B) Ea for E for Ea for overall
E + S  ES E + S  ES ES  EP for S  P
(C) Ea for Ea for Eoverall E for
ES  EP EP  E + P for S  P EP  E + P
(D) Ea for Ea for Ea for Eoverall
E + S  ES ES  EP EP  E + P for S  P
(E) E for Eoverall E for l
Ea for
E + S  ES for S  P EP  E + P EP  E + P
26. A simple mechanism for enzyme-catalyzed reaction is given by the following set of equations
E + S ES
(enzyme) (reactant) (intermediate-1)
ES EP
(intermediate-1) (intermediate-2)
EP E + P
(intermediate-2) (enzyme) (product)
This is known as the Michaelis–Menten mechanism. The potential energy diagram is shown in the fig. Which
of the following sets of identifications is correct ? (Assume that the temperature and pressure are constant).
(1) (2) (3) (4)
(A) E + P. EP ES E+S
(B) ES Activated complex EP Activated complex
(C) EP Activated complex ES Activated complex
(D) E+S ES EP E+P

More than one choice type
27. Decomposition of 3 A(g)  2 B(g) + 2C(g) follows first order kinetics. Initially only A is present in the
container. Pressure developed after 20 min. and infinite time are 3.5 and 4 atm respectively. Which of the
following is true.
(A) t50% = 20 min (B) t75% = 40 min (C) t99% = 64/3 min (D) t87.5% = 60 min
28. The polarimeter readings in an experiment to measure the rate of inversion of cane suger (1st order reaction)
were as follows
time (min) : 0 30 
angle (degree) : 30 20 – 15
Identify the true statement (s) log 2 = 0.3, log 3 = 0.48, log 7 = 0.84
(A) the half life of the reaction is 75 min.
(B) the solution is optically inactive at 120 min.
(C) The equimolar mixture of the products is dextrorotatory.
(D) The angle would be 7.5° at half time.
29. Consider the decay of P to A and B by two parallel first order reactions as shown in Fig. Given
Reaction H Rate constant Energy of activation

PA HA kA EA
PB HB kB EB
Which of the following is(are) true?

(A) a = EB (B) b = EA (C) HA = b  d (D) HB = c  a
30. A reaction takes place in three steps. The rate constant of the three steps are K1, K2 and K3 respectively. The
K1K 3
overall rate constant K = K .
2
The energy of activation for the three steps are 40, 30 and 20 KJ respectively. Therefore :
(A) Overall energy of activation is 10 KJ
(B) Overall energy of activation is 30 KJ
K1
(C) The reaction mechanism is 2A A* + A ; A * product and overall order is one.
K2
K1
(D) The reaction mechanism is A  K2 K3
 B ; B  C ; C  product and overall order is one
31. For the reaction CH4 + Br 2  CH3Br + HBr the experimental data require the following rate equation :
d k 1[CH4 ][Br2 ]
[CH3Br] = 1  k [HBr ] /[Br ]
dt 2 2
Which of the following is/are true regarding this ?

(A) The reaction is a single step reaction
(B) The reaction is 2nd order in the initial stages {[HBr]  0}
(C) The reaction is 2nd order in the final stages {[Br2]  0}
(D) The molecularity of the reaction is two
32. Rate of radioactive disintegration (–dN/dt) is also known as :
(A) Activity (B) Radioactivity
(C) Half-life period (D) Average life period

PART - III : MATCH THE COLUMN
1. Match the following :
Column-I Column-II
(Graph) (Slope)
(A) C Vs t (abscissa) for zero order (p) unity
(B) log C Vs t (abscissa) for first order (q) zero
  dc 
(C)  dt  Vs c for zero order (r) – k
 
  dc  k
(D) ln  dt  Vs lnc for first order (s) –
  2.303

Column-I Column-II
(A) A + B  C + D (p) Unit of rate constant possess concentration unit
r = k1 [A] [B]
(B) A + B  C + D (q) Rate constant for the reaction of both the reactants are equal
r = k2 [A] [B]º
(C) A + B  C + D (r) Rate of consumption of at least one of the reactants is equal to rate of
r = k3 [A]º [B]º production of at least one of the products
(D) 2A + B  2C + 3D (s) If both reactants are taken in stoichiometric ratio, half life for both
r = k3 [A]º [B]º reactants are equal.

Column-I Column-II
(A) If the activation energy is 65 kJ then how much time (p) 2
faster a reaction proceed at 25°C than at 0°C
(B) Rate constant of a first - order reaction is 0.0693 min–1. (q) Zero
If we start with 20 mol L–1, it is reduced to 2.5 mol L–1
in how many minutes
(C) Half - lives of first - order and zero order reactions are same. (r) 11
Ratio of rates at the start of reaction is how many times of 0.693
Assume initial concentration to be same for the both.
(D) the half-life periods are given , (s) 30
[A]0 (M) 0.0677 0.136 0.272
t1/2 (sec) 240 480 960
order of the reaction is
PART - IV : COMPREHENSION
COMPREHENSIONS :
Read the following passage carefully and answer the questions.
Comprehension # 1
A(g)  2B(g) + C(g)
Initially at t = 0 gas A was present along with some amount of gas (C). At t = 0 mole fraction of gas C is
1/3. After some time t = t1, total pressure is half of the final total pressure at t = tx (a very long time). Assume
this decomposition is a first order, at a constant temperature. It is also given at t = tx, final total pressure is
35 bar.

1. At t = t1 pressure of gas B is :
(A) 2.5 bar (B) 1.25 bar (C) 5.0 bar (D) data is insufficient
2. Rate constant (k) = (log 64 – log 49) s–1. Value of t1 in seconds is :

(A) 2.15 s (B) 1.5 s (C) 2.3 s (D) 1.15 s
3. Ratio of rate constant at t = 0 to t = t1 to t = tx is :

(A) 2 : 3 : 4 (B) 1 : 1 : 1 (C) 1 : 3 : 5 (D) 1 : 3 : 5
Comprehension # 2
4. For the (Set-1) :

(A) if T1 > T2, k1 > k2 always
(B) if T1 > T2, k1 > k2 (for exothermic reaction)
(C) if T1 > T2, k1 < k2 (for endothermic reaction)
(D) Ea1  Ea2
5. For the (Set-1) :
(A) Ea1 > Ea2 if T1 > T2 (B) Ea1 < Ea2 if T1 > T2
(C) Ea1 = Ea2 (D) Ea1 = 0.5 Ea2
6. Comparing set-I and II :
(A) k4 > k3 & k2 > k1 , if T2 > T1 (endothermic)
(B) k4 < k3 & k2 > k1 , if T2 < T1 (endothermic)
(C) k4 > k3 & k2 > k1 , if T2 < T1 (exothermic)
(D) k4 < k3 & k2 < k1, if T2 > T1 (exothermic)
Comprehension # 3
Competing First-Order Reactions
Frequently a species can react in different ways to give a variety of products. For example, toluene can be
nitrated at the ortho, meta, or para positions, We shall consider the simplest case, that of two competing
irreversible first-order reactions :
A  k1 C and A k 2 D
 
where the stoichiometric coefficients are taken as unity for simplicity. The rate law is
 d[A] 
  = – k [A] – k [A] = – (k + k ) [A]  [A] = [A]0 e (k1 k 2 )t .
 dt  1 2 1 2
 d [C] 
For C, we have   = k [A] = k [A] e (k1 k 2 )t . Multiplication by dt and integration from time 0
 dt  1 1 0
k 1[ A ]0 ( k 1  k 2 ) t
(where [C]0 = 0) to an arbitary time t gives [C] = k  k (1  e )
1 2
 d [D]  k 2 [ A ]0
Similarly, integration of   gives [D] = k  k (1 – e (k1  k 2 )t )
 dt  1 2
The sum of the rate constants k1 + k2 appears in the exponentials for both [C] and [D].
[C] k1
At any time we also have = k
[D] 2

7. A starting initially with only A Which of the following is correct at time t
(A) [A]0 = [A]t +[B]t + [C]t (B) [A]0 = [A]t + 2 [B]t + 3 [C]t
[B] t [C] t 2
(C) [A]0 = [A]t + + (D) [A]0 = [A]t +[B]t + [C]t
2 3 3
[ X] t
8. X starting with only 'X', ratio [ Y ]  [ Z]
t t
1
(A) Independent of time (B) kt
(e  1)
(C) Depends upon initial concentration of X (D) [A]0 (ekt –1)
9. At high temperature acetic acid decomposes into CO2 & CH4 and simultaneously into CH2CO (ketene) and
H2O
1
(i) k1 3s
CH3COOH   CH4 + CO2
1
(ii) k 2  4s
CH3COOH   CH2CO + H2O
What is the fraction of acetic acid reacting as per reaction (i) ?
3 3 4
(A) (B) (C) (D) none of these
4 7 7
10. For A starting with pure A ratio of rate of production of B to C is
(A) Independent of time (B) Independent of temperature

(C) Depends upon initial concentration of A (D) Independent of mechanism of reaction
PART - I : IIT-JEE PROBLEMS (PREVIOUS YEARS)

* Marked Questions may have more than one correct option.
1. The rate constant for the reaction,2N2O5  4NO2+ O2, is 3 ×10–5 s–1. If the rate is 2.4 × 10–5 mol L–1 s–1,
then the concentration of N2O5 (in mol L–1) is : [JEE-2000, 1/35]
(A) 1.4 (B) 1.2 (C) 0.04 (D) 0.8
2. 238 is radioactive and it emits  and  particles to form 206 . Calculate the number of  and  particles
92 U 82 Pb
emitted in this conversion. An ore of 238 is found to contain 238 and 206 in the weight ratio of 1 : 0.9
92 U 92 U 82 Pb
the half life period of 238 is 4.5 × 10 years. Calculate the age of the ore.
9
[IIT-JEE-2000]
92 U
3. A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the presence of a
catalyst at the same rate, the temperature required is 400 K. Calculate the activation energy of the reaction
if the catalyst lowers the activation barrier by 20 kJ mol–1. [JEE-2000, 3/100]

4. If '' is the intensity of absorbed light and 'C' is the concentration of AB for the photochemical process,
AB + hv  AB * , the rate of formation of AB * is directly proportional to [JEE-2001, 1/35]
(A) C (B)  (C) 2 (D) C.
5. The rate of a first order reaction is 0.04 mole litre–1 s–1 at 10 minutes and 0.03 mol litre–1 s–1 at 20 minutes
after initiation. Find the half life of the reaction. [JEE-2001, 5/100]
6. Consider the chemical reaction,
N2(g) + 3H2(g)  2NH3(g)
The rate of this reaction can be expressed in terms of time derivatives of conc. of N2(g) , H2(g) or NH3(g).
Identify the correct relationship amongst rate expressions : [JEE-2002, 3/90]
d [N2 ] 1 d [H2 ] 1 d [NH3 ] d [N2 ] d [H2 ] d [NH3 ]
(A) Rate =    (B) Rate =  3 2
dt 3 dt 2 dt dt dt dt
d [N2 ] 1 d [H2 ] 1 d [NH3 ] d [N2 ] d [H2 ] d [NH3 ]

(C) Rate =   (D) Rate =   
dt 3 dt 2 dt dt dt dt
7. 64Cu (half life = 12.8 hours) decays by  – emission(38%),  + emission(19%) and electron capture(43%).
Write the decay products and calculate partial half lives for each of the decay processes. [IIT-JEE-2002]
8. In the biologically-catalysed oxidation of ethanol, the concentration of ethanol decreases in a first order
reaction from 800 mol dm–3 to 50 mol dm–3 in 2 ×104 s. The rate constant (s–1) of the reaction is :
[JEE-2003, 3/84]
(A) 3.45 × 10–5 (B) 1.38 × 10–4 (C) 1.00 × 10–4 (D) 5.00 × 10–5
9. Given X  product (Taking 1st order reaction)
conc 0.01 0.0025
(mol/lit)
time (min) 0 40
Initial rate of reaction is in mol /l/min. [JEE-2004, 3/84]
(A) 3.43 × 10–4 (B) 1.73 × 10–4 (C) 3.43 × 10–5 (D) 1.73 × 10–5
10. Initial rates, r0, of the A + B  P at different initial concentrations of A and B ([A]0 and [B]0) are given below:
––––––––––––––––––––––––––––––––––––––––––––
[A]0 [B]0 r0
(mol L–1) (mol L–1) (mol L–1 s–1)
––––––––––––––––––––––––––––––––––––––––––––
0.1 0.1 0.05
0.2 0.1 0.10
0.1 0.2 0.05
––––––––––––––––––––––––––––––––––––––––––––
(a) Write the rate equation.
(b) Calculate the rate constant of the reaction. [JEE-2004, 2/60]
11. For a reaction 2X(g)  3Y(g) + 2Z(g) the following data is obtained.
Px (mm of Hg)
Time (min)
(Partial pressure of X)
0 800
100 400
200 200
Find order with respect to X, rate constant of the reaction, time taken for 75% completion and find the total
pressure when partial pressure of X, Px = 700 mm of Hg. [JEE-2005, 2/60]
Comprehension #
Carbon–14 is used to determine the age of organic material. The procedure is based on the formation of 14C
by neutron capture in the upper atmosphere.
14 N  n1  14C  p1
7 0 6 1

C is absorbed by living organisms during photosynthesis. The 14C content is constant in living organism,
14
once the plant or animal dies, the uptake of carbon dioxide by it ceases and the level of 14C in the dead
being, falls due to the decay which C14 undergoes
14
6C  14
7N  
The half life period of 14C is 5770 years. The decay constant () can be calculated by using the following
0.693
formula  = t
1/ 2
The comparison of the  – activity of the dead matter with that of the carbon still in circulation enables
measurement of the period of the isolation of the material from the living cycle. The method however, ceases
to be accurate over periods longer than 30,000 years. The proportion of 14C to 12C in living matter is 1 : 1012.
12. Which of the following option is correct? [IIT-JEE 2006]

(A) Rate of exchange of carbon between atmosphere and living is slower than decay of 14C.
(B) Carbon dating can be used to find out the age of earth crust and rocks
(C) Rate of exchange of 14C between atmosphere and living organism is so fast that an equilibrium is set up
between the intake of 14C by organism and its exponential decay.
(D) Carbon dating can not be used to determine concentration of 14C in dead beings.
13. What should be the age of fossil for meaningful determination of its age? [IIT-JEE 2006]
(A) 6 years (B) 6000 years
(C) 60,000 years (D) It can be used to calculate any age
14. A nuclear explosion has taken place leading to increase in concentration of 14C in nearby areas. 14C
concentration is C1 in nearby areas and C2 in areas far away. If the age of the fossil is determined to be T1
and T2 at the places respectively then [IIT-JEE 2006]
1 C1
(A) The age of the fossil will increase at the place where explosion has taken place and T1 – T2 = ln C
 2
1 C1
(B) The age of the fossil will decrease at the place where explosion has taken place and T1 – T2 = ln C
 2
(C) The age of fossil will be determined to be same

1T C
1
(D) T  C
2 2
15. Consider a reaction aG + bH  Products. When concentration of both the reactants G and H is doubled,
the rate increases by eight times. However, when concentration of G is doubled keeping the concentration
of H fixed, the rate is doubled. The overall order of the reaction is : [JEE-2007, 3/81]
(A) 0 (B) 1 (C) 2 (D) 3
16. Under the same reaction conditions, initial concentration of 1.386 mol dm–3 of a substance becomes half in
 k1 
40 seconds and 20 seconds through first order and zero order kinetics, respectively. Ratio  k  of the rate
 0
constant for first order (k1) and zero order (k0) of the reaction is. [JEE-2008, 3/82]
(A) 0.5 mol–1 dm3 (B) 1.0 mol dm–3 (C) 1.5 mol dm–3 (D) 2.0 mol–1 dm3
17. For a first order reaction A  P, the temperature (T) dependent rate constant (k) was found to follow the
1
equation log k = – (2000) + 6.0. The pre-exponential factor A and the activation energy Ea, respectively,,
T
are : [JEE-2009, 3/80]
(A) 1.0 × 106 s–1 and 9.2 kJ mol–1 (B) 6.0 s–1 and 16.6 kJ mol–1
(C) 1.0 × 106 s–1 and 16.6 kJ mol–1 (D) 1.0 × 106 s–1 and 38.3 kJ mol–1

18. The concentration of R in the reaction R  P was measured as a function of time and the following data is
obtained : [JEE-2010, 3/163]
[R](molar ) 1.0 0.75 0.40 0.10

t(min.) 0.0 0.05 0.12 0.18
The order of the reaction is :
19. Plots showing the variation of the rate constant (k) with temperature (T) are given below. The plot that follows
Arrhenius equation is : [JEE-2010, 3/163]
(A) (B) (C) (D)
20.* For the first order reaction 2N2O5 (g)  4NO2(g) + O2 (g) [JEE-2011, 4/180]
(A) The concentration of the reaction decreases exponentially with time
(B) The half-life of the reaction decreases with increasing temperature
(C) The half-life of the reaction depends on the initial concentration of the reactant
(D) The reaction proceeds to 99.6% completion in eight half-life duration
21. An organic compound undergoes first-order decomposition. The time taken for its decomposition to 1/8 and
[1t / 8 ]
1/10 of its initial concentration are t1/8 and t1/10 respectively. What is the value of  10 ?(log102 = 0.3)
[ t1/ 10 ]
[JEE-2012, 4/136]
22. In the reaction, P + Q  R + S

the time taken for 75% reaction of P is twice the time taken for 50% reaction
of P. The concentration of Q varies with reaction time as shown in the figure.
The overall order of the reaction is : [JEE(Advanced) 2013, 2/120]
(A) 2 (B) 3
(C) 0 (D) 1
PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)

1. Units of rate constant of first and zero order reactions in terms of molarity M unit are respectively
[AIEEE- 2002]
(A) sec–1, M sec–1 (B) sec–1, M (C) M.sec–1, sec–1 (D) M, sec–1
2. For the reaction A + 2B  C, rate is given by R = [A] [B]2 then the order of the reaction is : [AIEEE- 2002]
(A) 3 (B) 6 (C) 5 (D) 7
3. The differential rate law for the reaction H2 + I2  2HI is : [AIEEE- 2002]
dH2  d[I ] d[HI] dH2  d[I2 ] 1 d[HI]
(A)   2  (B)  
dt dt dt dt dt 2 dt
1 dH2  1 d[I2 ] d[HI] dH2  d[I ] d[HI]
(C)   (D)  2  2 2  
2 dt 2 dt dt dt dt dt
4. The rate law for a reaction between the substances A and B is given by rate = k [A]n [B]m. On doubling the
concentration of A and halving the concentration of B, the ratio of the new rate to the earlier rate of the
reaction will be as [AIEEE- 2003]
1
(A) m  n (B) (m + n) (C) (n – m) (D) 2(n – m).
2

5. For the reaction system: 2NO(g) + O2(g)  2NO2(g), volume is suddenly reduced to half its value by
increasing the pressure on it. If the reaction is of first order with respect to O2 and second order with respect
to NO, the rate of reaction will : [AIEEE- 2003]
(A) diminish to one-fourth of its initial value (B) diminish to one-eighth of its initial value
(C) increase to eight times of its initial value (D) increase to four times of its initial value.
6. In the respect of the equation k = Ae –Ea/RT in chemical kinetics, which one of the following statements is
correct : [AIEEE- 2003]
(A) k is equilibrium constant (B) A is adsorption factor
(C) Ea is energy of activation (D) R is Rydberg constant.
7. In a first order reaction, the concentration of the reactant, decreases from 0.8 M to 0.4 M in 15 minutes. The
time taken for the concentration to change from 0.1 M to 0.025 M is : [AIEEE- 2004]
(A) 30 minutes (B) 15 minutes (C) 7.5 minutes (D) 60 minutes
8. The rate equation for the reaction 2A + B  C is found to be : rate = k[A] [B]. The correct statement in
relation to this reaction is that the : [AIEEE- 2004]
(A) unit of k must be sec–1
(B) t1/2 is a constant
(C) rate of formation of C is twice the rate of disappearance of A
(D) value of k is independent of initial concentrations of A and B.
9. The half - life of a radioisotope is four hours. If the initial mass of the isotope was 200 g, the mass remaining
after 24 hours undecayed is : [AIEEE- 2004]
(A) 1.042 g (B) 2.084 g (C) 3.125 g (D) 4.167 g.
10. Consider an endothermic reaction X  Y with the activation energies Eb and Ef for the backward and
forward reaction, respectively. In general [AIEEE- 2005]
(A) Eb < Ef (B) H = U (C) H < U (D) H > U
11. A reaction involving two different reactants can never be : [AIEEE- 2005]
(A) unimolecular reaction (B) first order reaction
(C) second order reaction (D) bimolecular reaction
12. A reaction was found to be second order with respect to the concentration of carbon monoxide. If the
concentration of carbon monoxide is doubled, with everything else kept the same, the rate of reaction will
be [AIEEE- 2006]
(A) remain unchanged (B) tripled
(C) increased by a factor of 4 (D) doubled
13. The following mechanism has been proposed for the reaction of NO with Br2 to form NOBr.
NO (g) + Br2 (g) NOBr2 (g) ; NOBr2 (g) + NO (g)  2NOBr (g) (slow step)
If the second step is the rate determining step, the order of the reaction with respect to NO(g) is
[AIEEE- 2007, 3/120]
(A) 1 (B) 0 (C) 3 (D) 2
14. The energies of activation for forward and reverse reactions for A2 + B2 2AB are 180 kJ mol–1 and 200
kJ mol–1 respectively. The presence of a catalyst lowers the activation energy of both (forward and reverse)
reactions by 100 kJ mol–1. The enthalpy change of the reaction (A2 + B2 2AB) in the presence of catalyst
will be (in kJ mol–1). [AIEEE- 2007, 3/120]
(A) 280 (B) 20 (C) 300 (D) 120
15. A radioactive element gets spilled over the floor of a room. Its half-life period is 30days. If the initial activity
is ten times the permissible value, after how many days will it be safe to enter the room :
[AIEEE- 2007, 3/120]
(A) 10 days (B) 100 days (C) 1000 days (D) 300 days

1
16. For a reaction A  2B, rate of disappearance of 'A' related to the rate of appearance of 'B' by the
2
expression. [AIEEE- 2008, 3/105]
d [ A ] 1 d [B] d [ A ] d [B] d[A] d [B] d [ A ] 1 d [B]
(A)   (B)   (C)  4 (D)  
dt 4 dt dt dt dt dt dt 2 dt
17. The half life period of a first order chemical reaction is 6.93 minutes. Time required for the completion of 99%
of the chemical reaction will be (log 2 = 0.301) : [AIEEE - 2009, 8/144]
(A) 23.03 minutes (B) 46.06 minutes (C) 460.6 minutes (D) 230.3 minutes
18. The time for half life period of a certain reaction A  Products is 1 hour. When the initial concentration
of the reactant ‘A’, is 2.0 mol L–1 , how much time does it take for its concentration to come from 0.50 to
0.25 mol L–1. If it is a zero order reaction? [AIEEE - 2010, 8/144]
(A) 4 h (B) 0.5 h (C) 0.25 h (D) 1 h
19. Consider the reaction [AIEEE - 2010, 4/144]

Cl2 (aq) + H2S(aq)  S(s) + 2H+ (aq) + 2Cl– (aq)
The rate equation for this reaction is, rate = k [Cl2][H2S]
Which of these mechanisms is/are consistent with this rate equation?
A. Cl2 + H2S  H+ + Cl– + Cl+ + HS– (slow) ; Cl+ + HS–  H+ + Cl– + S (fast)
B. H2S  H+ + HS– (fast equilibrium) ; Cl2 + HS–  2Cl– + H+ + S (slow)
(A) B only (B) Both A and B (C) Neither A nor B (D) A only
20. The rate of a chemical reaction doubles for every 10ºC rise of temperature. If the temperature is raised by
50ºC, the rate of the reaction increases by about : [AIEEE - 2011, 4/120]
21. A reactant (A) forms two products :
1 k
A 
 B, Activation Energy Ea1 ;
k
2
A 
 C, Activation Energy Ea2
If Ea2 = 2 Ea1, then k1 and k2 are related as : [AIEEE - 2011, 4/120]
(A) k 2  k 1eEa1 / RT (B) k 2  k 1eEa 2 / RT (C) k 1  Ak 2 eEa1 / RT (D) k 1  2k 2 eEa 2 / RT
22. For a first order reaction (A)  products the concentration of A changes from 0.1 M to 0.025 M in 40
minutes. The rate of reaction when the concentration of A is 0.01 M is : [AIEEE - 2012, 4/120]
(A) 1.73 × 10–5 M/min (B) 3.47 × 10–4 M/min
(C) 3.47 × 10–5 M/min (D) 1.73 × 10–4 M/min
23. The rate of a reaction doubles when its temperature changes from 300 K to 310 K. Activation energy of
such a reaction will be : (R = 8.314 JK–1 mol–1 and log 2 = 0.301) [JEE(Main) - 2013, 4/120]
(A) 53.6 kJ mol–1 (B) 48.6 kJ mol–1 (C) 58.5 kJ mol–1 (D) 60.5 kJ mol–1
PART -III : CBSE PROBLEMS (PREVIOUS YEARS)

1. Rate of a reaction is given by the equation : Rate = k [A]2 [B] What are the units for the rate and the rate
constant for this reaction ? [DSB 2001, 1 M]
2. Give an example of a pseudo first order reaction. [AISB, DSB 2004; DSB 2006 C, 1 M]
3. Define the term 'order of reaction' for chemical reactions. [AISB 2008, DSB 2008, 2010, 1 M]
1
4. What is the molecularity of the reaction, Cl –– Cl (g) ? [CBSE Sample Paper 2008, 1 M]
2 2

5. The decomposition reaction of ammonia gas on platinum surface has a rate constant = 2.5×10–4molL–1s–1.
What is the order of the reaction ? [CBSE Sample Paper 2008, 1 M]
6. How does the value of rate constant vary with reactant concentration ? [DSB 2005 C set I, 1 M]
7. A reaction is 50% complete in 2 hours and 75% complete in 4 hours. What is the order of reaction?
[AISB 2006, 1 M]
8. Express the rate of the following reaction in terms of disappearance of hydrogen in the reaction
3H2(g) + N2(g) ––– 2NH3(g) [AISB 2007, 1 M]
9. States the factors that influence the rate of a chemical reaction. [Foreign-2008, 2 M]
10. A reaction is second order with respect to a reactant ‘A’. How is the rate of this reaction altered if the
concentration of ‘A is : [Foreign-2008, 2 M]
(i) doubled (ii) reduced to Half
11. A first order decomposition reaction takes 40 minutes for 30% decomposition. Calculate its t1/2 value ?
[Delhi-2008, 2 M]
12. What is meant by the ‘rate constant’ K of a reaction ? If the concentration be expressed in mole L–1 units
and time in seconds. What would be the unit for K.
(i) for a zero order reaction (ii) for a first order reaction [Delhi-2008, 2 M]
13. (a) List the factors on which the rate of a chemical reaction depends.
(b) The Half-life for decay of radio active 14C is 5730 years. An archaeological artefact containing wood has
only 80% of the 14C activity as found in living trees. Calculate the age of the artefact. [Delhi-2008, 3 M]
14. The rate of a reaction increase to four times when the prevailing temperature is raised from 300 K to 320 K.
Calculate the energy of activation of this reaction assuming that it does not change with temperature
(R = 8.314 J mol–1 K–1) [Foreign-2008, 3 M]
15. (a) Derive the general from of the expression for the Half life of a first order reaction. [Delhi-2008, 2 M]
(b) The decomposition of NH3 on platinum surface is a zero order reaction. What are the rates of production
of N2 and H2 if K = 2.5 × 10–4 mole L–1 S–1 ? [Delhi-2008, 3 M]
16. Define the following : [All India-2009, 2 M]
(i) Elementary step in a reaction (ii) Rate of a reaction
17. A first order reaction has a rate constant of 0.0051 Min–1. If we begin with 0.10 M concentration of the
reactant, what concentration of reactant will remain in solution after 3 hours ? [Antilog (0.3986) = 2.503]
[Delhi-2009, 3 M]
18. For a decomposition reaction the values of rate constants K at two different temperature are given below :
K1 = 2.15 × 10–8 L mol–1 S–1 at 650 K
K2 = 2.39 × 10–7 L mol–1 S–1 at 700 K
Calculate the value of activation energy for this reaction. (R = 8.314 J K–1 mol–1)
Given that : log (23.9) = 1.3783 ; log (2.15) = 0.3324 [All India-2009, 3 M]
19. Decomposition of phosphine (PH3) at 120ºC proceeds according to the equation :
4PH3(g)  P4(g) + 6H2(g)
It is found that this reaction follows the following equation :
Rate = K [PH3]
The Half life of PH3 is 37.9 sec at 120ºC [Foreign-2009, 5 M]
(i) How much time will be required for 3/4 of PH3 to decompose ?
(ii) What fraction of the original amount of PH3 will remain undercomposed after 1 minute?
20. Hydrogen peroxide H2O2 (aq) decomposes to H2O(  ) and O2(g) in a reaction that is of first order in H2O2 and
has a rate constant K = 1.06 × 10–3 min–1
(i) How long will it take 15% of a sample of H2O2 to decompose ?
(ii) How long will it take 85% of sample of H2O2 to decompose ? [Foreign-2009, 5 M]

21. A reaction is of first order in reactant A and of second order in reactant B. How is the rate of this reaction
affected when
(i) The concentration of B alone is increased to three times.
(ii) The concentrations of A as well as B are doubled ? [Delhi-2010, 2 M]
22. The rate constant for a reaction of zero order in A is 0.0030 mole L–1 S–1. How long will it take for the initial
concentration of A to fall from 0.10 M to 0.075 M ? [All India-2010, 2 M]
23. (a) Explain the difference between the average rate and instantaneous rate of a chemical reaction.
(b) In a pseudo first order hydrolysis of ester in water, the following results are obtained.
t in sec . 0 30 60 90
[Ester ] M 0.55 0.31 0.17 0.085
(i) Calculate the average rate of reaction between the time interval 30 to 60 seconds.
(ii) Calculate the pseudo first order rate constant for the hydrolysis of ester. [All India-2010, 5 M]
24. (a) Distinguish between molecularity and order of a reaction.
(b) The activation energy for the reaction, 2H(g)  H2(g) + 2(g)
is 209.5 KJ/mole at 581 K.
Calculate the fraction of molecules having energy equal to or greater than activation energy
(R = 8.31 JK–1 mol–1) [All India-2010, 5 M]
25. Distinguish between ‘rate expression’ and ‘rate constant’ of a reaction. [Delhi-2011, 2 M]
26. The thermal decomposition of HCOOH is a first order reaction with a rate constant of 2.4 × 10–3 s–1 at a
certain temperature. Calculate how long will it take for three-fourths of initial quantity of HCOOH to decompose.
(log 0.25 = – 0.6021) [All India-2011, 2 M]
27. Nitrogen pentoxide decomposes according to equation :

2N2O5(g)  4NO2(g) + O2(g)
This first order reaction was allowed to proceed at 40ºC and the data below were collected.
[N2O 5 ] (M) Time (MM)

0.400 0.00
0.289 20.0
0.209 40.0
0.151 60.0
0.109 80.0
(a) Calculate the rate constant. Include unit with your answer ?
(b) What will be the concentration of N2O5 after 100 minutes ?
(c) Calculate the initial rate of reaction. [Delhi-2011, 5 M]
28. What do you understand by the rate law and rate constant of a reaction ? Identify the order of a reaction if
the units of its rate constant are :
(i) L–1 Mol S–1 (ii) L Mol–1 S–1 [All India 2011, 2012, 2 M]
29. For the reaction ; 2NO(g) + Cl2(g)  2NOCl(g) [CBSE 2012, 3 M]
the following data were collected. All the measurements were taken at 263 K:
Experiment Initial rate of disappearance

Initial [NO] (M) Initial [Cl2] (M)
No. of Cl2 (M/min)
1 0.15 0.15 0.60

2 0.15 0.30 1.20
3 0.30 0.15 2.40
4 0.25 0.25 ?

(a) Write the expression for rate law.
(b) Calculate the value of rate constant and specify its units.
(c) What is the initial rate of disappearance of Cl2 in exp. 4 ?
30. (a) A reaction is second order in A and first order in B.

(i) Write the differential rate requation.
(ii) How is the rate affected on increasing the concentration of A three times ?
(iii) How is the rate affected when the concentrations of both A and B are doubled ?
(b) A first order reaction takes 40 minutes for 30 % decomposition. Calculate t1/2 for this reaction.
(Given, log 1.428 = 0.1548) [CBSE 2013, 5 M]
31. (a) For a first order reaction, show that time required for 99% completion is twice the time required for the
completion of 90% of reaction.
(b) Rate constant ‘K’ of a reaction varies with temperature ‘T’ according to the equation :
Ea  1 
log k = log A –  
2.303 R  T 
1
Where Ea is the activation energy. When a graph is plotted for log k vs , a straight line with a sloped of
T
–4250 K is obtained. Calculate Ea for the reaction. (R = 8.314 J K–1 mol–1) [CBSE 2013, 5 M]

BOARD LEVEL EXERCISE : HINT & SOLUTIONS

1. First order reaction.
2. Zero order reaction

because t100% = 2t1/2 and reaction is complete in case of zero order reaction.
3. The catalyst increase rate of reaction by lowering activation energy. It provides an alternative short cut path
to the reaction.
4. Threshold energy is the minimum energy which must be possessed by reacting molecules in order to
undergo effective collision which leads to formation of product molecule.
Ea
5. It is a straight line whose. Slope =  2.303 R
6. In extra energy which must be possessed by reactant molecule so that collision between reactant
molecules is effective and leads to the formation product molecule.
7. Order Molecularity
(1) It is sum of powers to which concentration terms are
(1) It is number of molecules taking part in the reaction
raised in rate law.
(2) It is determined experimentally (2) It is determined theoretically
(3) It can be zero or even in fraction (3) It is always in whole number
(4) The order of complex reaction can be determine by rds

(4) Molecularity of each step is determined separately.
(rate determing step)
8. Temperature coefficient is the ratio of two rate constant at two different temperature that differ by 10 K. If its
value is two. It means the reaction rate gets almost doubled and so on.
K T 10
Temperature coefficient = K T = 2 or 3
9. r = K [A]
Ct d[ A] 
d [ A ]    Kdt
= K [A]  
dt C0 [ A ] 0
Ct kt
ln C = – Kt  Ct = C o e
0
10. t1/2 = 693

0.693 0.693
K= t1/ 2 = = 10–3 S–1
693
2.303 [ A ]0
t90% = log10 10 [ A ]
K 0
100
2.303
= log10 10 = 2303 sec.
0.001

11. K1 = K2
2000 1000
1016 e  T = 1015 e  T
1000
10 = e T
1000 1000
= 10 × 2.303 ; T= = 43.42 K
T 23.03
0.693
12. Half-life period of a first order reaction is given by t1/2=
k
0.693 0.693
(i) t1/2= 1 =0.346 × 10–2 s = 3.46 × 10–3s (ii) t 1/2= = 0.346 min
200 s 2 min 1
dx
13. = K [N2O4] [F2]
dt
[N2O 4 ]
K’ =  [N2O4] = K’ [NO2]2
[NO2 ] 2
dx dx
= K K’ (NO2]2[F2]  = K”(NO2]2[F2]
dt dt
Overall order is 2 +1 = 3 (3rdorder)
Slow step is rate determing step.
2.303 [ A ]0 2.303 4
14. (a) K = log10 75 [ A ] = log10 = 0.0096 min–1 .
30 0 30 3
100
0.693
(b) t1/2 = = 72.18 min.
K
15. Here, [A0] = 5g, [A] = 3g, k = 1.15 × 10–3 s –1. As the reaction is of 1st order,
2.303 [A] 2.303 5g
t= log 0 = log
3g = 2.00 × 10 (log 1.667)s
3
 3 1
t [A] 1.15  10 s
= 2.0 × 103 × 0.2219 s = 443.8 s 
~ 444 s.
dx
16. (i) = k [A] [B]2 . (ii) Rate = k ab2
dt
If [B] is tripled, Rate = Ka (3 b)2 = k a×9b2 = k 9ab2 = 9 times.
(iii) If both [A] and [B] are doubled, Rate = k (2 a) (2 b) = 8 k ab2 = 8 times.
17. Let order of reaction w.r.t A = 

Let order of reaction w.r.t B = 
(i) (r0)1 = 5.07 × 10–5 = (0.2) (0.3)
(r0)2 = 5.07 × 10–5 = (0.2) (0.1)
(r0)3 = 1.43 × 10–4 = (0.4) (0.05)
(r0 )1 5.07 10 –5 (0.2) (0.3)

(r0 )2 = 5.07 10 – 5 = (0.2) (0.3)

 0. 3 
=1=    = 1 = (3)
 0.1 
=0


(r0 )2 5.07 10 –5 (0.2) (0.1)  1
 
(r0 )3 = 5.07 10 – 5 = (0.4) (0.45) =  2 
=0
Thus order w.r.t A = 1
Thus order w.r.t B = 0
18. The rate of any reaction depends on the following factors :

(1) Nature of the reactants : Different reactants require different amount of energy for breaking of
different bonds and different amount of energies are released in the formation of different bonds.Hence
the reaction rate depends upon the energies gained or released during the reaction
(2) Concentration of the reactants : When the concentration of the reactants is greater the reaction
will be faster .As soon as the concentration decreases the rate of reaction will also decreases
(3) Temperature : The rate of reaction increases with the increase of temperature.
(4) Presence of catalyst : A catalyst generally increases the speed of a reaction without consuming of
it self in case of reversible reaction a catalyst help to attain the equilibrium quickly.
(5) Surface area of the reactants : For solid reactants greater is the surface area, the faster is the
reaction.
(6) Presence of light : Some reaction take place in the presence of light e.g., H2+ Cl2 2HCl'
CH4+ Cl2 CH3Cl + HCl
19. (CH3)2CH N = N CH(CH3)2(g)  N2(g) + C6H14(g)

Initial pressure P0 0 0
After time t P0–p p p
Total pressure after time t (Pt) = (P0–p) + p + p = p0 + p or p = Pt–P0;
  P0 and (a - x)  P0– p or substituting the value of p,
a – x  P0 – (Pt– P0), i.e.,(a – x)  P0 – Pt
As decomposition of azoisopropane is a first order reaction,
2.303 a 2.303 P0
k= log = log 2P  P
t ax t 0 t
2.303 35.0 2.303 35 2.303

when t = 360 sec, k = 360 s log = 360 s log = (0.3400)=2.175×10–3 s–1
2  35.0  54.0 16 360 s
2.303 35.0 2.303 2.303

when t = 720 sec, k = 720 s log = 720 s log 5 = 720 s (0.6990) = 2.235 × 10–3 s–1
2  35.0  63.0
2.175  2.235
 Average value of k = ×10–3 = 2.20 × 10–3 s–1.
2
H
20. (a) CH3COOC2H5 + H2O 
 CH3COOH + C2H5OH
order =1 Molecularity = 2
CH3COOC2H5 + NaOH CH3COONa + C2H5OH
order = 2 Molecularity = 2
2.303 Pi 2.303 800
(b) (i) K = log10 P = log10
t t 100 400
2.303
K= log10 2 = 6.93 × 10–3 min–1
100
2.303
K= log10 4 = 6.93 × 10–3 min–1
200
It is first order reaction

0
2.303 75
(ii) t25% = log10 0
K 100
2.303
t25% = log10 4 = 4.15 × 10 = 41.5 min
6.93  10 3 3
(iii) 2X (g)  3Y(g) + 2Z(g)
initial 800 0 0
final 800 – 2x 3x 2x
800 – 2x = 600
x = 100 mm of Hg
Total pressure = 800 – 2x + 3x + 2x = 800 + 3 × 100 = 1100 mm of Hg.
21. (a) (i) second order (ii) L mole –1s–1

R0  R
(b) K =
t
R0  R0 / 2 R0
t1/2 = =
K 2K
R0
time for complection = 2t1/2 =
K
–E a
(c) slope = 2.303 R
Ea = – 2.303 R (slope) = – 2.303 × 8.314 (–6670) = 127.7 J KJ/mol
EXERCISE - 1
PART - I
A-1. (a) 4.5 × 10–3 M sec–1 (b) 3.0 × 10–3 M sec–1
A-2. (a) 40.5 gm min–1 (b) 76.5 gm min–1
A-3. (a) 1.6 × 10–2 atm min–1 (b) 1.09 × 10–5 mol liter–1 sec–1
A-4. (a) 3 ; (b) Both rates are 3.6 x 10  3 mole dm  3 s  ; (c) No effect ; (d) Decreased by a factor of 8 ; No effect
10
B-1. (i) 9.994 M (ii) (iii) 5 × 106 min
2  (2  10  6 )
B-2. (a) 5 x 105 M/s (b) 4.2 x 105 M/s B-3. 0075.
B-4. 1.73 time. C-1. 1.25  104 min ; 2.5  104 min
C-2. 1.84 × 102 min1
 k  k 2 ( 2  1)
C-3. (a) A t =  A 0  2 t  (b) straight line with slope – (c) [ A ]0
  2 K
D-1. (i) rate = [A] [B] (ii) k = 4 x 102M1s1 (iii) rate = 2.8 x 103M·s1
D-2. (a) n = 2, (b) First Order D-3. 2
1  P0  1  P0 
 1  P 
 1  P 
D-4. (a) k = ln (b) k = ln (c) k = ln (d) k = ln  
t  Pt  t  2P0 – Pt 
 t  P – Pt 
 t  P – Pt 
D-5. 1.58 × 10–2, 2.33 atm. E-1. 3.27 × 10–3 min–1

50
E-2. 0.000844 ×10–4 sec–1 E-3. (i) 2.484 hr–1 (ii) min.
3
9 ln 2 14
F-1. k1 = ; k2 = ln 2 F-2. Eoverall = E/3(2n+1)
2300 2300
0.693
F-3. t=
K f  Kb
F-4. (a) 131.8 sec, (b) 0.58 mol dm–3, (c) [A] = 5.53 × 10–4 mol dm–3, [B] = 0.123 mol dm–3, [C] = 0.877 mol dm–3
G-1. (i) 2, 1 (ii) 2.67 × 108 mol–2 litre2 sec–1 (iii) 55.13 kJ mol–1 (iv) 1.147 × 1018 mol–2 litre2 sec–1
G-2. 80.65%.
G-3. (A) y + z (B) z (C) x + y + z (D) x (E) x + y (F) – y
H-1. – 1000 H-2. k [N2O5] H-3. Rate = k [NO]2 [Br2]
H-4. (a) 2 B+F  2E; (b) A; (c) C,D; (d) rate = k [B][C]; (e) rate = k'[A][B] (f) 2.
I-1. 30 days, 0.0231 per day I-2. 12.01 × 10–5 years –1, 1/4
I-3. 0.9375 gram. I-4. t = 4.5 × 109 year.
PART - II
A-1 (A) A-2 (B) A-3 (D) A-4* (A,D) A-5 (B)
A-6 (B) A-7 (C) A-8* (B,D) A-9 (A) A-10 (D)
B-1 (B) B-2 (C) B-3 (C) B-4 (A) B-5 (A)
B-6 (B) B-7 (D) B-8 (B) B-9* (A,B,C) C-1 (D)
C-2 (C) C-3* (A,D) C-4 (A) C-5 (D) C-6 (C)
C-7 (C) C-8 (A,B) C-9 (C) D-1 (B) D-2 (D)
D-3 (B) E-1 (B) E-2 (D) E-3* (A,B,C,D) E-4 (C)
E-5 (B) E-6 (B) E-7 (B) F-1 (C) F-2 (B)
F-3 (B) F-4 (C) F-5 (A) G-1 (B) G-2 (B)
G-3 (D) H-1 (B) H-2 (B) H-3 (B) H-4 (A)
H-5* (B,D) H-6 (B) I-1 (B) I-2* (A,B) I-3 (B)
I-4 (D) I-5 (B) I-6 (C) I-7 (B) I-8 (B)
I-9* (A,B,C) J-1 (D) J-2 (A) K-1 (C) K-2 (C)
K-3 (C) K-4 (B) K-5 (A) K-6 (B) K-7* (A,B,C,D)
L-1 (D) L-2 (A) L-3 (B) L-4 (C) L-5 (D)
L-6 (A) L-7 (B) L-8 (D) L-9 (C) L-10 (A)
L-11 (A)
PART - III
1. (C) 2. (B) 3. (A) 4. (B) 5. (D)

EXERCISE - 2
PART - I
1. (a) Rate of decomposition of NH3 ; (b) Rate of formation of N2 and rate of formation of H2
(c) 2.5 × 10–4 M sec–1 , 7.5 × 10–4 M sec–1 ; (d) (i) 1 , (ii) 0
2. 17min. (approx.) 3. a = 1, b = 1 4. 0.022 hr1
5. k = 0.736 litre/mol/minute 6. k = 2.07 x 102 min1 7. 0.531
8. Kf = kb = 2.71 x 10- 4 sec -1

9. kf = 6.18 × 10–2 min–1, kb = 1.71 × 10–3 min–1
10. 42%. 11. 0.198 12. k = 0.0327 min-1 13. 0.001607
ka  kb
14. EC1 = 75.44 kJ, EC2 = 70.975 kJ. 15. Rate = k  2 k [N2O5]
a b
d[HBr ] k 2 (k1 / k 5 )1/ 2 [Br2 ]1/ 2 [H2 ]

16. = . 17. 31.25 cm3
dt 1  (k 4 / k 3 ) [HBr ] / [Br2 ]
PART - II
1. (B) 2. (C) 3. (B) 4. (C) 5. (C)
6. (B) 7. (A) 8. (C) 9. (C) 10. (C)
11. (B) 12. (B) 13. (C) 14. (B) 15. (A)
16. (B) 17. (A) 18. (D) 19. (A) 20. (D)
21. (B) 22. (C) 23. (A) 24. (D) 25. (B)
26. (D) 27. (A,B,D) 28. (A,B,D) 29. (A,B,C) 30. (B,C)
31.* (B,C) 32.* (A,B)

PART - III
1. (A  r) ; (B  s) ; (C  q) ; (D  p) 2. (A - p, q, r, s) ; (B - q, r, s) ; (C - p, q, r, s) ; (D - p, r, s)
3. (A – r) ; (B – s) ; (C – p) ; (D – q)
PART - IV
1. (A) 2. (D) 3. (B) 4. (A) 5. (C)
6. (A) 7. (C) 8. (B) 9. (B) 10. (A)
EXERCISE - 3
PART - I
1. (D) 2. t = 7.097 × 108 years. 3. EA = 100 KJ/mol
4. (B) 5. t1/2 = 24 min. 6. (A)

7. (t1/2)1 = 36.1 hr–1, (t1/2)2 = 72.2 hr–1, (t1/2)3 = 27.44 hr–1. 8. (B)
9. (A) 10. (a) R0 = k[A0], (b) 0.5 sec–1. 11. 950 mm of Hg

12. (C) 13. (B) 14. (A) 15. (D) 16. (A)
17. (D) 18. 0 19. (A) 20.* (A,B,D) 21. 9
22. (D)

PART - II
1. (A) 2. (A) 3. (D) 4. (D) 5. (C)
6. (C) 7. (A) 8. (D) 9. (C) 10. (A)
11. (A) 12. (C) 13. (D) 14. (B) 15. (B)
16. (A) 17. (B) 18. (C) 19. (D) 20. (C)
21. (C) 22. (B) 23. (A)
PART -III
1. Units of rate = mol L–1 s–1
Rate mol L1 s 1
Units of k = 2 = = L2 mol–2 s–1
[ A ] [B] (mol L1 )(mol L1 ) 2
2. Acid catalysed hydrolysis of ethyl acetate

H 
CH3COOC2H5 + H2O 
 CH3COOH + C2H5OH Rate = k [CH3COOC2H5] [H2O]0
3. The sum of the exponents (powers) of the concentration of reactant in the rate law is termed as order of the
reaction. It can be in fraction and can be zero also.
4. One
5. Zero order (on the basis of units of k)

6. For a particular reaction at a particular temperature, rate constant is constant and does not depend upon
concentrations of the reactants.
7. t1/2 = 2 hours. As 75% completion takes two half lives, this shows that t1/2 is independent of initial concentration.
Hence, it is a reaction of first order.
1 d [H2 ]
8. Rate = –
3 dt
9. (i) Nature of reactants (ii) Physical state and surface area (iii) Concentration of reactants
(iv) Temperature (v) Catalyst
dx
10. = K [A]2
dt
(i) rate = K [2A]2 = 4K [A]2
The rate will become four times.
2
A  [ A ]2 1
(ii) rate =     The rate will become .
2 4 4
2.303 [R]0 2.303 R0

11. K= log10 = log10 = 8.917 × 10–3 Min–1
t [R] 40 70 R
0
100
0.693 0.693
t1/2 =  = 77.716 Min.
K 8.917  10 3
12. Rate constant is defined as equal to rate of reaction when molar concentration of reactant(s) is equal to
unity.
(i) rate = K [A]0 [B]0
K = Mole L–1 S–1 (zero order)
(ii) rate = K [A]1
Unit of K = Sec–1 (first order)

13. (a) (i) Nature of reactants (ii) Concentration of reactants
(iii) Temperature (iv) Physical state and surface area
(v) Catalyst (vi) Activation energy
(b) t1/2 = 5730 year
0.693 2.303 N0
K= year–1  t= log10
5730 K N
2.303 100
= × 5730 log10
0.693 80
= 1845 years
K2 Ea  1 1 
14. log10 K  2.303 R   
1  T1 T2 
Ea  1 1 
log10 4 = 2.303  8.314   
 300 320 
Ea = 55.336 kJ/mole
1 a
15. (a) K = ln
t ax
a
t1/2 x=
2
1 a 1
K= ln  K= ln2
t1/ 2 a t1/ 2
a
2
0.693
t1/2 =
K
(b) 2NH3 (g)  N2(g) + 3H2(g)
1 d d [N2 ] 1 d [H2 ]
– [NH3] = =
2 dt dt 3 dt
d [NH3 ] d [NH3 ]
– = K [NH3]0  – = 2.5 × 10–4
dt dt
d [N2 ] 1
= × 2.5 × 10–4 = 1.25 × 10–4 M/sec
dt 2
1 d 1 d [H2 ]
 – [NH3] =
2 dt 3 dt
d [H2 ] 3 7 .5
= × 2.5 × 10–4 = × 10–4 = 3.75 × 10–4 M/sec
dt 2 2
16. (i) Each step of a complex reaction (taking place in more than one step) is called elementary step of a
reaction.
(ii) The change in concentration of reactant or products per unit time is called rate of a reaction.
2.303 A0
17. K= log10
t A
2.303 0.10
0.0051 = log10
180 [A]
[A] = 0.04 M

K2 Ea  1 1 
18. log10 K  2.303 R   
1 T
 1 T2
2.39  10 7 Ea  1 1 
log10 = 2.303 R   
8  650 700 
2.15  10
Ea = 182.23 kJ/Mole.
0.693
19. (i) t1/2 = 37.9 s, k =
37.9
2.303 [A 0 ] 2.303
t3/4 = log = log 4
k 1 k
[A 0 ]
4
2.303  0.6021 2.303  0.6021

= = × 37.9 = 75.8 min
k 0.693
0.693 0.693 –1
(ii) k= t1/ 2 = 37.9 s
2.303 [A 0 ]
k= log
t [A]
0.693 2.303 1
= log
37.9 1 60 [A]
1 0.693  60 41.58 1
 log = = = 0.4796  = Antilog (0.4764) = 2.995
[A] 2.303  37.9 87.28 [A]
1
 [A] = = 0.334
2.995
2.303 [A 0 ]
20. (i) k= log
t [A]
2.303 [A 0 ] 2.303
t= 3 log 85 = [log20–log17]
1.06  10 [A 0 ] 1.06  10 3
100
2.303
= × (1.3010 – 1.2304)
1.06  10 3
2.303  0.0706 0.1626  10 3

= 3 =
1.06  10 1.06
= 1.534 × 102 = 153.4 min
2.303 [A 0 ]
(ii) t= log
1.06  10 3 15
[A 0 ]
100
2.303
= [log20 – log3]
1.06  10 3

2.303
= ×(1.3010 – 0.4771)
1.06  10 3
2.303
= × 0.8239
1.06  10 3
1.897
= ×1000 = 1790.0 min
1.06
21. (i) Rate = k[A]1[B]2 ; Rate = k[A][3B]2 ; Rate = 6k[A][B]2

If concentration of ‘B’ alone increases three times, the rate will increase nine times.
(ii) If concentration of ‘A’ as well as ‘B’ is double, rate = k [2A]1 [2B]2, the rate will increase eight times
so rate = 8k [A][B]2
22. k = 0.0030 mol L–1s–1

[R 0 ]  [R]
k=
t
[R 0 ]  [R] 0.10  0.075 0.025 25 1000

 t= = = = × = 8.33 s
k 0.0030 0.0030 1000 3
23. (a) Average rate : The rate of reaction measured over a long time interval is called average rate of reaction,
it is equal to x/t. e.g.,
H2(g) + Cl2(g)  2HCl(g)
(H2 ) (HCl) 1 (HCl)
Rate of reaction = – =– =+
t t 2 t
Instantaneous rate It is the rate of reaction when the average rate is taken over a very small interval of
time.It is equal to dx/dt.
Instantaneous rate = Average rate as t apporaches zero.
 C 2  C1   0.17  0.31 
(b)(i) Average rate = –  t  t  = –  
 2 1   60  30 
0.14
= = 4.67 × 10–3 mol L–1 s–1
30
2.303 [ A ]0 2.303 0.55

(ii) K = log10 = log10
t [ A ] 30 0.31
2.303
= [1.7404–1.4914] = 1.91 × 10–2 s–1
30
24. (a) (i) Order of a reaction : The sum of the exponents (powers) of the concentration of reactants in
the rate law is termed as order of the recation. It can be fractional. It can be zero also.
(ii) Molecularity of reaction : Total number of atoms, ions or molecules of the reactants involved
in the reaction is termed as its molecularity. It is always in whole number. It is never more than
three. It cannot be zero.
k2 Ea  1 1 
(b) log k =   
1 2.303R  T1 T2 
Ea  1 1 
log4=   
2.303  8.314  300 320 

19.147  0.6021  300  320
Ea =
20
Ea = 55.336 kJ mol–1.
25. Rate of reaction is defined as change in concentration of reactants or products per unit time. Its unit is
mol L–1s–1.
Rate expression is a way of expressing rate of reaction e.g., N2(g) + 3H2(g)  2NH3(g)
d [N2 ] 1 d [H2 ] 1 d [NH3 ]
 
dt 3 dt 2 dt
Rate constant is defined as equal to rate of reaction when molar concentration of reactants is unity. Its unit
depends upon order of reaction.
2.303 [R ] 2.303 [R 0 ]
26. k= log 0  2.4 × 10–3 s–1 = log
t [R] t 1
[R 0 ]
4
2.303
t= log 4 = 5.77 × 102 s
2.4  10 3
2.303 [R ] 2.303 0.400

27. (a) k= log 0 = log
t [R] 20 0.289
2.303
= [ 1 .6021  1 .4609] = 0.01625 min–1
20
2.303 0.400
k= log = 0.01623 min–1
40 0.209
2.303 0.400
k= log
60 0.151
2.303
= [ 1 .6021  1 .1790] = 0.01623 min–1
60
0.01625  0.01623  0.01623

k= = 0.016236 min–1
3
2.303 [R ]
(b) k= log 0
t [R]
2.303 0.4
1.6236 × 10–2 = log
100 [R]
[R] = 0.07889 M
(c) Initial rate = k[N2O5] = 0.016236 × 0.4 = 0.00649 mol L–1 s–1.
28. Rate law is expression which gives relationship between rate of reaction and concentration of reactans
dx
e.g., = k [A]x [B]y
dt
Rate constant is equal to rate of reaction when concentration of reactants is equal to unity. ‘k’ is rate
constant in above expression.
(i) Zero order (ii) Second order
dx
29. = k[A]x [B]y
dt

dx
= k[NO]x [Cl2]y
dt
0.60 = k(0.15)x (0.15)y ...(i)
1.20 = k (0.15)x (0.30)y ...(ii)
Dividing (i) by (ii) we get
1 1
= y  2y = 21  y=1
2 2
2.40 = k(0.30)x (0.15)y
Dividing (i) by (iii) we get ...(iii)
1 1
= x  2x = 22  x=2
4 2
dx
(a) = k[NO]2 [Cl2]1
dt
(b) 0.60 = k(0.15)2 (0.15)
0.60
k=
(0.15 )2 (0.15 )
k = 1.77.77 L2 mol–2 min–1 = 1.78 102 L2 mol–2 min–1
dx
(c) = 1.78  102  (0.25)2 (0.25)
dt
= 2.781 mol L–1 min–1
dx
30. (a) (i) Reaction is first order in A and second order in B, hence differential rate equation is = k[A] [B]2.
dt
(ii) Let rate = k[A] [B]2
If [A] is tripled, Rate = k [3A] [B]2 i.e., rate increases 3 times.
(iii) If both [A] and [B] are doubled,
Rate = k [2A] [2B]2 = 8K [A] [B]2
i.e., Rate of reaction increases 8 times.
(b) 30% decomposition means that
x = 30% or R0 or, R = R0 – 0.3 R0 = 0.7 R0
For reaction of 1st order,
2.303 R0  2.303 R0
k=
t
log
R 40 log 0.7 R
0
2.303 10 2.303
= log min 1  log1.428 min 1
40 7 40
2.303
=  0.1548 min 1 = 8.913 × 10–3 min–1
40
For a 1st order reaction,
0.693 0.693
t1/2 = =  77.7 min
K 8.913 10 3 min 1
1 100
31. (a) t90% = ln
k 10
2.303
t90% =
k
1 100
t99% = ln
k 1

2.303  2
t99% =
k
t99% = 2 × t90%
E a
(b) log k = log A – 2.303 RT
1 E a
 plot k = log k vs gives a straight line with slope equal to 2.303 RT
T
E a
 2.303 RT = – 4250
Ea = 4250 × 2.303 × R
Ea = 4250 × 2.303 × 8.314 = 81375.35 J mol–1
= 813.75 kJ mol–1.

91
PART - I : OBJECTIVE QUESTIONS
Single Choice Type

1. For the complex Ag+ + 2NH3 [Ag(NH3)2+]
 dx 
  = 2 × 107 L2 mol–2 s–1 [Ag+] [NH ]2 – 1 × 10–2 s–1 [Ag(NH ) +]
 dt  3 3 2
Hence, ratio of rate constants of the forward and backward reactions is :

(A) 2 × 107 L2 mol–2 (B) 2 × 109 L2 mol–2 (C) 1 × 10–2 L2 mol–2 (D) 0.5 × 10–9 L2 mol–2
2. In the reaction N2 + 3H2 2NH3
 dx  [N2 ] [H2 ]3
  = 1 × 102 [N ] [H ]3 – 1 × 10–3 [NH ]2 and at some instant if = 10–5 M2
 dt  2 2 3 [NH3 ]2
 dx 
then at this instant value of  dt  is :
 
(A) 0 (B) 1 × 105 (C) 1 × 10–5 (D) 1 × 10–3
3. In the following graphical representation for the reaction A  B there are two types of regions :
(A) I and II both represent kinetic region at different interval

(B) I and II both represent equilibrium regions at different time interval
(C) I represents kinetic while II represents equilibrium region
(D) I represents equilibrium while II represents kinetic region
4. Rate law of the reaction A  Product is, rate = k[A].

Graphically it is represented as
Hence, rate constant is :
(A) 3 × 10–4 s–1
(B) 1 × 10–2 s–1
(C) 3 × 10–2 s–1
(D) 1 × 10–4 s–1

92
5. For a given reaction A  Product, rate is 1 × 10–4 M s–1 when [A] = 0.01 M and rate is 1.41 × 10–4 M s–1 when
[A] = 0.02 M. Hence, rate law is :
d[A] d[A] d[A] k d[A]
(A)  = k [A]2 (B)  = k[A] (C)   [A ] (D)  = k[A]1/2
dt dt dt 4 dt
k1
6. Following reaction can take place in both direction A B,
k2
It is given that for the forward reaction :
Rate (M s–1)
and for the backward reaction
[B] Rate
0.01 M 1 × 10–2 Ms–1
0.02 M 2 × 10–2 Ms–1 [A],M
Hence, net reaction rate of B is :

(A) = k1 [A] – k2 [B] (B) = k1 – k2 [B] (C) = k1 [A] – k2 (D) = k1 – k2
7. For the following reaction

 dx 
(CH3)3CCl + H2O  (CH3)3 COH + HCl ,  dt  = k[CH3)3CCl], hence, rate determining step can be:
 
(A) (CH3)3CCl  (CH3)3C+ + Cl– (B) (CH3)3CCl + H2O  (CH3)3COH + HCl
(C) (CH3)3C+ + H2O  (CH3)3COH + H+ (D) H+ + Cl–  HCl
8. For the non-equilibrium process, A + B products, the rate is first-order w.r.t. A and second-order w.r.t. B. If
1.0 mole each of A and B introduced into a 1.0 L vessel and the initial rate was 1.0 × 10–2 mol L–1 s–1, rate
when half reactants have been turned into products is :
(A) 1.25 × 10–3 mol L–1 s–1 (B) 1.0 × 10–2 mol L–1 s–1
(C) 2.50 × 10 mol L s
–3 –1 –1
(D) 2.0 × 10–2 mol L–1 s–1
9. Select the correct statements out of I, II and III for zero order reaction
I : Quantity of the product formed is directly proportional to time
II : Larger the initial concentration of the reactant, greater the half-life period
III : If 50% reaction takes place in 100 minutes, 75% reaction take place in 150 minutes.
(A) I only (B) I and II only (C) II and III only (D) I, II and III
10. A certain zero order reaction has k = 0.025 M s–1 for the disappearance of A. What will be the concentration
of A after 15 seconds if the initial concentration is 0.50 M ?
(A) 0.50 M (B) 0.375 M (C) 0.125 M (D) 0.060 M
11. A reaction of first-order completed 90% in 90 minutes, hence, it is completed 50% in approximately :
(A) 50 min (B) 54 min (C) 27 min (D) 62 min
12. T50 (Half-life period) of first-order reaction is 10 minute. Starting with 10 mol L–1, rate after 20 minute is :
(A) 0.0693 mol L–1 min–1 (B) 0.0693 × 2.5 mol L–1 min–1
(C) 0.0693 × 5 mol L min
–1 –1
(D) 0.0693 × 10 mol L–1 min–1
13. For the first-order reaction Tav (average life), T50 and T75 in the increasing order are :
(A) T50 < Tav < T75 (B) T50 < T75 < Tav (C) Tav < T50 < T75 (D) Tav = T50 < T75
14. Which is not true for a second order reaction ?

(A) It can have rate constant 1 × 10–2 L mol–1 s–1
(B) Its half-life is inversely proportional to its initial concentration
(C) Time to complete 75% reaction is twice of half-life
1
(D) T50 = K  Initial conc.

93
KI
15. N Cl  I2
COCH3
Kinetics can be studied by titration using :
(A) Na2S2O3 (B) KMnO4 (C) H2C2O4 (D) OH
M M8
16. Z A ( g)  Z  4 B( g) + ( - particles)
(-particles are helium nuclei, so will form helium gas by trapping electrons)
The radioactive disintegration follows first-order kinetics Starting with 1 mol of A in a 1-litre closed flask at
27ºC pressure developed after two half-lives is approximately :
(A) 25 atm (B) 12 atm (C) 61.5 atm (D) 40 atm
17. A.G.M. counter is used to study the radioactive process of first-order. In absence of radioactive substance A,
it counts 3 disintegration per second (dps). When A is placed in the G.M. counter, it records 23 dps at the
start and 13 dps after 10 minutes. It records x dps after next 10 minutes and A has half-life period y minutes.
x and y are :
(A) 8 dps, 10 min (B) 5 dps, 10 min (C) 5 dps, 20 min (D) 5 dps, 5 min
18. Saponification of ethyl acetate (CH3COOC2H5) by NaOH (Saponification of ethyl acetate by NaOH is second
order Rxn) is studied by titration of the reaction mixture initially having 1:1 molar ratio of the reactants. If
10 mL of 1 N HCl is required by 5 mL of the solution at the start and 8 mL of 1 N HCl is required by another
5 mL after 10 minutes, then rate constant is :
2.303 10 2.303 10 1 1 1 1 1 1
(A) k = log (B) k = log (C) k = 10  8  10  (D) k = 10  2  10 
10 8 10 2    
dx
19. For the reaction A (g) + 2B(g)  C(g) + D(g) = k [A] [B]2
dt
Initial pressure of A and B are respectively 0.60 atm and 0.80 atm. At a time when pressure of C is 0.20 atm,
rate of the reaction, relative to the initial value is :
1 1 1 1
(A) (B) (C) (D)
6 48 4 24
 dx 
20. If  dt  = k [H+]n and rate becomes 100 times when pH changes from 2 to 1. Hence, order is :
 
(A) 1 (B) 2 (C) 3 (D) 0
21. Consider following reaction, Zn + 2 H+  Zn2+ + H2

Half–life period is independent of concentration of Zn at constant pH. At constant Zn concentration, half–life
is 10 minutes at pH = 2 and half–life is 100 minutes at pH = 3. Hence , rate law is :
(A) k [Zn][H+] (B) k [Zn][H+]2 (C) k [Zn]0 [H+] (D) k [Zn]0 [H+]2
22. Following are the values of Ea and H for three reactions carried out at the same temperature :
I : Ea = 20 kJ mol–1 , H = – 60 kJ mol–1
II : Ea = 10 kJ mol–1 , H = – 20 kJ mol–1
III: Ea = 40 kJ mol–1 , H = + 15 kJ mol–1
If all the three reaction have same frequency factor then fastest and slowest reactions are :
Fastest Slowest
(A) I II
(B) II III
(C) I III
(D) can’t be predicted.

94
23. Milk turns sour at 400C three times as faster as 00C. Hence Ea in cal of process of turning of milk sour is :
2.303  2  313  273 2.303  2  313  273  1
(A) log3 (B) log  3 
40 40  
2.303  2  40
(C) log3 (D) None of the above
273  313
1
24. Graph between log k and (k is rate constant in s–1 and T is the temperature
T
in K) is a straight line. As shown in figure if OX = 5 and slope of the
1
line = – then Ea is :
2.303
2
(A) 2.303 × 2 cal (B) cal
2.303
(C) 2 cal (D) None of these
25. If the fermentation of sugar in an enzymatic solution that is 0.12 M , the concentration of the sugar is
reduced to 0.06 M in 10 h and to 0.03 M in 20 h. What is the order of the reaction ?
(A) 1 (B) 2 (C) 3 (D) 0
26. A reaction is catalysed by H+ ion;and in the rate law the dependence of rate is of first order with respect to the
concentration of H+ ions, in presence of HA rate constant is 2 × 10–3 min–1 and in presence of HB rate
constant is 1 × 10–3 min–1. HA and HB have relative strength as :
(A) 0.5 (B) 0.002 (C) 0.001 (D) 2
27. For the first-order reaction (C = C0 e k1t ) and Tav = k1–1. After two average lives concentration of the reactant is
reduced to :
100 100
(A) 25% (B) 75% (C) % (D) 2 %
e e
28. Number of natural life times (Tav) required for a first-order reaction to achieve 99.9% level of completion is :
(A) 2.3 (B) 6.9 (C) 9.2 (D) 0.105
29. Match the graphical study with the order of the reactions :
I : Rate II : Half life III : (a – x)–1
I II III I II III
(A) A B C (B) B C A
(C) C B A (D) C A B
30. The bromination of acetone that occurs in acid solution is represented by
CH3COCH3 (aq) + Br2 (aq)  CH3COCH2 Br (aq) + HBr (aq)
Given : Initial Rate of
Initial concentrations Disapperance of
Br2 , Ms–1
Br2 [CH3COCH3] M [H+]
0.050 0.30 0.050 5.7 × 10–5
0.10 0.30 0.050 5.7 × 10–5
0.10 0.30 0.10 1.2 × 10–4
0.050 0.40 0.20 3.1 × 10–4
Based on the above data , rate law is :

 dx   dx 
(A)  dt  = k [CH3COCH3] [Br2] [H+] (B)  dt  = k [CH3COCH3] [H+]
   
 dx   dx 
(C)  dt  = k [CH3COCH3] [Br2] (D)  dt  = k [CH3COCH3] [Br2] [H+]2
   

95
31. A(g)  B(g) + C(g)
d [A]
– = k [A]
dt
At the start pressure is 100 mm and after 10 min , pressure is 120 mm. hence , rate constant (min–1) is :
2.303 120 2.303 100 2.303 100 2.303 100
(A) log (B) log (C) log (D) log
10 100 10 20 10 80 10 120
32. The rate law for the dimerisation of NO2 is

d [NO2 ]
– = k [NO2]2
dt
which of the following changes will change the value of the specific rate constant , k :
(A) Doubling the total pressure on the system (B) Doubling the temperature
(C) Both of (A) and (B) (D) None of the above
33. In the following reaction, how is the rate of appearance of the underlined product related to rate of disappearance
of the underlined reactant :
BrO3– (aq) + 5 Br– (aq) + 6 H+ (aq)  3 Br2 (l) + 3 H2O (l)
d [Br2 ] 5 d [Br – ] d [Br2 ] d [Br – ]

(A) =– (B) =–
dt 3 dt dt dt
d [Br2 ] d [Br – ] d [Br2 ] 3 d [Br – ]

(C) =– (D) =–
dt dt dt 5 dt
34. 3 A  B + C, It would be a zero order reaction when :

(A) the rate of reaction is proportional to square of concentration of A
(B) the rate of reaction remains same at any concentration of A
(C) the rate remains unchanged at any concentration of B and C
(D) the rate of reaction doubles if concentration of B is increased to double
35. The potential energy diagram for a reaction R  P is given below :
H0 of the reaction corresponds to the energy –

(A) x (B) y (C) z (D) (x+y)
36. Read the following industrial methods for the preparation of H2SO4 and answer the question at the end.
Professor Molina of the Massachusetts Institute of Technology won the 1995 Nobel Prize in Chemistry for his
work on atmospheric chemistry. One reaction that he has studied in detail is the acid rain reaction which
produces H2SO4 in the atmosphere. He has proposed two possible stoichiometric reactions :
Proposal A : H2O (g) + SO3 (g)  H2SO4 (g)
Proposal B : 2 H2O (g) + SO3 (g)  H2SO4 (g) + H2O (g)
Using simple collision theory , what reaction orders would be expected for proposal B ?
Proposal B is thought to proceed by the following two-step process :
SO3 + 2 H2O SO3.2 H2O (fast)
k2
SO3.2 H2O   H2SO4 + H2O (slow)
(SO3.2 H2O is a complex which is stabilized by hydrogen bonds and k2 << k1 or k–1 ).
(A) k [H2O] [SO3] (B) k [H2O]2 [SO3] (C) k [SO3] (D) k [H2O]

96
37. Two reaction, A  products and B  products have rate constants Ka and Kb at temperature T and
activation energies Ea and Eb respectively. If Ka > Kb and Ea < Eb and assuming that A for both the reactions
is same then :
(A) At higher temperatures Ka will be greater than Kb
(B) At lower temperature Ka and Kb will differ more and Ka > Kb
(C) As temperature rises Ka and Kb will be close to each other in magnitude
(D) All of the above
38. At room temperature, the reaction between NO and O2 to give NO2 is fast, while that between CO and O2 is
slow. It is due to :
(A) CO is smaller in size that of NO
(B) CO is poisonous
(C) The activation energy for the reaction, 2NO + O2  2NO2 is less then 2CO + O2  2CO2.
(D) None of the above
39. The rate law for a reaction between the substances A and B is given by rate = K[A]n [B]m. On doubling the
concentration of A and halving the concentration of B, the ratio of the new rate to the earlier rate of the
reaction will be as :
(A) 1/2m + n (B) (m + n) (C) (n – m) (D) 2(n – m)
40. In gaseous reactions important for the understanding of the upper atmosphere H2O and O react bimolecularly
to form two OH radicals. H for this reaction is 72 kJ at 500 K and Ea is 77 kJ mol–1, then Ea for the
bimolecular recombination of two OH radicals to form H2O and O is :
(A) 3 kJ mol–1 (B) 4 kJ mol–1 (C) 5 kJ mol–1 (D) 7 kJ mol–1
41. A reaction takes place in three steps having rate constants K1, K2, K3 respectively. The overall rate constant
K1K 3
K = K . If energies of activations for the three steps are 40, 30, 20 kJ respectively, the overal energy of
2
activation is :
(A) 10 (B) 15 (C) 30 (D) 60
More than one choice Type
42. Table I (reactions) and table II (methods) have been matched
Correct matching is :
P Q R P Q R
(A) X Y Z (B) Y X Z
(C) Z X Y (D) Z Y X
43. Which of the following statements are correct about half–period.
(A) It is proportional to initial concentration for zeroth order
(B) Average life = 1.44 half–life for first order reaction.
(C) Time of 75% completion of reaction is thrice of half–life(initial half life) period in second order reaction
(D) 99.9% reaction takes place in 100 minutes for the case when rate constant is 0.0693 min–1
44. Zn + 2 H+  Zn2+ + H2
Half–life period is independent of concentration of zinc at constant pH. For the constant concentration of Zn,
rate becomes 100 times when pH is decreased from 3 to 2. Hence ,
dx  dx 
(A) = k [Zn]0[H+]2 (B)  dt  = k [Zn][H+]2
dt  
(C) rate is not affected if concentration of zinc is made four times and that of H+ ion is halved
(D) rate becomes four times if concentration of H+ ion is doubled at constant Zn concentration

97
2000
45. Rate constant k varies with temperature by equation , log k(min–1) = 5 – T(K ) . We can conclude:
(A) pre–exponential factor A is 5 (B) Ea is 2000 kcal

(C) pre–exponential factor A is 105 (D) Ea is 9.212 kcal
46. Activation energy of a chemical reaction can be determined by :
(A) evaluating rate constant at standard temperature
(B) evaluating velocities of reaction at two different temperatures
(C) evaluating rate constant at two different temperatures
(D) changing concentration of reactants
47. Which of the following statements are correct ?
(A) Law of mass action and rate law expressions are same for single step reactions.
(B) Order of the slowest elementary reaction of a complex reaction gives the order of the complex reaction
(C) Both order and molecularity have normally a maximum value of 3
(D) Molecularity of a complex reaction, A + 2B  C is 3.
48. Which of the following statement are true regarding the log K vs.
1/T plot shown in the given diagram ? K  Ae Ea / RT
(A) Plot P shows that the energy of activation is independent of
temperature.
(B) Plot Q describes the behaviour of temperature dependence of energy
of activation
(C) Arrhenius behaviour is described by P
Ea
(D) The slope of curve P gives the value –
R
[SO 2 ]
49. Pt
If the rate of reaction, 2SO2(g) + O2(g)  2SO3(g) is given by : Rate = K
[SO 3 ]1/ 2
which statements are correct :
(A) The overall order of reaction is –1/2
(B) The overall order of reaction is +1/2
(C) The reaction slows down as the product SO3 is build up
(D) The rate of reaction does not depend upon concentration of SO3 formed
1
50. For a second order reaction plots are made for [ A ] vs time for the reaction, 2A  Product. Pick up the
correct sentences.
(A) the graph will show straight line with slope K
(B) the graph will show straight line with intercept [A]0
(C) the graph will show straight line with slope [A]0
1
(D) the graph will show straight line with intercept [ A ]
0
Comprehension # 1
Study the following experiment and answer the questions at the end of it.
The following reactions was studied at 250C in benzene solution containing 0.10 M pyridine
CH3OH + (C6H5)3 CCl  (C6H5)3 C . OCH3 + HCl

A B C
The following sets of data were observed :
Set Initial concentration time difference Final concentration [C]

[A]0 [B]0
I 0.10 M 0.05 M 25 min 0.0033 M
II 0.10 M 0.10 M 15 min 0.0039 M
III 0.20 M 0.10 M 7.5 min 0.0077 M

98
d [C ]
51. Rates in sets I , II and III are respectively (in M min–1) :
dt
I II III
(A) 1.30 × 10–4 2.6 × 10–4 1.02 × 10–3
(B) 0.033 0.0039 0.0077
(C) 0.02 × 10–4 0.04 × 10–4 0.017
(D) None of above
52. Rate law of the above experiment is :
(A) r = k [A] [B] (B) r = k [A]3 [B] (C) r = k [A] [B]2 (D) r = k [A]2 [B]0
53. Rate constant of the above experiment is :
(A) 1.3 × 10–1 (B) 2.6 × 10–2 (C) 2.6 × 10–1 (D) 1.3 × 10–2
Comprehension # 2
Study the two photochemical reactions and answer the question at the end.
For the overall reaction between A and B to yield C and D , two mechanisms are proposed :
I. A + B  AB*  C + D , k1 = 1 × 10–5 M–1 s–1
II. A  A*  E , k1 = 1 × 10–4 s–1
E + B  C + D , k2 = 1 × 1010 M–1 s–1
(species with * are short-lived)
54. Rate according to mechanism I when concentration of each reactant is 0.1 M will be :
(A) 1 × 10–7 Ms–1 (B) 1 × 10–6 Ms–1 (C) 1 × 10–5 Ms–1 (D) 1 × 10–4 Ms–1
55. Rate according to mechanism II when concentration of each reactant is 1 M will be :
(A) 1 × 10–4 Ms–1 (B) 1 × 1010 Ms–1 (C) 1 × 10–6 Ms–1 (D) 1 × 10–10 Ms–1
56. At what concentration of B, rates of two mechanism are equal :

(A) 1 M (B) 5 M (C) 7 M (D) 10 M
Comprehension # 3
The thermal decomposition of N2O5 occurs as : 2N2O5  4NO2 + O2
Experimental studies suggest that rate of decomposition of N2O5, rate of formation of NO2 or rate of formation
of O2 all becomes double if concentration of N2O5 is doubled.
57. The correct mechanism for decomposition of N2O5 is :
Slow Fast
(A) N2O5   NO2 + NO3 ; N2O5 + NO3   3NO2 + O2
Fast Slow
(B) N2O5  NO2 + NO3 ; N2O5 + NO3  3NO2 + O2
Fast 1
(C) N2O5   2NO2 + 2 O2
Slow Fast 1
(D) N2O5   NO + NO2 + 2O2 ; N2O5 + NO2   3NO2 + 2 O2
58. If rate constants for decomposition of N2O5, formation of NO2 and formation of O2 are K1, K2 and K3 respectively,
then :
(A) K1 = K2 = K3 (B) 2K1 = K2 = 4K3 (C) K1 = 2K2 = K3 (D) K1 = K2 = 2K3
59. If rate of formation of O2 is 16 g/hr, then rate of decomposition of N2O5 and rate of formation of NO2 respectively
is :
(A) can not be calculated without knowing rate constants (B) 108 g/hr, 92 g/hr
(C) 32 g/hr, 64 g/hr (D) 54 g/hr, 46 g/hr
60. The container of 2 litre contains 4 mole of N2O5. On heating to 100°C, N2O5 undergoes complete dissociation
to NO2 and O2. Select the correct answers if rate constant for decomposition of N2O5 is 6.2 × 10–4 sec–1.
1. The mole ratio before and after dissociation is 4 : 2.
2. Half life of N2O5 is 1117 sec and it is independent of temperature.
3. Time required to complete 40% of reaction is 824 sec.
4. If volume of container is doubled, the rate of decomposition becomes half of the initial rate :
(A) 1, 3, 4 (B) 1, 2, 3, 4 (C) 3, 4 (D) 2, 3, 4

99
Comprehension # 4
The instantaneous rate of an elementary chemical reaction : aA + bB cC + dD can be given by :
rate = Kf[A]a [B]b – Kb [C]c [D]d where, Kf and Kb are rate constants for forward and backward reactions
respectively for the reversible reaction. If the reaction is an irreversible one, the rate is expressed as : rate =
K[A]a [B]b where K is rate constant for the given irreversible reaction and (a + b) is order of reaction. It is also
a
evident from the stoichiometry of reaction that rate of disappearance of A is times the rate of disappearance
b
of B. The variation of rate constant K with temperature is expressed in terms of Arrhenius equation :
Kf
K = Ae E a / RT whereas the ratio K is expressed in terms of van’t Hoff isochore :
b
Kf  H / RT
K b = Ae , where Ea and H are energy of activation and heat of reaction respectively..
61. For a chemical reaction aA  bB ;

 d[ A ]   d[B] 
log  dt  = log  dt  + 0.3,
   
then the ratio of a and b is approximately :
(A) 3 (B) 0.3 (C) 2 (D) 0.5
Kf
62. The variation of K and K with increase in temperature shows the following effects :
b
Kf
(i) For endothermic reaction K increase, K also increases
b
Kf
(ii) For endothermic reaction K decreases, K also decreases.
b
Kf
(iii) For exothermic reaction K and K both increases.
b
Kf
(iv) For exothermic reaction K increases and K decreases
b
Kf
(v) For exothermic reaction K and K both decreases.
b
(A) i, iv (B) iii, v (C) ii, iii (D) ii, iii, v
63. For a gaseous phase I order reaction : A(g)  B(g) + 2C(g) (rate constant K = 10–2 time–1), in a closed
vessel of 2 litre containing 5 mole of A(g) at 27°C, which of the following is incorrect ?
(A) Rate of appearance of C(g) is 5 x 10–2 mol L–1 t–1
(B) Rate of disappearance of A(g) is 6.15 x 10–3 atm t–1
(C) Rate of disappearance of A(g) is 5.0 x 10–2 mol t–1
(D) Rate of appearance of B(g) is 5 x 10–2 mol L–1 t–1
  d[ A ] 
64. For an elementary reaction aA  product, the graph plotted between log  dt  vs. time gives a
 
straight line with intercept equal to 0.6 and showing an angle of 45° with origin, then :
(A) rate constant = 3.98 time–1 and a = 1 (B) rate constant = 3.98 mol L–1 t–1 and a = 1
(C) rate constant = 1.99 time–1 and a = 1 (D) rate constant = 1.99 mol–1 L1 t–1 and a = 2

100
PART - II : SUBJECTIVE QUESTIONS
1. Figure represents the variation of the concentrations of A and B with time for the reaction :
A  nB. Calculate the concentration of B at the point of intersection O.
2. The net rate of reaction for the change :

[Cu(NH3)4]2+ + H2O [Cu(NH3)3H2O]2+ + NH3 is,
dx
= 2.0 x 10–4 [Cu(NH3)4]2+ – 3.0 x 105 [Cu(NH3)3H2O]2+[NH3]
dt
Calculate :
(i) rate expression for forward and backward reaction.
(ii) the ratio of rate constants for forward and backward reaction.
(iii) the direction of reaction in which the above reaction will be more predominant.
3. The catalytic decomposition of formic acid may take place in two ways :
(i) HCOOH(g)  H2O(g) + CO(g) (ii) HCOOH(g)  H2(g) + CO2(g)
The rate constant and activation energy for reaction (i) are 2.79 x 10–3 min–1 at 237°C and 12.0 kcal mol–1
respectively. These values for reaction (ii) are 1.52 x 10–4 min–1 at 237°C and 24.5 kcal mol–1 respectively.
Find out the temperature at which equimolar quantities of H2O, CO, CO2 and H2 are formed. (R = 2 cal) ?
4. The energy of activation for a reaction is 100 kJ mol–1. Presence of a catalyst lowers the energy of activation
by 75%. What will be effect on rate of reaction at 20°C ; other things being equal ?
5. A follows parallel path  order reactions giving B and C as :
If initial concentration of A is 0.25 M calculate the concentration of C after 5 hrs. of reaction

Given : 1 = 1.5 x 10–5 sec–1 ; 2 = 5 x 10–6 sec–1
6. Two reactants A and B separately shows two chemical reactions. Both reactions are made with same initial
concentration of each reactant. Reactant A follows first order kinetics whereas reactant B follows second
order kinetics. If both have same half lives, compare their rates (a) at the start of reaction (b) after the lapse
of one half life.
7. The progress of the reaction, A nB with time is presented in the figure. Determine :
(i) the value of n (ii) the equilibrium constant K and (iii) the initial rate of conversion of A.

101
d[ A ]
8. The reaction, A + OH¯  Products, obeys rate law expression as, = k [A] [OH–]. If initial
dt
concentrations of [A] and [OH¯] are 0.002 M and 0.3 M respectively and if it takes 30 sec for 1% A to react
at 25°C, calculate the rate constant for the reaction.
9. Catalytic decomposition of nitrous oxide by gold at 900°C at an initial pressure of 200 mm was 50% in 53
minute and 73% in 100 minute. (a) What is order of reaction ? (b) Calculate velocity constant. (c) How much
will it decompose in 100 minutes at the same temperature but at an initial pressure of 600 mm ?
10. Show that for a first order reaction, time required for 99.0% completion is twice for the time required for the
completion of 90% of the reaction.
11. At 100°C, a gaseous reaction, A  B + 2C, is observed to be of  order. On starting with pure A, at the
end of 14 minute, the total pressure was found to be 264 mm of Hg. After a long time the total pressure of the
system was 450 mm of Hg. Calculate (a) initial pressure of A (b) rate constant of reaction (c) half life period
of reaction.
12. The conversion of trypsinogen (A) and trypsin (B) is an autocatalytic reaction, A  B, where B catalyses
dx
the reaction. The rate equation is = K . x . y, where x and y are concentration of tripsinogen at time t.
dt
2.303 y . x0
Integrate this equation for initial concentration of x0 and y0 for A and B. Show that, Kt = x  y log x . y .
0 0 0
13. The gas phase decomposition of dimethyl ether follows first order kinetics,
CH3OCH3(g)  CH4(g) + H2(g) + CO(g)
The reaction is carried out in a constant volume container at 500°C and has a half life of 14.5 minute. Initially
only dimethyl ether is present at a pressure of 0.40 atmosphre. What is the total pressure of the system after
12 minute ? Assume ideal gas behaviour.
14. The half time of first order decomposition of nitramide is 2.1 hour at 15°C.
NH2NO2(aq)  N2O(g) + H2O(l).
If 6.2 g of NH2NO2 is allowed to decompose, calculate : (i) time taken for NH2NO2 to decomposition 99% (ii)
volume of dry N2O produced at this point measured at STP.
15. The reaction :
CH3COF + H2O  CH3COOH + HF
has been studied under the following initial conditions :
Case-I Case-II
CH 2O  1.00 M CH 2O  0.02 M
C CH3COF  0.01 M C CH3COF  0.80 M

Concentrations were monitored as a function of time and are given below :
Case-I Case-II
t/min CCH3COF /M t/min CH2O /M
0 0.01000 0 0.0200
10 0.00857 10 0.0176
20 0.00735 20 0.0156
40 0.00540 40 0.0122
Determine the order of the reaction and the rate constant for the reaction.
16. The rate constant for the II order neutralization of 2-nitropropane by aqueous alkali obeys the equation
3163
log10 K = + 12
T
T is temperature in Kelvin.
Time and concentration were in minute and mol litre–1 respectively. Calculate half life at 43.3°C and for an
initial concentration of 0.001 mol litre–1 for each of the reactant.

102
17. In the decomposition of H2O2 at 300 K, the energy of activation was found to be 18 kcal/mol while it decreases
to 6 kcal/mol when the decomposition was carried out in the presence of a catalyst at 300 K. How many
times is the catalysed reaction faster than uncatalysed one ?
18. The rate of decomposition of a substance increases by a factor 2.25 for 1.5 times increase in concentration
of substance at same temperature. Find out order of reaction.
19. For a homogenous gaseous reaction, A  B + C + D, the initial pressure was P0 while pressure after
time t was P. Derive an expression for rate constant K in terms of P0 and t.
20. In a II order reaction, when the concentration of both the reactants are equal, the reaction is completed 20%
in 500 sec. How long it would take for the reaction to go to 60% completion ?
21. Half-life period for decomposition of NH3 over tungsten wire are given below :
Initial Pressure in min 50 100 200
T1/2 3.52 1.82 0.93
Calculate order of reaction.
22. A substance A is mixed with equal quantities of the substance B and C. At the end of 1000 second, half of the
amount of A has reacted. What fraction of A will be left unreacted at the end of 2000 second. If the reaction
is (a) zero order with respect to A ? (b) II order with respect to A ?
23. Acetone on heating gives CO and other hydrocarbons at 600°C. The reaction obeys Ist order kinetics with
respect to acetone concentration. The half life period is 81 sec. Calculate the time in which acetone taken in
a container at 600° reduces its pressure from 0.5 atm to 0.4 atm.
24. The specific rate constant of the decomposition of N2O5 is 0.008 min–1. The volume of O2 collected after 20
minute is 16 mL. Find the volume that would be collected at the end of reaction. NO2 formed is dissolved in CCl4.
25. A 22.4 litre flask contains 0.76 mm of ozone at 25°C. Calculate :
(i) the concentration of oxygen atom needed so that the reaction, O + O3  2O2 having rate constant equal
to 1.5 x 107 litre mol–1 sec–1 can proceed with a rate of 0.15 mol litre–1 sec–1.
(ii) the rate of formation of oxygen under this condition.
26. A vessel contains dimethyl ether at a pressure of 0.4 mm. Dimethyl ether decomposes as :
CH3OCH3(g)  CH4(g) + CO(g) + H2(g). The rate constant of decomposition is 4.78 x 10–3 min–1. Calculate
the ratio of initial rate of diffusion to rate of diffusion after 4.5 hours of initiation of decomposition. Assume the
composition of gas present and gas diffused to be same.
27. A certain reaction A + B  Product is first-order w.r.t. each reactant with k = 5.0 × 10–3 M–1 s–1. Calculate
the concentration of A remaining after 100 s if the initial concentration of A was 0.1 M and that of B was
6.0 M. State any approximation made in obtaining your result.
28. A flask contains a mixture of compounds A and B. Both compounds decompose by first-order kinetics. The
half-lives are 54.0 min for A and 18.0 min for B. If the concentrations of A and B are equal initially, how long will
it take for the concentration of A to be four times that of B ?
29. Compounds A and B react to form C and D in a reaction that was found to be second-order overall and
second-order in A. The rate constant at 30°C is 0.622 L mol–1 min–1. What is the half-life of A when
4.10 × 10–2 M of A is mixed with excess B ?
30. Acetoacetic acid, CH3COCH2COOH, in acid solution decomposes to CO2 and acetone by a firstorder
reaction. From the following data find the halflife time for this reaction at 370C.
A solution containing 6 mmol sodium acetoacetate was rapidly brought into about 0.2M HCl so that the total
volume was 200ml. After 220 min. at 370C, a sample of 10 ml was taken out and immediately put into an
excess of NaOH, which put an end to the decomposition. The acetone that had formed was blown away by
bubbling air. The sample was again acidified and boiled; all the remaining acetoacetic acid was then transformed
to acetone, which was distilled with water vapour. To this distillate, NaOH and 10.00 ml 50 mM I2 solution
were added, transforming all acetone to iodoform
CH3COCH3 + 3I2 + 4OH  CHI3 + CH3COO + 3I + 3H2O
After acidification the remaining iodine was decolorize by 4.5 ml thiosulfate solution. Ten ml 50 mM I2
solution was decolourized by 10 ml of the same thiosulfate solution. At pH = 0 to 3 the reaction rate is
independent of pH.

103
MATCH THE COLUMNS :
31. Match order of the reaction (in List – I) with the corresponding rate constant (in List – II) :
List I (order) List II (rate constant)
1  1 1
(A) Zero (p) k=  – 
2
2t  (a – x ) a2 
1  1 1
(B) First (q) k=  – 
t  (a – x ) a 
x
(C) Second (r) k=
t
1  a 
(D) Third (s) k= loge  (a – x ) 
t  
32. Match order of the reaction (in List - ) with the unit of rate constant (in List-II) :
List I (order) List II (unit)
(A) Zero (p) L2 mol–2 s–1
(B) First (q) L mol–1 s–1
(C) Second (r) mol L–1 s–1
(D) Third (s) s–1
33. Match the given reaction of various order (in List I) with method of study of kinetics (in List II) :
List  (reaction) List II (method)
(A) 2N2O5(g)  2N2O4(g) + O2 (g) (p) Titration by Na2S2O3
(B) S2O82– + 2I–  2SO42– + I2 (q) Titration by KMnO4
(C) 2H2O2  2H2O + O2 (r) Titration by NaOH
(D) C12H22O11+H2O  C6H12O6+C6H12O6 (s) Measuring pressure of the mixture in inert medium.
(E) CH3CHO(g)  CH4(g) + CO (g) (t) Measuring angle of rotation.


H
(F) CH3COOC2H5+H2O  CH3COOH+C2H5OH (u) Measuring pressure of the gas in CCl4 medium
(use the fact that N2O4 dissolves in CCl4 medium)
34. Match the order of reaction (in List I) with its property (in List II) :
List I (order) List II (Property)
1
(A) Zero (p) Half life  2
a
1
(B) First (q) Half life 
a
(C) Second (r) Half life is doubled on doubling the initial concentration
(D) Third (s) 50% reaction takes same time even if concentration is
halved or doubled.

104
PART - I
1. (B) 2. (A) 3. (C) 4. (B) 5. (D)
6. (B) 7. (A) 8. (A) 9. (D) 10. (C)

11. (C) 12. (B) 13. (A) 14. (C) 15. (A)
16. (C) 17. (A) 18. (C) 19. (A) 20. (B)
21. (A) 22. (B) 23. (A) 24. (C) 25. (A)
26. (D) 27. (D) 28. (B) 29. (D) 30. (B)
31. (C) 32. (B) 33. (D) 34. (B) 35. (A)
36. (B) 37. (C) 38. (C) 39. (D) 40. (C)
41. (C) 42. (B,C) 43. (A,B,C,D) 44. (B,C,D) 45. (C,D)
46. (B,C) 47. (A,B,C) 48. (A,B,C) 49. (B,C) 50. (A,D)
51. (A) 52. (B) 53. (C) 54. (A) 55. (A)
56. (D) 57. (A) 58. (B) 59. (B) 60. (C)
61. (C) 62. (A) 63. (D) 64. (A)
PART - II
nA 0
1. [B] =
1 n
2. (i) 3.0 x 105 [Cu(NH3)3H2O]2+[NH3] (backward), 2 × 10–4 [Cu(NH3)4]2+ (forward)

(ii) 6.6 x 10–10 litre mol–1
(iii) More predominant reaction is backward reaction.
3. (a) 3940C 4. 2.35 x 1013 5. 3.7 × 10–2 M. 6. (a) 0.693 (b) 1.386
7. (i) 2 (ii) 1.2 mol litre–1 (c) 0.1 mol litre–1 hour–1 8. 1.2 x 10–3 L mol–1 sec–1
9. (a) 1 (b) 1.308 x 10–2 (c) 73% 10. t99% = 2 × t90%
2.303 y. x 0
11. (a) 150 mm (b) 3.415 × 10–2 min–1 (c) 20.29 min 12. log
(x0  y0 ) x. y 0
13. 0.75 atm 14. (i) 13.95 hour (ii) 2.217 litre 15. 1.54 x 10–2 min–1
16. 10–19 minute 17. 4.8 x 108 times 18. 2
19. K = (2.303/t) log [2P0 / (3P0 – P)] 20. 3000 sec 21. II order
22. (a) zero, (b) 1/3 23. 26.07sec. 24. 108.23 mL 25. (i) 2.45 x 10–4 (ii) 0.30 mol L–1 t–1
26. 0.261 27. 0.005 M 28. t = 53 min 29. 39.2 min

30. 52.7 min.
31. (A )  (r) ; (B)  (s) ; (C)  (q) ; (D)  (p) 32. (A )  (r) ; (B)  (s) ; (C)  (q) ; (D)  (p)
33. (A )  (s, u) ; (B)  (p) ; (C)  (q, s, u) ; (D)  (t) ; (E)  (s, u) ; (F)  (r)
34. (A )  (r) ; (B)  (s) ; (C)  (q) ; (D)  (p)

SOLID STATE
105 SOLID STATE Chemistry
KEY CONCEPTS molecules together are so great, that

the material becomes rigid but there
1. Solids is no regularity in structure.
(c) They do not have sharp melting
Solids are characterised by the state of matter points.
in which particles are closely packed and held
(d) They are isotropic as they exhibit
together by strong intermolecular attractive
force. same physical properties in all the
directions.
1.1 Properties of solids :
(e) The general examples of this solids
(a) In solid state the particles are not able to are glass, Rubber, plastics etc.
move randomly.
1.3 Difference b/w crystalline and amorphous
(b) They have definite shape and volume. solids :
(c) Solids have high density .
S.No. Property Crystalline Amorphous
(d) Solids have high and sharp melting point
which depends on the strength or value of solids solids
binding energy. 1 Shape They have They do not
(e) They are very low compressible. definite and have
(f) They show very slow diffusion. regular definite and
geometrical regular
1.2 Types of Solids : form geometrical
Solids form
2 Melting point They have They do not
Crystalline Solids Amorphous Solids definite have
1.2.1 Crystalline solids : melting definite
point melting
(a) In this type of solids the atoms,
point
molecule or ions are arranged in a
regular pattern in the three 3 Heat of They have a They do not
dimensional network. fusion definite heat have
(b) They have sharp melting point and of fusion definite heat
definite heat of fusion. of fusion
(c) They are anisotropic in nature. 4 Compressibilit They are rigid These may be
Anisotropic means they exhibit y and compressed
different physical properties in incompressibl to any
different directions. eg. e appreciable
The electrical and thermal extent
conductivities are different in
different directions. 5 Isotropy and They are They are
Anisotropy anisotropic isotropic
(d) They are generally incompressible.
(e) The general examples of crystalline
2. Study of crystals
solids are Quartz, diamond etc.
1.2.2 Amorphous Solids : 2.1 Crystal :
(a) In this type of solids, the
A crystal is a homogenous portion of a
arrangement of building constituents
is not regular. However, they may solid substance made by regular pattern of
possess regular pattern upto very structural units bonded by plane surface
small distances and hence, they are making definite angles with each other.
also known as short range solids. 2.2 Space lattice :
(b) They are regarded as super cooled The arrangement of constituents atom,
liquids with high viscosity in which ions and molecules in different sites in
the force of attraction holding the

three dimensional space is called space intercepts of its face on the various
lattice. axes.
2.3 Unit cell : (b) Miller indices is a reciprocal of weiss
The smallest repeating unit in space lattice indices i.e. miller indices for a plane
which when repeats over and over again, may be obtained from weiss indices.
results in a crystal of the given substance Z
R
called unit cell.
2.4 Face :
The plane surface of the crystal are called C
faces. c
b Q
2.5 Edge : a
B Y
An edge is formed by the intersection of A
two adjacent faces. X
P
2.6 Interfacial angles : The angle between the (c) The distance between the parallel
perpendiculars two intersecting faces planes in a crystal are designated as
called interfacial angles. dhkl for different cubic lattices these
interplaner spacings are given by the
3. Laws of Crystallography
following general formula as -
3.1 The law of constancy of interfacial angle : dhkl=
a
(a) The interfacial angles for all the crystals of h2  k2  l 2
a given crystalline substance are always where, a = length of the cube side&
the same irrespective to the shape and size h,k,l = Miller indices of the plane
of crystal. This is known as law of
constancy of interfacial angles. 3.3 Law of constancy of Symmetry :
(b) The crystal of a substance can have (a) According to this law, all crystals of a
different shapes and size, depending on substance have the same elements of
the rate of formation of crystal, etc but the symmetry.
angle at which the two adjacent faces (b) A crystal possess following three types of
intersect remains always constant. symmetry - Plane, axis and centre of
symmetry. they are collectively called
elements of symmetry.
3.3.1 Plane of symmetry :
(I) (II) (III)
*3.2 Law of Rationality of indices :
(a) According to this law the ratio between
the intercepts on the axis for the different
faces of a crystal can always be expressed
by rational numbers. Means the intercepts Rectangular plane Diagonal plane of
of any face of plane of a crystal on suitable of symmetry symmetry
(No. = 3) (No. = 6)
crystallographic axes can be expressed by
small multiples of three unit distances a, b, It is an imaginary plane which passes
c or some sine integral multiple of these through the centre of a crystal and
unit distance i.e. ma : nb : pc. can divide it into two equal portions
(b) a, b, c called weiss indices. which are exactly the mirror images
to each other. For example - cubic
(c) This law was given by Hally. system have 2 types of plane of
*3.2.1 Miller indices : symmetry.
(a) It is a face of a crystal, which are 3.3.2 Axis of symmetry :
inversely proportional to the

(a) It is an imaginary line about which (No. = 1)

the crystal may be rotated so that it
3.3.3 Centre of symmetry :
presents the same appearance more
than once in a complete rotation (a) It is a point in the crystal that any line
through 360º. drawn through it intersects the
surface of the crystal at equal
(b) The axes of symmetry are called
distance on either side.
diad, triad, tetrad and hexad
respectively, depending on the Y
original appearance is repeated twice
(180º), thrice (120º), four times (90º) Centre of
and six times (60º) in one rotation. symmetry
(c) These axes of symmetry are also
called as two fold, three fold, four
X
fold and six fold respectively.
(d) Five fold symmetry is not found in Z
crystals. Note : Only simple cubic system have
one centre of symmetry. Other
system do not have centre of
symmetry.
(e)
3.3.4 Elements of Symmetry :
(a) The total number of planes, axes and
centre of symmetries possessed by a
(i) Axis of two fold symmetry. (No. = 6) crystal is termed as elements of
symmetry.
(b) A cubic crystal possesses total 23
elements of symmetry.
(i) Plane of symmetry (3 + 6) = 9
(ii) Axes of symmetry (3 + 4 + 6) = 13
(iii) Centre of symmetry (1) = 1
(ii) Axis of three fold symmetry. (No.
4) Total symmetry = 23
4. Crystal System
(a) the geometry of an unit cell is given by its
length along the three crystallopic axis and
the angle between them.
(b) On the basis of geometrical consideration
theoritically there can be 32 different
combinations of elements of symmetry of
(iii) Axis of four fold symmetry. crystal.
(No. = 3) (c) But on the other hand Bravais showed that
there are only seven types of crystal
system. These are :
(a) Cubic (b) Tetragonal (c) Orthorhombic
(d) Rhombohedral (e) Hexagonal
(d) Monoclinic (e) Triclinic
(d) There are 14 Bravais lattices under
seven crystal systems as follows : -
(iv) Axis of six fold symmetry.
The Bravais Lattices

S.No. Crystal system Axial Axial angles Space lattice
Unit cell
distance 
1. Cubic a=b=c  =  = = 90º a Simple :

y Lattice points at the
c eight corners of the unit
 cells.
 a
 x
b b. Body centered :
z Points at the eight
corners and at the body
centered.
c. Face centered :
points at the eight
corners and at the six
face centres.
2. Tetragonal a=bc =  =  = 90º d. Simple :

y Points at the eight
c corners of the unit cell.
 
a e. Body centered :
 x
b Points at the eight
z corners and at the body
centre.
3. Orthorhombic abc  =  =  = 90º f. Simple :

(Rhombic) Points at the eight
y corners of the unit cell.
c
 
b a
 g. End centered :
z x Also called side
centered or base
centered. Points at the
eight corners and at two
face centres opposite to
each other.
h. Body centered :
Points at the eight
corners and at the body
centre.
i. Face centered :
Points at the eight
corners and at the six
face centres.
4. Rhombohedral a=b=c a = b =   90º j. Simple :

or Points at the eight
Trigonal corners of the unit cell.

  x

y
5. Hexagonal a=bc =  = 90º k. Simple :
y  = 120º i. Points at the twelve
c corners of the unit cell
 out lined by thick line.
 or
b a
 ii. Points at the twelve
z x corners of the hexagonal
prism and at the centres
of the two hexagonal
faces.
6. Monoclinic abc  =  = 90º   l. Simple :

 
b a
x m. End centered :
z 
Point at the eight
corners and at two face
centres opposite to the
each other.
7. Triclinic abc  90º n. Simple :

 
b a
z 
x
5. Mathematical Analysis of Cubic 5.1 Atomic radius :

system (Types and Analysis) It is defined as the half of the distance
between nearest neighbouring atoms in a
Simplest crystal system is to be studied is crystal. It is expressed in terms of length of
cubic system. Three types of cubic systems are-
the edge (a) of the unit cell of the crystal.
(a) Simple Cubic (SC) : (a) Simple cubic structure (S.C.) :
Atoms are arranged at the corners of the
a
cube. Radius of atom ‘r’ =
2
(b) Body Centered Cubic (BCC) :
Atoms are arranged at the corners and at a
the centre of the cube.
(c) Face Centered Cubic (FCC) : Atoms are
r r
arranged at the corners and at centered of
the each faces.
(b) Face centered cubic structure (FCC): (i) Eight Corner atoms contribute one
a
atom per unit cell.
‘r’ =
2 2 (ii) Centre atom contribute one atom per
unit cell.
(c) Body centered cubic structure (BCC):
(iii) So, total 1 + 1 = 2 atoms per unit cell.
3a
‘r’ = 1
4 Z= 8 × +1=2
8
5.2 Number of atoms per unit cell / unit cell
Number of Atoms in Unit Cell
contents :
It can be determined by the simplest
The total number of atoms contained within
relation
the unit cell for a simple cubic called the unit
nc nf ni
cell content. =  
8 2 1
(a) Simple cubic structure (SC) : where nc = number of atoms at the corners
Each corner atom is shared by eight of the cube = 8
surrounding cubes. Therefore, it nf = number of atoms at six faces of the cube =
1 6
contributes for of an unit cell.
8
ni = number of atoms inside the cube = 1
1
 z =8× =1 Cubic unit cell nc nf ni Total atom in
8
per unit cell
1. Simple cubic 8 0 0 1
2. Body 8 0 1 2
centered
cubic
(b) Face centered cubic structure (FCC) : 3. Face 8 6 0 4
(i) The eight corners atoms contribute centered
for 1/8 of an unit cell and thus one cubic
atom per unit cell. 5.3 Co-ordination number (C.N.) :
(ii) Each of six face centered atoms is (a) It is defined as the number of nearest
shared by two adjacent unit cells and neighbours or touching particles with other
therefore one face centred atom particle present in a crystal.
contribute half of its share. Means
(b) It depends upon structure of the crystal.
1
6 × = 3 atom per unit cell. (c) It is 6 for simple cubic, 8 for bcc and 12 for
2
fcc.
5.4 Density of lattice matter :
(a) It is defined as the ratio of mass of unit cell
to the total volume of unit cell.
(iii) So, total Z = 3 + 1 = 4 atoms per unit

(b) Density of lattice matter
cell.
mass per unit cell
(c) Body centered cubic structure (BCC) : =
Volume of unit cell

Z  Atomic. weight Number of atoms per unit cell = 4

=
N  volume of unit cell
2a 4r
and r = a=
Where Z is the number of atoms per unit 4 2
cell and N is the Avogadro number.
4 3
4 r
5.5 Packing fraction (P.F.) : P.F. = 3 = 0 .74
3
It is defined as ratio of the volume of the  4r 
 
unit cell that is occupied by spheres of the  2
unit cell to the total volume of the unit cell. % P.F. = 74 %
(a) Simple cubic unit cell : % of void = 100 – 74 = 26 %
1 6. Packing of Constituents in Crystals
Number of atoms per unit cell = 8 × =1
8
6.1 Close packing in two dimensions :
The two possible arrangements of close
packing in two dimensions.
6.1.1 Square close packing :
a In which the spheres in the adjacent
and r =  a = 2r
2 row lie just one over the other and
4 3
r
show a horizontal as well as vertical
therefore, P.F. = 3 3 = 0.52 alignment and form square. Each
(2r ) sphere in this arrangement is in
%P.F. = 52% contact with four other spheres.
% of void = 100 – 52 = 48 % 6.1.2 Hexagonal close packing :
(b) Body centered cubic unit cell : In which the spheres in every second
row are seated in the depression
Number of atoms per unit cell between the spheres of first row. The
1 spheres in the third row are vertically
= 8× +1=2
8 aligned with spheres in first row. The
similar pattern is noticed throughout
3a 4r
and r = a= the crystal structure.
4 3
(square close packing) (Hexagonal

4 3 close packing)
2 r
P.F.= 3 = 0.68% = 68 % 6.1.3 Tetrahedral void :
4 r / 3 
3
(i) This type of void is formed when a
% of void = 100 – 68 = 32 % triangular void of a hexagonal closed
(c) Face centered cubic unit cell : plane is covered by an atom of
another atomic layer.
(ii) In any closed packed structure each
atom has two tetrahedral void.

3. In square close packing the vacant spaces

(voids) are between four touching spheres,
whose centres lie at the corners of a
1 4 2 square. These are called square voids.
or While in hexagonal close packing the
vacant spaces (voids) are between three
3 touching spheres, whose centres lie at the
corners of an equilateral triangle. These
are called triangular voids.
A A A A A
C
B
C
B
C
B
C
6.2 Close packing in three dimensions :
A A A A There are also different ways to arrange
C C C
B B
spheres in three dimensional close packing.
A A A A A
6.2.1 Hexagonal close packing (hcp) :
(a)
When the spheres in every layer is
placed above only one type of voids (B
or C) of previous layer, the spheres of
B
B
B
B
every third layer lie strictly above the
C C C spheres of first layer. This arrangement
if continued infinitely in the same
B B
A A A A A
sequence is represented as AB AB AB
............. .
(b)
6.1.4 Octahedral void : A

B
(i) The unoccupied space surrounded by A
six atoms or ions is called octahedral B
void.
(ii) In any closed packed structure each (a) (b)
atom has one octahedral void. The arrangement is found to
(iii) This type of void is obtained when represent hexagonal close packing
triangular void of another layer of (hcp) symmetry which means that
whole structure possesses one six fold
hexagonal close packed layer is
of symmetry.
placed over it.
6.2.2 Cubic close packing (ccp) :
5 When the spheres are placed
alternatively above the voids B and C
1 2 type, then the spheres of every
or fourth layer lie strictly above the
4 6 spheres of first layer. This
3 arrangement, If continued infinitely
in the same sequence, is represented
as ABC ABC ABC........This
Comparison between Hexagonal Close arrangement is exactly same as fcc.
Packing and Square Close Packing
C
1. Hexagonal close packing is more dense
B
than square close packing.
A
2. In hexagonal close packing about 60.4% of
C
available space is occupied by spheres, B
whereas, square close packing occupies A
only 52.4% of the space by spheres.

(a) (b) configuration is such that there is little

6.2.3 Body centered cubic arrangement : transfer of electrons between their atoms.
This structure will be obtained if the eg. Noble gases.
spheres in first layer (marked A) of
cubic closed packing are slightly (c) The molecules having H-atom attached on
opened up and thus none of these is N, O or F give hydrogen bonding crystals.
in contact with each other. The existence of H-bonding in the crystal
lattice is beyond doubt.
One can put the second layer of the
spheres (marked B) on the top of the e.g. Ice Crystal etc.
first layer in such a way that each
sphere of the second layer is in 7.4 Metallic Crystals :
contact with four spheres of the layer In metallic crystals, the lattice consists of
below it. assemblage of positive ions immersed in a
A A sea of mobile electrons. The binding force is
A A A A due to-
B B B A A
A A A A B (a) Attraction between positive ions or ion
B B B A A cores of the metal and electron cloud .
A A A A
A A (b) The mutual repulsion of free electrons.
7. Classification of Crystals (c) The mutual repulsion of ion cores.
The attractive force which hold crystal together 8. Limiting Radius Ratio & Packing in ionic solids
are generally of four types and thus crystal can
be classified into four types : 8.1 Limiting radius ratio :
7.1 Ionic Crystals : The packing in ionic solids are based on the
(a) The lattices in ionic crystal consists of following fundamentals :
alternative positive and negative ions in (i) Similarly charged ions should be placed at
equivalent amount arranged in an order so maximum distance and oppositvely
that the potential energy of the ions in the charged ions, at minimum distance.
lattice is minimum. (ii) The number of oppositively charged ions
(b) Such crystal are normally found in ionic around an ion should be maximum.
compound. Hence, packing is performed in such a way
+ – that both the conditions should be full
e.g. NaCl 
 Na + Cl
filled. These conditions depends on the
7.2 Covalent Crystals : sizes of cation and anion. In order to
(a) In covalent crystals, atoms at their lattice determine the closest packing, the limiting
point are held together by shared pairs of radius ratio, which is r+/r¯, is calculated.
electrons between them. Example : Figure show the smaller positive
(b) The covalent bonding extends through out ion of radius r+ in contact with three larger
the crystals in spatial direction and has no negative ions of radius r¯.
small molecules in the conventional sense. Plainly AB = BC = AC = 2r¯, BE = r¯,
BD = r+ + r¯. Further, the angle A – B – C is
eg. Diamond, Graphite. 60º, and the angle
7.3 Molecular Crystals : A

(a) In molecular crystals, the repeating unit is D
chemically identifiable atoms or molecules
which do not carry a net charge.
B C
(b) Molecular bonds are formed for those E
elements or compounds whose electronic
D – B – E is 30º. By trigonometry
cos 30º = BE/BD ; BD = BE/cos 30º 0.732 – 0.999 8 BCC

r+ + r–= r–/cos 30º = r– /0.866 = r– ×
1.155 8.2 Packing in ionic solids :
r+ = (1.155r¯) – r¯ = 0.155r¯ Ionic crystal
hence r+/r– = 0.155

AB type AB2 type
Limiting Radius Ratios and Structure :
NaCl type ZnS type CsCl type
Limiting radius C.N. Shape
ratio
(r+) / (r–)
CaF2 type TiO2 type SiO2 type
< 0.155 2 Linear
0.155 – 0.225 3 Planar triangle
0.225 – 0.414 4 Tetrahedral
0.414 – 0.732 4 Square planar
Crystal Structure of Some Cubic Ionic Solids

Crystal Structure Brief description Co-ordination No. of formula
Units and Examples Number per Unit cell
1. Rock Salt Cl¯ ions in C.C.P, Na+ ions occupy all Na+ – 6 4
(NaCl - type) the octahedral voids. Cl¯ – 6
Example : Halides of Li, Na, Kand
Rb, AgCl, AgBr, NH4Cl etc.
2. CsCl - type Cl¯ ions at the corner of a cube and Cs+ – 8 1

Cs+ ions in the cubic void Cl¯ – 8
Example : CsCl, CsBr, CsI etc.
3. Zinc. Blende S–2 ions in C.C.P., Zn+2 ions occupy Zn+2 – 4 4

(ZnS) alternate tetrahedral voids i.e. only S–2 – 4
half of the total number of tetrahedral
voids are occupied
Examples : ZnS, CuCl, CuBr, CuI,
AgI etc.
4. Fluorite Structure Ca+2 ions (+ve ions) in C.C.P. and F¯ Ca+2 – 8 4

(CaF2 – type) ions (-ve ions) in all the tetrahedral F¯ – 4
voids. Example : CaF2, SrF2, BaF2,
BaCl2 etc.
5. Antiflurote Negative ions in CCP and Positive ions Na+ – 4 4

Structure in all the tetrahedral voids. Example : O–2 – 8
Na2O
Na+ ion surrounded by six Cl¯ ion
8.2.1 NaCl type :
and each Cl– ion is surrounded
r by six Na+ ions. In the octahedral
In NaCl value is 0.52. This
r structure of NaCl, Cl– ion. may
value suggests it to be be regarded as having c.c.p
octahedral in shape. In this each
`
arrangement in which all the

octahedral holes are filled by
Na+ ions.
Other examples of this structure Zn+2
are halide of Li, Na, K, Rb and Ag 2 1
Sn2–
(except AgF) oxide and sulphides
of Mg, Sr, Ba. 4
Tetrahedral void
3 filled by Zn2+
2
Zinc blende
Zns
6
Na+
3
Octahedral 1 Cl–
void filled 5 8.2.3 CsCl type :
by Na+ r
The value of in CsCl is 0.93.
4
r
Sodium chloride This value suggests b.c.c.
NaCl structure. In this each Cs+ ion is
8.2.2 ZnS type : surrounded by eight Cl¯ ions and
In ZnS the radius ratio is 0.40 vice-versa.
which suggests it to be It should strictly be noted that
tetrahedral in shape. Each Zn2+ the structure of CsCl is not
ion is tetrahedrally surrounded strictly body-centered cubic
by four S2– ions and each S2– is because ions at the center and
tetrahedrally surrounded by at the corners are not identical.
four Zn2+ ions. i. e., coordination Other examples :- CsBr, CsI, TiCl,
no. of ZnS is 4. TiBr, TiI.
Thus this structure is termed as
4:4 arrangement.
Cl–
It should be noted that zinc Cs+
blend (ZnS) has ccp structure

while wurtzuite (ZnS) has hcp
structure.
8.2.4 Fluorite structure (CaF2) :
Other examples having similar
structure are :- CuCl, CuBr, CuI, In CaF2 the radius ratio of Ca2+
and BeS. ions and F¯ ion is 0.73 suggest
b.c.c. arrangement of F¯ ions.
Since there are twice as many F¯
ions as Ca2+ ions, the
coordination number of both
ions is different; and four Ca2+
ions are tetrahedrally arranged.
around each F¯ ion. The
coordination numbers are

`
therefore 8 and 4, so this is 9.1 Electronic imperfection :

called 8:4 arrangement. Generally, electrons are present in
fully occupied lowest energy states.
But at high temperatures, some of the
Ca2+ electrons may occupy higher energy
state depending upon the
F–
temperature.
For example, in the crystals of pure Si
or Ge some electrons are released
thermally from the covalent bonds at
8.2.5 Rutile structure (TiO2) : temperature above 0 K. These
electrons are free to move in the
r
The value of for this crystal crystal and are responsible for
r electrical conductivity. This type of
is in between 0.41 and 0.73. This conduction is known as intrinsic
suggest a coordination number conduction.
of
The electron deficient bond formed
6 for one ion, and from the
by the release of an electron is called
formula it follows that the
a hole. In the presence of electric field
coordination number of other
the positive holes move in a direction
ion must be 3. This is 6:3
opposite to that of the electrons and
structure. Each Ti4+ is
conduct electricity.
octahedrally surrounded by six
O2– ion and each O2– ion has 9.2 Atomic imperfection or point defects
three Ti4+ ion it in a plane :
triangular arrangement. The compounds in which the number
of irregularity present in the
arrangement of atoms or ions are
called atomic imperfections. It is of
O2– two types -
Ti4+
9.2.1. Stoichiometric Defects :
Rutile (TiO2) Those compounds in which the
structure
number of positive and negative
ions are exactly in the ratio
9. Imperfections in Solids
indicated by their chemical
formula are called
Any deviation from the perfectly ordered stoichiometric compounds. eg.
arrangement constitutes a defect or NaCl (1 : 1)
imperfection. These defects sometimes These solids show following
called thermodynamic defects because types of defects :
the number of these defects depends on
(a) Schottky defect :
the temperature. Crystals may also
possess additional defect due to the This type of defect is created
presence of impurities. when the numberof positive and
Imperfection not only modify the negative ion are missing in the
properties of solids but also give rise to same ratio as in their formula
new properties. units, from their respective

`
positions leaving behind a pair negative ions present in the

of holes. Schottky defect is more compound differs from that
common in ionic compounds required by ideal formula of the
with high co-ordination number compound. Such compounds are
and where the size of positive called Non-stoichiometric
and negative ions are almost compounds. eg.
equal. VOx(Where x can vary between
M +
X –
M +
X – 0.6 to 1.3.)
In these compounds balance of
X– X– M+ positive and negative charges is
maintained by having extra
M+ X– M+ X– electrons or extra positive
charge on cations.
X– M+ M+
These defects are of following
types :
Schottky Defect
(a) Metal excess defects due to
The presence of large number of
anion vacancies :
schottky defects in crystal
results in significant decrease in A compound may have excess
its density. metal ion if a negative ion is
Eg. NaCl, KCl, CsCl, KBr etc. absent from its lattice site,
leaving a hole which is occupied
(b) Frenkel Defect : by electron to maintain
This type of defect is created electrical neutrality.
when an ion leaves its correct The holes occupied by electrons
lattice site and occupies an are called F-centres and are
interstitial site. responsible for the colour of the
M+ X– M+ X– compound.
X– M+ X– M+
M+ X– M+ X–
X– M+ X– X– M+ e– M+
+
M F-Centre
X– M+ X– M+ + – + –
M X M X
Frenkel Defect X– M+ X– M+
Frenkel defects are common in Metal excess defects
ionic compounds which have due to anion vacancies
low co-ordination number and
in which there is large difference eg.
in size between positive and
• The excess sodium in NaCl
negative ions.
makes the crystal appears
eg. ZnS, AgCl, AgBr, AgI etc. yellow.
9.2.2 Non Stoichiometric Defect : • Excess potassium in KCl makes
There are many compound in it voilet.
which the ratio of positive and
`
• Excess lithium in LiCl makes it M+ X– M+ X– M+

Pink.
Greater the number of F- X– X– M+ X–
centres greater is the intensity F-Centre
of colour. This type of defects M+ X– X– M+
are found in crystal which are
likely to possess schottky
X– M+ X– M+ X–
Defects.
(b) Metal excess defects due to
interstitial cations : Metal deficiency due to cations vacancies
Metal excess defects due to anion vacancies
It may occur if an extra positive
ion is present in an interstitial
site. Electrically neutrality is 10. Magnetic Properties
maintained by the presence of
an electron in the interstitial
site. On the basis of magnetic properties of the
This type of defects are solid substances are classified as follows.
exhibited by the crystals which
(a) Diamagnetic material :
are likely to exhibit “Frenkel
defects”. (i) Materials which are feebly
eg. Yellow colour of ZnS. repelled by magnetic fields.
M+ X– M+ X– (ii) They contains paired electrons

and unpaired electrons are
always absent
X– M+ X– M+
M+ (iii) Examples of diamagnetic
M +
X –
M +
X – material are NaCl, sulphur, TiO2
e– etc.
X– M+ X– M+ (b) Paramagnetic material :
Metal excess defects
due to interstitial cations
(i) Materials which are attracted by
the magnetic field.
(c) Metal deficiency due to cation
vacancies : (ii) They always contain unpaired
electrons.
The non-stoichiometric
compound may have metal (iii) In this material magnetic dipole
deficiency due to the absence of tend to orient themselves
a metal ion from its lattice site. parallel to the direction of the
The charge is balanced by an field and thus produce
adjacent ion having higher magnetization in the substance.
positive charge.
(iv) There substances however, lose
This type of defects are their magnetic character as soon
generally shown by compounds
as the field is removed.
of transition metals.
(v) Examples of this type of material
are O2, Cu2+, Fe3+ etc.

`
(c) Ferromagnetic material : phenomenon is called piezo

electric effect.
(i) These materials show
permanent magnetism even (ii) If an electric field is applied to a
when the magnetic field is crystal, a mechanical stress is
removed. developed in the crystal. Thus, a
piezo electric crystal acts as a
(ii) Ferromagnetism is due to
mechanical-electrical
spontaneous alignment of the
transducer.
magnetic dipole in the same
direction. (2) Pyro electricity : Those materials
(iii) Each ferromagnetic material which can produce small electric
losses its magnetic character current. This phenomenon is termed
above a critical temp. This temp as pyro electric effect. The electricity
is called the curie temperature. so produced is termed a pyro
electricity.
(iv) They contains a number of
unpaired electrons (3) Ferro electricity :- In some
piezoelectric crystals, the dipoles are
(v) Examples of these materials are
permanently orriented However, the
Fe, Ni, Co, Cr, etc.
direction can be changed by the
(d) Antiferromagnetic materials : application of electric field. This
(i) These are the materials, in phenomenon is called ferro
which alignment of the dipole is electricity.
compensatory so as to give zero Examples :- BaTiO3, KH2PO4
net dipole moment
(4) Anti ferro electricity :- If the dipoles in
(ii) MnO is the example of alternate polyhedral of the crystal are
antiferromagnetic material. oriented so as to cancel each dipole
(e) Ferrimagnetic materials : These are moment, then crystal is said to be anti
the material in which dipoles are ferro electric.
oriented in parallel and antiparallel Example :- PbZrO3.
direction in unequal numbers, so that
12. Experimental Methods of Determining
there is a net magnetic moment.
Crystal Structure
eg. Fe3O4, Ferrite etc.
11. Dielectric Properties Crystal structure has been obtained by

studying on the diffraction of X-rays by
solids.
(1) Piezo electricity : A crystal, having constituents particles
(i) When a polar crystal is arranged in planes at very small distances
subjected to a mechanical in three dimension array, acts as
stress, electricity is produced. diffraction grating for
The electricity so produced is X - rays which have wavelengths of the
called piezo electricity. This same order as the spacing in crystal.

`
Thus X - ray diffraction results from the 2d sin  = n

scattering of X - rays by a regular where, ‘n’ is an integer. For
arrangement of atoms or ions. monochromatic
Diffraction pattern
X - rays is fixed and there are some
specific angles 1, 2, 3, ...... etc,
Lead-box Crystal corresponding to n = 1, 2, 3, ........... etc, in
with slit Photographic plate the above equation. Thus, if the X - rays
are incident at one of these, they are
10,000–40,000
Spots from diffraction reflected ; otherwise they are absorbed.
volts
X-rays When they are reflected, the laws of
Spots from incident beam
reflection are obeyed i.e. (a) the angle of
Photographic plate
(Front view) incidence is equal to the angle of
reflection and (b) the incident ray, the
Bragg’s Law reflected ray and the normal to the
X - rays are electromagnetic waves of reflecting plane are co-planar.
short wavelength and may be diffracted By using a monochromatic X - ray beam
by suitable diffracting centres. and noting the angles of strong reflection,
In solid crystals, atoms are arranged in the interplaner spacing d and several
fairly regular pattern with interatomic informations about the structure of the
gaps of the order of 0.1 nm. Common salt solid can be obtained.
is an example of a crystalline solid. Almost
all the metals at ordinary temperature are
crystalline. These metals may act as a
natural three-dimensional gratings for the
diffraction of
X-rays.
 
The structure of a solid can be showed as

a series of parallel planes of atoms
separated by a distance d. Suppose, an X -
ray beam is incident on a solid, making an
angle  with the planes of the atoms.
These X - ray are diffracted by different
atoms and the interference is constructive
and we are obtained strong reflected X-
ray. The analysis shows that there will be
a strong reflected X - ray beam only if
SOLID STATE
Ex.1 Identify molecular solid, covalent solid, ionic solid : P4(s), S8 (s), SiC (s), Al2O3(s), He (s), Al2Cl6(s).
Sol. Molecular solid  P4(s), S8 (s), He (s), Al2Cl6(s)
Covalent solid  SiC
Ionic solid  Al2O3(s).
Ex.2 The lattice parameters of a given crystal are a = 5.62 Å, b = 7.41 Å and c = 9.48 Å.
The three coordinate axes are mutually perpendicular to each other. The crystal is :
(A) tetragonal (B) orthorhombic (C) monoclinic (D) trigonal.
Ans. (B)
Sol. abc &  =  =  = 90° the cr ystal system is orthorhombic.
Ex.3 Tetragonal cr ystal system has the following unit cell dimensions:
(A) a = b = c and  =  =  = 90° (B) a = b  c and  =  =  = 90°
(C) a  b  c and  =  =  = 90° (D) a = b  c and  =  = 90°,  = 120°
Ans. (B)
Ex.4 In a face centered cubic arrangement of A and B atoms whose A atoms are at th e
corner of the unit cell and B atoms at the face centres. One of the A atom Is missing
from one corner in unit cell. The simplest formula of the compound is
(A) A 7 B 3 (B) AB 3 (C) A 7 B 2 4 (D) A 2 B 3
Ans. (C)
Sol. A = 7  1/8 =7/8 ; B = 6  = 3
Formula = B 3 or A 7 B 2 4
Ex.5 A compound has cubical unit cell in which X atom are present at 6 corner, Y atom are at remaining
corner & only at those face centers which are not opposite to each other & Z atoms are present at
remaining face center & body center then find.
(i) Formula of compound (ii) Density if edge length = 2 Å.
Given : Atomic mass of X = 40 amu, Y = 60 amu, Z = 80 amu.
Sol. (i) X = 1/8 × 6 = 3/4
Y = 1/8× 2 + 1/2× 3 = 7/4
Z = 1/2 × 3 + 1 + 1 =5/2 = 10/4
X 3 Y 7 Z 10
For formula : 4 4 4 =X Y Z
3 7 10
(ii) 1 amu = 1.67 × 10–24 gram
1
1 amu = 6.02  10 23 gram.
3 7 10
 40   60   80
Mass 4 4 4
Density = Volume =
( 2  10 8 )3 amu/cc = 69.8 gram/cc.
Ex.6 How many 'nearest' and 'next nearest' neighbours respectively does potassium have
in b.c.c. lattice
(A) 8, 8 (B) 8, 6 (C) 6, 8 (D) 8, 2
Ans. (B)
Ex.7 If a metal has a bcc crystal structure, the coordination number is 8, because :
(A) each atom touches four atoms in the layer above it, four in the layer below it

and none in itsown layer.

(B) each atom touches four atoms in the layer above it, four in the layer below it
and one in its own layer.
(C) two atoms touch four atoms in the layer above them, four in the layer below
them, and none in their own layer.
(D) each atom touches eight atoms in the layer above it, eight in the layer below it
and none in its own layer.
Ans. (A)
Ex.8 Potassium crystallizes in body centered cubic lattice with a unit cell length a = 5.2 Å
(A) W hat is the distance between nearest neighbours
(B) W hat is the distance between next nearest neighbours
(C) How many nearest neighbours does each K atom have
(D) How many next nearest neighbours does each K have
(E) W hat is calculated density of crystalline K.
Sol. (A) 4.5 Å, (B) 5.2, (C) 8 , (D) 6 (E) 0.92 g/mL
3a 3  5.2
(A) 2r = 2 = 2 = 4.5 Å (B) distance = a = 5.2 Å
(C) 8 (D) 6
2  39
(E) d =
(5.2  10 8 )3  6.02  10 23 = 0.92 g/ml
Ex.9 A metal crystallizes in two cubic phases i.e., FCC and BCC whose unit cell lengths
are 3.5Å and 3.0 Å respectively. The ratio of their densities is :
(A) 3.12 (B) 2.04 (C) 1.26 (D) 0.72
Ans. (C) (3 )3
ZM d1 4
Sol. d = = 3
 = 1.26
3 d2 (3 .5 ) 2
a NA
Ex.10 In a ccp structure, the :

(A) first and third layers are repeated
(B) first and fourth layers are repeated
(C) second and fourth layers are repeated
(D) first, third and sixth layers are repeated.
Ans. (B)
Ex.11 Lithium borohydride crystallizes in an orthorhombic system with 4 molecules per unit
cell. The unit cell dimensions are a = 6.8 Å, b = 4.4 Å and c=7.2 Å. If the molar mass
is 21.76, then the density of cr ystals is :
(A) 0.6708 g cm – 2 (B) 1.6708 g cm – 3 (C) 2.6708 g cm – 3 (D) None of these.
Ans. (A)
ZM 4  21.76
Sol. d = = 8 8
= 0.6708 g cm 2 – .
3
a NA 6.8  10  4.4  10  7.2  10 8  6.023  10 23
Ex.12 An fcc lattice has lattice parameter a = 400 pm. Calculate the molar volume of the
lattice including all the empty space:
(A) 10.8 mL (B) 96 mL (C) 8.6 mL (D) 9.6 mL
Ans. (D)
Sol. Volume of 4 atoms = a 3 = (4  10 – 8 ) 3 cm 3
volume of N A atoms = ( 4  10 8 )  6.023  10 2 3 = 9.6 ml.

4
Ex.13(a) In a face centred cubic arrangement of metallic atoms, what is the relative ratio of
the sizes of tetrahedral and octahedral voids?
(A) 0.543 (B) 0.732 (C) 0.414 (D) 0.637

Ans. (A) 0.225R

rtetrahedra l
Sol. = = 0.543
roctahedral 0.414R
(b) The numbers of tetrahedral and octahedral holes in a ccp array of 100 atoms are
respectively
(A) 200 and 100 (B) 100 and 200 (C) 200 and 200 (D) 100 and 100
Ans. (A)
Ex.14 Copper has a face-centred cubic structure with a unit-cell edge length of 3.61Å. What is the size of
the largest atom which could fit into the interstices of the copper lattice without distorting it?
Figure
(Hint. : Calculate the radius of the smallest circle in the figure)
Ans. 0.53Å
Sol. roctahedral = 0.414 R
for FCC 4R = 2 a
2 a
R= 4
r= 0 . 414 2 a = 0.414 2  3.61= 0.53 Å
4 4
Ex.15 A mineral having formula AB 2 crystallize in the cubic close packed lattice, with the A
atoms occupying the lattice points. W hat is the co-ordination no. of A atoms? of the
B atoms? what fraction of tetrahedral sites is occupied by B atoms.
Ans. 8, 4, 100%.
It has fluorite (CaF 2 ) structure.
Ex.16 CsBr has b.c.c. structure with edge length 4.3 A. The shortest inter ionic distance in
between Cs + and Br – is:
(A) 3.72 (B) 1.86 (C) 7.44 (D) 4.3
Ans. (A)
3a 3  4 .3
Sol. r+ + r– = = = 3.72 Å .
2 2
Ex.17 Which of the following is incorrect
(A) The defect is known as schottky defect

(B) Density of compound in the defect decreases
(C) NaCl(s) is example which generally shows this defect
(D) Stoichiometry of compound will change slightly.
Ans. (D)
Ex.18 Ferrous oxide (FeO) is experimentally found to have the formula Fe0.93O.Find the %age of Fe ions
in +3 state.

Fe0.93O
Some Fe atom Some Fe atom

Sol. are in +2 state are in +3 state
Let there is xFe atom in +3 state

3x + 2(93 – x) = 200
x = 14 14 1400
% Fe3+ = × 100% = %
 15.54%93 93
Ex.19 What is a semiconductor? Name the two main types of semiconductors.

Ans. Substances whose conductance lies in between that of metals (conductors) and insulators are
called semiconductors. Two main types of semiconductors are n-type and p-type.
Ex.20 Explain the following with suitable examples:
(i) Ferromagnetism (ii) Paramagnetism (iii) 12-16 and 13-15 group compounds.
Ans. (i) Ferromagnetism : When substances show permanent magnetism even in the absence of the
magnetic field this phenomenon is called as Ferromagnetism and such substances as called as
Ferromagnetic substances e.g. Fe Ni Co and CrO2.
This type of magnetism arise due to the spontaneous alignment of magnetic moments due to
unpaired electron in the same direction.
(ii) Paramagnetism : When substances which are attracted by the external magnetic field are
called paramagnetic substances and the phenomenon is called as paramagnetism. Atoms ion or
molecules containing unpaired electron show this property, eg. O2 Cu2+, Fe3+ etc. these substances
lost their magnetism in the absence of magnetic field.
(iii) 13-15 Compouds : The solid state materials are porudced by combination of elements of
goups 13 and 15 the compounds thus obtianed are called 13-15 compouds e.g. InSb, AlP GaAs.
.
12-16 Compounds : The solid state compounds are obtianed by combination of elements fof
groups 12 and 16 the compounds are called 12-16 compouds e.g. ZnS, CdS, CdSe and HgTe.
1. Calculate the number of formula units in each of the following types of unit cells :
(a) MgO in a rock salt type unit cell
(b) ZnS in zinc blende structure
(c) platinum in a face-centred cubic unit cell.
Sol. (a) 4 (the same as in NaCl)
(b) 4
(c) 4 (1 at the corner, 3 at the face-centres)
2. A mineral having the formula AB2 crystallises in the cubic close-packed lattice, with the A
atoms occupying the lattice points. What is the coordination number of the A atoms and B
atoms ? What percentage fraction of the tetrahedral sites is occupied by B atoms ?
Sol. C.N. of A atom = 8
C.N. of B atom = 4
tetrahedral sites occupied by atoms B = 100% (all tetrahedral voids are occupied).
3. (a) What is the C.N. of Cr atom in bcc structure ?
(b) Cobalt metal crystallises in a hexagonal closest packed structure. What is the C.N. of
cobalt atom ?
(c) Describe the crystal structure of Pt, which crystallises with four equivalent atoms in a cubic
unit cell.
Sol. (a) 8, (b) 12, (c) fcc or cubic close packed.

4. Titanium metal has a density of 4.54 g/cm3 and an edge length of 412.6 pm. In what cubic unit
cell does titanium crystallise? (Ti = 48)
zM
Sol. Density d =
a3N0
d = 4.54 g/cm3 , M = 48g mol–1 , Z = ? N0 = 6.023 × 1023 mol–1
If value of z is known, structure can be decided
z= dN0a 3 23
= 4.54  6.023  10  ( 412.6  10
–10 3
) =4
M 48
Thus, titanium has face-centred cubic structure.
5. MgO has a structure of NaCl and TiCl has the structure of CsCl. What are the coordination
numbers of ions in each (MgO and TiCl).
Sol. C.N. of Na+ in NaCl = 6
C.N. of Cl– in NaCl = 6
hence C.N. of Mg2+ is also = 6
and that of O– – or O2– = 6 in MgO
We know in CsCl
C.N. of Cs+ = 8
C.N. of Cl– = 8
Hence, Ti+ and Cl– , in TiCl, have also C.N. 8 each.
6. A solid AB has the NaCl structure, If radius of cation A+ is 120 pm, calculate the maximum
possible value of the radius of the anion B–.
Sol. We know for the NaCl structure, for maximum of radius of B–, the ratio r+ / r– should be
minimum for octahedral void i.e. 0.414.
radius of cation/radius of anion = 0.414
rA 
= 0.414
rB –
rB – rA  120
= = = 290 pm.
0.414 0.414
7. The C.N. of the barium ion Ba2+, in BaF2 is 8. What must be the C.N. of F– ion ?
Sol. C.N.of barium ion tells us that it is surrounded by eight fluoride ions (charge 8 × (–1) = – 8). In
order to balance out the eight negative charges, we need four barium ion (charge 4 × (+2) =
+8). Hence, the C.N. of F– ions must be 4.
8. The radius of calcium ion is 94 pm and of oxide ion is 146 pm. Predict the crystal structure of
calcium oxide.
94
Sol. The ratio = = 0.644
146
The prediction is an octahedral arrangement of the oxide ions around the calcium. Because
the ions have equal but opposite charges, there must also be an octahedral arrangement of
calcium ions around oxide ions. Thus CaO structure is similar to Rock Salt(NaCI) structure.
9. Sodium metal crystallises in body centred cubic lattice with cell edge = 4.29 Å. What is radius
of sodium atom?
Sol. In ‘BCC’ structure
body diagonal = 4 × rNa = 3 a
 4 × rNa = 3  4.29
rNa = 3
 4.29 = 1.86 Å
4
10. CsCI crystallises in a cubic that has a CI– at each corner and Cs+ at the centre of the unit
cell. If (rCs+) = 1.69 Å and rCI – = 1.81 Å, what is value of edge length a of the cube?
Sol. We assume that the closest Cs+ to CI– distance is the sum of the ionic radii of Cs and Cl.

= 1.69 + 1.81 = 3.50 Å a 3

This distance is one-half of the cubic diagonal =
2
a 3
 = 3.50 Å  a = 4.04 Å
2
11. Platinum (atomic radius = 1.38 Å) crystallises in a cubic closest packed structure. Calculate
the edge length of the face-centred cubic unit cell and the density of the platinum (Pt = 195).
Sol.
a
r= (for fcc), a = 2 r = 3.9 Å
2 2
Mz 4  195
density = = 
= 21.83 g/cm3 .
dN0 (3.9  10 )3  6.023  10 23
8
12. Calculate the edge length of the unit cell of sodium chloride given density of NaCI is 2.17 × 103
kg m–3 and molecular weight 58.5 × 10–3 kg mol–1.
Sol. NaCI is face-centred cubic lattice so that number of NaCI molecules in a unit cell (z) = 4.
zM
We know density d =
a3N0
where a = length of the unit cell
Mz 4  58.8  103
Volume = a3 = = = 1.79 × 10–28 m3
dN0 2.17  103  6.02  1023
a = 5.64 × 10–10 m
a = 5.64 Å = 564 pm.
13. The effective radius of an iron atom is 1.42 Å. It has a rock-salt structure. Calculate its density
(Fe = 56).
Sol. Due to rock-salt (fcc) structure, number of atoms in a unit cell (z) = 4.
zM
Thus, d (density) = a = 2 r = 2 × 1.42 × 10–8 cm
a3N0
4  56
d= = 5.743 g/cm3
6.02  1023  ( 2 2  1.42  10 8 )3
14. In a CPS (close packed structure) of mixed oxides, it is found that lattice has O2– (oxide ions),
and one-half of octahedral voids are occupied by trivalent cations (A3+) and one-eighth of
tetrahedral voids are occupied by divalent cations (B2+). Derive formula of the mixed oxide.
Sol. Number of octahedral voids per ion in lattice = 1
1 1
Hence, number of trivalent cations (A3+) = 1 × 
2 2
number of tetrahedral voids per ion in lattice = 2
1 1
Hence, number of divalent cations (B2+) = 2 × 
8 4
Thus, formula is A1/2 B1/4O or A2BO4.
15. An element crystallises as face-centred cubic lattice with density as 5.20 g/cm3 and edge
length of the side of unit cell as 300 pm. Calculate mass of the element which contains 3.01 ×
1024 atoms.
Sol. z = 4 in fcc lattice M = ?,d = 5.20 g/cm3
a = 300 pm = 3 × 10–8 cm
 a3 = 27 × 10–24 cm3
N0 = 6.02 × 1023
dN0 a3 5.20 g / cm3  6.02  1023 mol1  27  10 24 cm3

 M= = 4
= 21.13 g mol–1
z
Thus, 6.02 × 1023 atoms have = 21.13 g
21.13
CHAITANYA’S ACADEMY 6.02  1023 www.chaitanyasacademy.com
 3.01 × 1024 atoms have = × 3.01 ×1024 g = 105.65 g
16. Calcium crystallises in a face-centred cubic unit cell with a = 0.556 nm. Calculate the density
if it contained 0.1% Vaccancy defects. zM
Sol. Thus, density can be determined using d = 3
a N0
3.996  40
d(with Vaccance defect) = = 1.5448 g/cm3
(0.556  10 7 )3  6.02  1023

Type (I) : Very Short Answer Type Questions : [01 Mark Each]
1. Define the term ‘space lattice.’
2. What is the percentage of free space in bodycentred cubic crystal ?

3. What is the number of tetrahedral voids in a unit cell of a cubic close-packed structure ?
4. What is the percentage efficiency of packing in case of a simple cubic lattice?
5. Octahedral voids are larger than tetrahedral voids or not. Give reason.
6. Solid elements of group 13 or 15 impurities with group 14 elements are found to exhibit unusual electrical
properties. Why ?
7. What is doping ? Why is it done ?
8. Explain the term dislocation in relation to crystals.

9. What type of semiconductor is obtained when Si is doped with boron?
10. Given an example of antiferromagnetic solid.
Type (II) : Short Answer Type Questions : [02 Marks Each]

11. Classify the following solids on the basis of bonding considerations :
CO2, MgO, Al, H2, Si, Gd, Pb, AgCl.
12. (i) Name the type of crystal shown in .
(ii) What is the relationship between a, b and c ?

(iii) What is the relationship ,  and ?
Are they equal to 90º or not ?
(iv) Give one example of a crystalline Fig. solid having this type of crystal lattice.
13. Define the following terms in relation of crystalline solids :
(i) Unit cell (ii) Coordination number
Give one example in each case.
14. Explain how you can determine the atomic mass of an unknown metal if you know its mass density and the
dimensions of unit cell of its crystal.
15. Calculate the packing efficiency of a metal crystal for a simple cubic lattice.
16. The length of the unit cell edge of a body centred metal crystal is 352 pm. Calculate the radius of an atom of
a metal.
17. An element (atomic mass = 60) having facecentred cubic structure has a cell edge of 400 pm. What is its
density ? [NA = 6.023 × 1023 ]
18. Copper crystallizes in to an fcc lattice with , edge length of 3.61x10–8 c.m. Calculate the density of copper.
(Given : At. No. of Cu :63.5g/mol.,NA: 6.023 x 1023)
19. Explain the following terms with suitable examples : (i) Schottky defect (ii) Interstitial defect
20. In corundum, oxide ions are arranged in hcp arrangement and the Al3+ ions occupy two third of the octahedral
voids. What is the formula of corundum ?

Type (III) : Long Answer Type Questions: [03 Marks Each]
21. An element crystallized in the simple cubic structure. Its density is 8 g cm–3 and its 200 g contains 24 × 1023
atoms. Calculate the edge length.
22. An element crystallises in a structure having fcc unit cell with edge length of 200 pm. Calculate its density, if
200 g of this element contains 24 × 1023 atoms.
23. An alloy of Cu, Au and Ag is found to have Cu forming simple cubic strcture, Ag atom occupy edge centres and
Au is at body centre. What is the formula of alloy ? Explain.
24. (a) Diamond and solid rhombic sulphur both are covalent solids but the latter has very low melting point then
former. Explain why ?
(b) Out of SiO2(s), Si(s), NaCl(s) and Br2(l) which is best electrical conductor and why ?
(c) Sodium metal has bcc structure with edge length 4.29 Å. What is the radius of an atom ? What is length of
body diagonal of unit cell ?
25. Calcium metal crystallizes in face cented cubic lattice with length 556 pm. Calculate the density of metal if it
contains, (i) 0.5% Frenkel defects (ii) 0.2% Schottky defects.
26. Account for the following :
(i) Fe3O4 is ferrimagnetic at room temperature but becomes paramagnetic at 850 K.
(ii) Zinc oxide on heating becomes yellow.
(iii) Frenkel defect does not change the density of AgCl crystals.
27. Define the following deffects (i) Stoichiometric point defect (ii) Non-stoichiometric point defect
28. What is meant by (i) 12–16 compound and (ii) 13–15 compound ? Give example.
29. How do electrical resistivity of the following class of materials vary with temperature ?
Semiconductor,metallic conductor, insulator.
30. Explain the following terms with one suitable example of each :
(i) Ferromagnetism (ii) Paramagnetism
Type (IV) : Very Long Answer type Questions [2 + 3 = 5 Marks]
31. (a) In reference to crystal structure, explain the meaning of ‘coordination number’. What is the number of
atoms in a unit cell of (i) a face centred cubic structure ? (ii) a body centred cubic structure ?
(b) The density of lead is 11.35 g cm–3 and the metal crystallizes with fcc unit cell. Estimate the radius of lead
atom. (At. mass of lead = 207 g mol–1 and NA = 6.02 × 1023 mol–1).
32. (a) Chromium metal crystallises in a body centred cubic lattice. The length of the unit cell edge is found to be
287 pm. Calculate the atomic radius of chromium.
(b) Silver crystellies in fcc lattice. If the edge length of unit cell is 4.07 x 10–8 c.m. and density of crystel is 10.5
g/cm3., calaulate the atomic mass of silver. (NA = 6.02 x 1023 atom/mole)
33. (a) An element (atomic mass=60) having face-centred cubic unit cell has a density of 6.23 g cm–3. What is
edge length of unit cell ?
(b) A metal (atomic mass=50) has a body-centred cubic crystal lattice. The density of the metals is
5.91 g cm–3. Find out the volume of the unit cell. [NA = 6.023 × 1023 ]
34. (i) What type of close packing is shown in Fig. ?
(ii) What is coordination number of central sphere ?
(iii) What is free space in this packing ?
(iv) How many atoms are present in single unit cell having this type of packing ?
1
35. (a) In a mixed oxide of a compound, th of tetrahedral voids are occupied by cation ‘A’. half of octahedral
8
voids are occupied by cation ‘B’ whereas oxide ion froms cubic close packed structure.
What will be the formula of oxide ? Explain.
(b) Calculate the efficiency in body centrad cubic crystal.

36. (a) What are ‘point defects’ in crystals ?
(b) Copper has fcc structure. If its density is 8.92 g cm–3, calculate its radius if atomic weight of Cu is 63.5 g mol–1.
37. (a) How are the following properties of crystals affected by Schottky and Frenkel defects :
(i) Density (ii) Electrical conductivity
(b) With the help of suitable diagrams, on the basis of band theory, explain the difference between
(i) a conductor and an insulator.
(ii) a conductor and a semiconductor.

Section (A) : Basics of solid state
A-1. Classify each of the following solids.
(a) Tetra phosphorus decoxide (P4O10) (b) Graphite
(c) Brass (d) Ammonium phosphate [(NH4)3 PO4 ]
(e) SiC (f) Rb
(g) 2 (h) LiBr
(i) P4 (j) Si
(k) Plastic.
A-2. We are good at matching things let us try our hand on the following columns:
Solid Constituent particle Binding force
(a) Diamond (e) Ion (i) Metallic
(b) Sodium Chloride (f) Atom (j) Dipole dipole
(c) HCl (g) Kernel (k) Ionic
(d) Aluminium (h) Molecule (l) Covalent
A-3. Given below are two dimension lattices with nicely shaded regions.You just have to find the contributions(in
fractions) of particles marked to the shaded regions and the total number of particles in the regions.
(a) (b) (a) (b) (a) (b)
(iv) (a)
(a)
(b)
(i) (ii) (iii) (v)
A-4. What are the crystallographic parameter of hexagonal, monoclinic and triclinic unit cell respectively.
Section (B) : Simple cubic structure, BCC and CsCl structure

B-1. Following diagrams show identical cubes such that edge of cube2 lies exactly in the middle of one of the faces
of Cube1 and Cube 4 has a corner at the body center of the Cube3. Find the contributions(in fraction) of the
spheres shown to each of the cubes.
Atom
4
1
2 Atom
3
B-2. Iron has body centred cubic lattice structure. The edge length of the unit cell is found to be 286 pm. What is the
radius of an iron atom?

B-3. The inter metallic compound Li Ag crystallizes in a cubic lattice in which both lithium and silver atoms have
coordination no. of 8. To what crystal class does the unit cell belong?
B-4. At room temperature, Polonium cryatsllises in Cubic primitive cell. If edge length is 3.0 Å, calculate the theoretical
density of Po.(Atomic wt of Po = 207g)
B-5. Chromium metal crystallizes with a body centered cubic lattice. The length of the unit cell is found to be 287
pm. Calculate the atomic radius. What would be the density of chromium in g/cm3.
Section (C) : Closest packing

C-1. A student wants to arrange 4 identical spheres(of radius R) on a two dimensional floor as close as possible.Finally
he could arrange them.Identify the type and dimensions of the figure obtained by joining their centers.Could
Mr. Nura occupy the whole available space, if not, then what type of voids were generated.Calculate their
number and radius of small ball that can be fitted in them.
C-2. Illustrate an octahedral void in the close packing of spheres. Why is it so called ?
C-3. In the close packed structure of AB type solid have cation radius of 75 pm, what would be the maximum and
minimum sizes of the anions which formed voids in unit cell ?
C-4. In which type of 3D arrangement have Ist and IV layer’s of sphere are identical.
C-5. In a hypothetical solid C atoms form CCP lattice with A atoms occupying all Plane
the Tetrahedral Voids and B atoms occupying all the octahedral voids.A and
B atoms are of the appropriate size such that there is no distortion in the
CCP lattice.Now if a plane is cut(as shown) then type of voids and their
numbers whic are present at the cross section would be.
CCP unit cell
Section (D) : ccp structure/fcc structure
D-1. What is the number of atoms in a unit cell of face-centred cubic crystal?
D-2. Following figure shows an FCC unit cell with atoms of radius r marked 1(corner),
2(face center), 3(face center). A quadrilateral is also shown by joining the centers of
4 face centered atoms.
Find : (i) The distances between atoms 1&2, 2&3 and 1&3.
(ii) The shape and dimensions of the quadrilateral.
D-3. Aluminium metal (atomic weight = 27g) crystallises in the cubic system with edge length 4.0Å. The density of
metal is 27/16 amu/ Å 3 . Determine the unit cell type and calculate the radius of the Aluminium metal.
D-4. What is the number and closest distance between octahedral voids and tetrahedral voids in fcc unit cell ?
Section (E) : hcp structure

E-1. “Tom” cat arrange the glass balls, in a particular 3D array ; that two (I and II) continuous layer are not identical,
but all (I and III) alternative layers are identical, this type of arrangement is known as :
E-2. Metallic magensium has a hexagoanl close-packed structure and a density of 1.74 g/cm3. Assume magnesium
atoms to be spheres of radius r. 74.1% of the space is occupied by atoms. Calculate the volume of each atom
and the atomic radius r. (Mg = 24.31) e d
g Layer A
f c
E-3. Consider a corner atom of Ist layer of an HCP unit cell showing alternate AA a b
layers. Find
(i) Find identical atoms (III layer) with respect to the distances from the atom 1.
(ii) Arrange the distances in ascending order. Layer A
Atom 1
E-4. The number of tetrahedral and octahedral voids in hexagonal primitive unit cell are _______ and _______.

Section (F) : Radius ratio rule and Type of ionic structures
F-1. Suggest the probable structues of the unit cells of following each compound with the help of given data :
Cationic radius Anionic radius
(a) RbBr 1.48 Å 1.95 Å
(b) MeTe 0.65 Å 2.21 Å
(c) MgO 0.65 Å 1.40 Å
(d) BaO 1.35 Å 1.40 Å
F-2. In the sodium chloride structure, each Na+ ion is surrounded by six Cl ions nearest neighbours and ______
Na+ ions next nearest neighbours.
F-3. A unit cell of sodium chloride has four formula units. The edge length of the unit cell is 0.564 nm. What is the
density of sodium chloride ?
F-4. Why does ZnS not crystallize in the NaCl structure?

F-5. Try to answer the following:
(i) In Zinc Blende structure there is one Zn+2 ion per S2– ion.But the radius ratio lies in the range of Tetrahedral
void and there are two tetrahedral voids available per S2–.Can you give the idea about the arrangement of the
lattice.
(ii) What is the striking difference between the Fluorite and the Anti-fluorite structures.
F-6. KBr crystallizes in NaCl type of unit cell. K+ radius = 1.33Å , Br¯ radius = 1.95 Å
(a) How many K+ ions and how many Br¯ ions are in each unit cell?
(b) Assuming the additivity of ionic radii, what is a ?
(c) Calculate the density of a perfect KBr crystal.
(d) What minimum value of r+/r– is needed to prevent anion-anion contact in this structure.
F-7. Ionic compound in which anion (A) present at HCP unit cell lattice point and cation (B) occupy all tetrahedral
voids in unit cell. What is the formula of ionic compound ?
F-8. Try to answer the following:
What is the striking difference between the Fluorite and the Anti-fluorite structures.
F-9. Silicon crystallizes in a unit cell to that of diamond. Find the ‘Z’ (effective number of atom) for Si.
[Hint : Diamond has a face-centred cubic unit cell containing a tetrahedron of atoms.]
Section (G) : Crystal defects and Properties of solids
G-1. What do you understand by imperfections in ionic crystals ? name the types of imperfections which generally
occur in ionic crystals.
G-2. Calculate the concentration of cation vacancies if NaCl is doped with 10–3 mole % of SrCl2.
G-3. How would you explain that (i) non-stoichiometric NaCl is yellow ; (ii) non-stoichiometric ZnO is yellow ?
G-4. Account the following :

Silicon is an insulator but silicon doped with phosphorus acts as a semiconductor.
G-5. How does the conductivity of a semiconductor change if its temperature is raised?

Section (A) : Basics of solid state
A-1. Which of the following is/are pseudo solids ?
. KCI . Barium chloride dihydrate
. Rubber V. Solid cake left after distillation of coal tar
(A) , (B) ,  (C) , V (D) only 

A-2. The smallest repeating pattern which when repeated in three dimensions results in the crystal of the substance
is called
(A) Space lattice (B) Crystal lattice (C) Unit cell (D) coordination number
A-3. The crystal system for which a  b  c and  =  =  = 900 is said to be :

(A) triclinic (B) tetragonal (C) cubic (D) orthorhombic
A-4. Which of the following are the correct axial distance and axial angles for rhombohedral system?
(A) a = b = c,  =  =  900 (B) a = b  c,  =  =  = 900
(C) ab c,  =  =  = 900 (D) ab c,   900
A-5. Choose the correct statements

(A) equivalent points in unit cells of a periodic lattice lie on a Bravais lattice
(B) equivalent points in unit cells of a periodic lattice do not lie on a Bravais lattice
(C) There are four Bravais lattices in two dimensions
(D) There are five Bravais lattices in three dimensions
Section (B) : Simple cubic structure, BCC and CsCl structure

B-1. Body centred cubic lattice has co–ordination number of :
(A) 8 (B) 12 (C) 6 (D) 4
B-2. A metal crystallizes in a body centered cubic lattice (bcc) with the edge of the unit cell 5.2Å. The distance
between the two nearest neighbour is
(A) 10.4 Å (B) 4.5 Å (C) 5.2Å (D) 9.0Å
B-3. Lithium crystallizes in a body centered cubic lattice. How many next–nearest neighbors does each Li have?
(A) 6 (B) 8 (C) 12 (D) 4
B-4. Consider a Body Centered Cubic(bcc) arrangement, let de, dfd, dbd be the distances between successive atoms
located along the edge, the face-diagonal, the body diagonal respectively in a unit cell.Their order is given by:
(A) de < dfd < dbd (B) dfd > dbd > de (C) dfd > de > dbd (D) dbd > de > dfd,
Section (C) : Closest packing.
C-1. You are given 4 identical balls. What is the maximum number of square voids and triangular voids (in separate
arrangements) that can be created ?
(A) 1, 2 (B) 2, 1 (C) 3, 1 (D) 1, 3
C-2. The empty space between the shaded balls and hollow balls as shown in the diagram is called
(A) hexagonal void (B) octahedral void (C) tetrahedral void (D) double triangular void
C-3. Which one of the following schemes of ordering closed packed sheets of equal sized spheres does not generate
close packed lattice.
(A) ABCABC (B) ABACABAC (C) ABBAABBA (D) ABCBCABCBC
Section (D) : ccp structure/fcc structure

D-1. In a ccp structure, the (according to cubic 3D arrangement) :
(A) first and third layers are repeated (B) first and fourth layers are repeated
(C) second and fourth layers are repeated (D) first, third and sixth layers are repeated.

D-2. Which of the following shaded plane in fcc lattice contains arrangement of atoms as shown by circles :
(A) (B) (C) (D)
D-3. Following three planes( P1, P2, P3) in an FCC unit cell are shown:
Consider the following statements and choose the correct
option that follow:
(i) P1 contains no voids of three dimensions.
(ii) P2 contains only Octahedral voids.
(iii) P3 contains both Octahedral and Tetrahedral voids.
(A) All are true (B) Only (i) & (ii) are true
(C) (i) & (iii) are true (D) Only (iii) is true.
D-4. Copper crystallises in a structure of face centerd cubic unit cell. The atomic radius of copper is 1.28 Å. What
is axial length on an edge of copper.
(A) 2.16 Å (B) 3.62 Å (C) 3.94 Å (D) 4.15 Å
D-5. The maximum percentage of available volume that can be filled in a face centred cubic system by atoms is-
(A) 74% (B) 68% (C) 34% (D) 26%
D-6. In a face centred cubic lattice the number of nearest neighbours for a given lattice point are :
(A) 6 (B) 8 (C) 12 (D) 14
D-7. In an FCC unit cell a cube is formed by joining the centers of all the tetrahedral voids to
generate a new cube.Then the new cube would contain voids as :
(A) 1 full Tetrahedral void, 1 full Octahedral void
(B) 1 full Tetrahedral void only
(C) 8 full Tetrahedral voids and 1 full Octahedral void
(D) 1 full Octahedral void only
Section (E) : hcp structure

E-1. The crystal system of a compound with unit cell dimensions, a = 0.387 and b = 0.387 and c = 0.504nm and
 =  = 90º and  = 120º is :
(A) Cubic (B) Hexagonal (C) Orthorhombic (D) Rhombohedral
E-2. The shortest distance between Ist and Vth layer of HCP arrangement is :
2 3 2 3
(A) 8 r (B) 4 r (C) 16 r (D) 8 r
3 2 3 2
E-3. Volume of HCP unit cell is :

(A) 24 2 r3 (B) 8 2 r3 (C) 16 2 r3 (D) 24 3 r3
E-4. Fraction of empty space in ABAB type arrangement in 3D :

(A) 0.74 (B) 0.26 (C) 0.68 (D) 0.32
E-5. If the anions (A) form hexagonal closest packing and cations (C) occupy only 2/3 octahedral voids in it, then
the general formula of the compound is
(A) CA (B) CA2 (C) C2A3 (D) C3A2

Section (F) : Radius ratio rule and Type of ionic structures
F-1. The radius of Ag+ ion is 126 pm and that of – ion is 216 pm. The co-ordination number of Ag+ ion is.
(A) 2 (B) 4 (C) 6 (D) 8
F-2. The tetrahedral voids formed by ccp arrangement of Cl¯ ions in rock salt structure are
(A) Occupied by Na+ ions (B) Occupied by Cl¯ ions
(C) Occupied by either Na+ or CI¯ ions (D) Vacant
F-3. Antifluorite structure is derived from fluorite structure by :

(A) heating fluorite crystal lattice
(B) subjecting fluorite structure to high pressure
(C) Inter changing the positions of positive and negative ions in the lattice
(D) none of these
F-4. In zinc blende structure the coordination number of Zn2+ ion is

(A) 2 (B) 4 (C) 6 (D) 8
F-5. Strontium chloride has a fluorite structure, which of the following statement is true for the structure of strontium
chloride ?
(A) the strontium ions are in a body–centered cubic arrangement
(B) the strontium ions are in a face–centered cubic arrangement
(C) each chloride ion is at the center of a cube of 8 strontium ions
(D) each strontium ion is at the center of a tetrahedron of 4 chloride ions
F-6. The spinal structure (AB2O4) consists of an fcc array of O2– ions in which the :
(A) A cation occupies one-eighth of the tetrahedral holes and B cation occupies one-half of octahedral holes
(B) A cation occupies one-fourth of the tetrahedral holes and the B cations the octahedral holes
(C) A cation occupies one-eighth of the octahedral hole and the B cation the tetrahedral holes
(D) A cation occupies one-fourth of the octahedral holes and the B cations the tetrahedral holes
F-7. In the crystal lattice of diamond, carbon atoms adopt :

(A) fcc arrangement along with occupancy of 50% tetrahedral holes
(B) fcc arrangement along with occupancy of 25% tetrahedral holes
(C) fcc arrangement along with occupancy of 25% octahedral hole
(D) bcc arrangement
F-8. Cesium chloride on heating to 760 K changes into

(A) CsCI(g) (B) NaCI structure
(C) antifluorite structure (D) ZnS structure
Section (G) : Crystal defects and Properties of solids

G-1. In a solid lattice the cation has left a lattice site and is located at an interstitial position, the lattice defect is :
(A) Interstitial defect (B) Valency defect (C) Frenkel defect (D) Schottky defect
G-2. Which of the following statements are correct in context of point defects in a crystal ?
(A) AgCl has anion Frenkel defect and CaF2 has Schottky defects
(B) AgCl has cation Frenkel defects and CaF2 has anion Frenkel defects
(C) AgCl as well as CaF2 have anion Frenkel defects
(D) AgCl as well as CaF2 has Schottky defects
G-3. F–centers are
(A) the electrons trapped in anionic vacancies
(B) the electrons trapped in cation vacancies
(C) non-equivalent sites of stoichiometric compound
(D) all of the above
G-4. Which of the following is true about the charge acquired by p-type semiconductors?
(A) positive (B) neutral
(C) negative (D) depends on concentration of p impurity

PART - III : ASSERTION / REASONING
DIRECTIONS :
1. Statement-1 : In HCP structure the contribution of hexagonal face corner per atom is 1/12.
Statement-2 : It is shared by 6 different unit cell.
2. Statement-1 : An ionic structure is composed of oppositely charged ions.
Statement-2 : If the larger ions are close packed, then he smaller ions may occupy either the octahedral holes
or the tetrahedral holes depending on their size.
3. Statement-1 : ZnO becomes yellow when it is heated.
Statement-2 : NaCl becomes yellow when heated in the presence of Na vapours due to anion vacancy.

1. Classify each of the following solids as ionic, metallic, molecular network (covalent) or amorphous.
(a) S8 (b) Diamond (c) Bronze (d) ZnSO4
(e) SiO2 (f) Fe (g) 2 (h) NaCl
(i) Glass (j) Si (k) Rubber.
2. The 2D unit cell of an element is shown. The two layers are placed one over the other and touching each other.
Calculate :
(a) effective number of atoms in the unit cell (b) packing efficiency
3. Four identical spheres of radius r are arranged such that centers of three of them form an equilateral triangle
and the fourth one rests symmetrically above the triangle touching all of them. Find :
(i) The area of the triangle thus formed.
(ii) Perpendicular distance between the triangle and the center of the fourth atom.
(iii) Are all the balls identical in the arrangement ?
4. How many number of atom effectively present in a cubic unit formed by arrangement of eight B.C.C unit cell.
5. Consider a cube containing n unit cells of a cubic system.
D B
A plane ABCD obtained by joining the mid points of the edges on one of its identical faces had atoms arranged
as shown. Let p be the packing fraction.what is the value of n and p ?

6. An element has body centered cubic structure with a cell edge of 3.0Å. The density of the metal is
2 amu/Å3. How many atoms are present in 243 × 1024 amu of the element.
7. Potassium crystallises in a body-centered cubic lattice (Fig.),

with a unit cell length a = 5.20Å.
(a) What is the distance between nearest neighbors?
(b) What is the distance between next-nearest neighbors?
(c) How many nearest neighbors does each K atom have?
(d) How many next-nearest neighbors does each K atom have?
(e) What is the calculated density of crystalline K?
8. The interstitial hole is called tetrahedral because :
9. (i) What is the number of octahedral voids in case of H.C.P and F.C.C ?
(ii) True or False
Number of octahedralvoids is a whole number multiple of the number of tetrahedral void where n is any
integer.
10. Metallic gold crystallizes in the face-centered cubic lattice. The length of the cubic unit cell (a = 4.070 Å.)
(a) What is the closest distance between gold atoms?
(b) How many "nearest neighbours” does each gold atom have at the distance calculated in (a)?
(c) What is the density of gold?
(d) Prove that the packing factor for gold, the fraction of the total volume occupied by the atoms themselves,
is 0.74.
11. An element of atomic mass 98.5 g mol–1 occur in fcc structure. If its unit cell edge length is 500 pm and its
density is 5.22 g cm–3. What is the value of Avogadro constant?
12. In a face centered lattice of X and Y, X atoms are present at the corners while Y atoms are at face centers,
(a) What is the formula of the compound ?
(b) What would be the formula of the compound if
(i) one of the X atoms is missing from a corner in each unit cell
(ii) two atoms of X are missing from the corners,
(iii) one of the X atoms from a corner is replaced by Z atoms (also monovalent) ?
13. Distance between 2 layers in HCP unit cell or ABAB type arrangement in 3D lattice (distance between A & B
layers).
14. Titanium has hexagonal close packing with cell edge length a = b = 295.5 pm, height = c = 472.9 pm. Calculate
its density (At. mass of Ti = 47.8).
15. (a) Ferric oxide crystallizes in a hexagonal close - packed array of oxide (O2–) ions with two out of every three
octahedral holes occupied by iron ions. What is the formula of ferric oxide?
(b) In cadmium iodide every alternate octahedral hole in an HCP array of iodide – ions is occupied by a
cadmium ion. What is the formula of cadmium iodine.

16. Calculate the value of Avogadro's number from the internuclear distance of adjacent ions in NaCI, 0.282 nm,
and the density of solid NaCI, 2.17 × 103 kg/m3.
17. In a crystalline solid having molecular formula A2B anion (B) are arranged in cubic close packed lattice and
cations (A) are equally distributed between octahedral and tetrahedral voids.
(i) What percentage of octahedral voids is occupied?
(ii) What percentage of tetrahedral voids is occupied?
18. FeO crystalizes into a cubic structure and has edge length 5.0 Å . The density is 4.0 g cm 3, calculate
the number of Fe2+ & O 2 ions present in each unit cell .
19. Let MgTiO3 exists in pervoskite structure. In this lattice, all the atoms of one of the face diagonals are removed.
Calculate the density of unit cell if the radius of Mg2+ is 0.7 Å and the corner ions are touching each other.
[given atomic mass of Mg = 24, Ti = 48]
20. What is meant by ‘Point Defects’ in crystals?
21. It is believed that non stoichiometric compound Fe0.93 O forms by dopping of Fe3+ ions in FeO crystal by
replacement of Fe2+. Calculate total no. of cationic vacancies in 0.1 mole of Fe0.93 O and also calculate the total
no. of cationic vacancies if now all the Fe2+ ions are replaced by Si4+ ions in 0.1 mole of Fe0.93O.
22. What is the difference between ferro magnetic and ferrimagnetic substances?
23. Why does pure silicon, which is an insulator, behave as a semiconductor on heating?

Single choice type
1. Which of the following solids are not correctly matched with the bonds found between the constituent particles:
(A) Solid CO2 : Vanderwaal's (B) Graphite : Covalent and Vanderwaal
(C) Grey Cast Iron : Ionic (D) Metal alloys : Ions-delocalised electrons
2. You are given 6 identical balls.What is the maximum number of square voids and triangular voids(in separate
arrangements) that can be created?
(A) 2 , 4 (B) 4 , 2 (C) 4 , 3 (D) 3 , 4
3. Square packed sheets are arranged on the top of other such that a sphere in the next layer rests on the center
of a square in the previous layer. Identify the type of arrangement and find the the coordination number.
(A) Simple Cubic, 6 (B) Face Centered Cubic, 8
(C) Face Centered Cubic, 12 (D) Body Centered Cubic, 8
4. In a CCP lattice of X and Y, X atoms are present at the corners while Y atoms are at face centers.Then the
formula of the compound would be if one of the X atoms from a corner is replaced by Z atoms (also monovalent)?
(A) X7Y24Z2 (B) X7Y24Z (C) X24Y7Z (D) XY24Z
5. Consider a cube 1 of Body Centered Cubic unit cell of edge length a now atom at the body center can be
viewed to be lying on the corner of another cube 2.Find the volume common to cube 1 and cube 2.
a3 a3 a3 a
3
(A) (B) (C) (D)
27 64 2 2 8
6. An element (atomic mass = 100 g/mole) having bcc structure has unit cell edge 400 pm. The density of the
element is (no. of atoms in bcc(Z) = 2).
(A) 2.144 g/cm3 (B) 5.2 g/cm3 (C) 7.289 g/cm3 (D) 10.376 g/cm3
7. In a simple cubic lattice of anions, the side length of the unit cell is 2.88 Å. The diameter of the void in the body
centre is
(A) 1.934 Å (B) 0.461 Å (C) 2.108 Å (D) 4.988 Å
8. In a compound, oxide ions are arranged in cubic close packing arrangement. Cations A occupy one-sixth of
the tetrahedral voids and cations B occupy one-third of the octahedral voids. The formula of the compound is
(A) A2BO3 (B) AB2O3 (C) A2B2O2 (D) ABO3

9. Three lines are drawn from a single corner of an FCC unit cell to meet the other corner such that they are
found to pass through exactly only 1 octahedral void, no voids of any type and exactly 2 tetrahedral voids with
1 octahedral void. Identify the line in the same order.
(A) Edge, Face diagonal, Body diagonal (B) Face diagonal, Edge, Body diagonal
(C) Body diagonal, Face diagonal, Edge (D) Edge, Body diagonal, Face diagonal
10. In a multi layered close-packed structure

(A) there are twice as many tetrahedral holes as many close-packed atoms
(B) there are as many tetrahedral holes as many closed packed atoms
(C) there are twice as many octahedral holes as many close-packed atoms
(D) there are as many tetrahedral holes as many octahedral holes
11. Platinum crystallizes in a face-centered cubic crystal with a unit cell length 'a'. The distance between nearest
neighbors is :
3 2 2
(A) a (B) a (C) a (D) a
2 2 4
12. Platinum crystallises in a face centered cube crystal with a unit cell length of 3.9231 Å. The density and atomic
radius of platinum are respectively. [Atomic mass of Pt = 195]
(A) 45.25 g. cm–3, 2.516 Å (B) 21.86 g. cm–3, 1.387 Å
(C) 29.46 g. cm , 1.48 Å
–3
(D) None of these
13. Metallic gold crystallises in face centered cubic. Lattice with edge-length 4.070 Å. Closest distance between
gold atoms is :
(A) 2.035 Å (B) 8.140 Å (C) 2.878 Å (D) 1.357 Å
14. Given an alloy of Cu, Ag and Au in which Cu atoms constitute the CCP arrangement.If the hypothetical formula
of the alloy is Cu4Ag3Au. What are the probable locations of Ag and Au atoms.
(A) Ag - all Tetrahedral voids; Au - all Octahedral voids
(B) Ag - 3/8th Tetrahedral voids; Au - 1/4th Octahedral voids
(C) Ag - 1/2 Octahedral voids; Au - 1/2 Tetrahedral voids
(D) Ag - all Octahedral voids; Au - all tetrahedral voids
15. In an arrangement of type ABABA... identical atoms of I layer A and III layer A are joined by a line passing
through their centers. Suggest the correct statement.
(A) No void is found on the line
(B) Only Tetrahedral voids are found on the line
(C) Only octahedral voids are found on the line
(D) Equal number of tetrahedral and octahedral voids are found on the line
16. The co-ordinatation number of a metal crystallizing in a hexagonal closed packed structure is :
(A) 12 (B) 4 (C) 8 (D) 0
17. The number of nearest neighbours to each sphere in hexagonal close packing pattern in its own layer will be:
(A) 4 (B) 6 (C) 12 (D) 8
18. Which of the following statements is correct in the rock-salt structure of ionic compounds?
(A) co-ordination number of cation is four whereas that of anion is six.
(B) co-ordination number of cation is six whereas that of anion is four.
(C) co-ordination number of each cation and anion is four.
(D) co-ordination number of each cation and anion is six.
19. The coordination number of cation and anion in Fluorite CaF2 and Rutile TiO2 are respectively :
(A) 8 : 4 and 6 : 3 (B) 6 : 3 and 4 : 4 (C) 6 : 6 and 8 : 8 (D) 4 : 2 and 2 : 4
20. The compound AB crystallizes in a cubic lattice in which both A and B atoms have
coordination numbers of 8. To what crystal class does the unit cell belong ?
(A) CsCI structure (B) NaCI structure (C) ZnS structure (D) AI2O3 structure

21. The distance between adjacent, oppositely charged ions in rubidium chloride is 3.285 Å; in potassium chloride
is 3.139Å; in sodium bromide is 2.981 Å and in potassium bromide is 3.293 Å. The distance between adjacent
oppositely charged ions in rubidium bromide is
(A) 3.147 Å (B) 3.385 Å (C) 3.393 Å (D) 3.439 Å
22. Zinc sulphide exists in two different forms-zinc blende and wurtzite. Both occur as 4:4 co-ordination compounds.
Choose the correct option from among the following :
(A) zinc blende has a bcc structure and wurtzite an fcc structure
(B) zinc blende has an fcc structure and wurtzite an hcp structure
(C) zinc blende as well as wurtzite have a hcp structure
(D) zinc blende as well as wurtzite have a cpp structure
23. A mineral having the formula AB2, crystallises in the cubic close - packed lattice, with the A atoms occupying
the lattice points. The co-ordination number of the A atoms, that of B atoms and the fraction of the tetrahedral
sites occupied by B atoms are
(A) 8, 4, 100% (B) 2, 6, 75% (C) 3, 1, 25% (D) 6, 6, 50%
24. BaO has a rock-salt type structure. When subjected to high pressure, the ratio of the coordination number of
Ba+2 ion to O–2 changes to
(A) 4 : 8 (B) 8 : 4 (C) 8 : 8 (D) 4 : 4
25. A crystal of NaCl, which has sodium ions and chloride ions missing from the lattice point, is said to exhibit
(A) Surface defect (B) Lattice defect (C) Frenkel defect (D) Schottky defect
26. In the Schoottky defect :
(A) cations are missing from the lattice sites and occupy the interstitial sites
(B) equal number of cations and anions are missing
(C) anion are missing and electrons are present in their place
(D) equal number of extra cations and electrons are present in the interstitial sites
27. NaCl shows Schottky defects and AgCl Frenkel defects. Their electrical conductivity is due to :
(A) motion of ions and not the motion of electrons
(B) motion of electrons and not the motion of ions
(C) lower co-ordination number of NaCl
(D) higher co-ordination number of AgCl
28. Zinc Oxide, white in colour at room temperature, acquires yellow colour on heating due to:
(A) Zn being a transition element
(B) paramagnetic nature of the compound
(C) trapping of electrons at the site vacated by Oxide ions
(D) Both (A) & (B)

29. Which of the following statements is/are false.
(A) It is the isotropic nature of amorphous solids that all the bonds are of equal strength.
(B) Entropy of a crystalline solid is higher than that of an amorphous solid.
(C) Amorphous solids have definite volume but not definite shape.
(D) Amorphous solids can become crystalline on slow heating(annealing).
30. Which statements is/are true about HCP and CCP lattice
(A) Number of tetrahedral voids are twice of octahedral holes
(B) 12 tetrahedral and 6 octahedral voids are present in one HCP unit cell
(C) C.N. of HCP unit cell is 12
(D) If atom of tetrahedral voids displace into octahedral voids then it is Schootky defect.
31. The co-ordination number of FCC structure for metals is 12, since
(A) each atom touches 4 others in same layer, 3 in layer above and 3 in layer below.
(B) each atom touches 4 others in same layer, 4 in layer above and 4 in layer below.
(C) each atom touches 6 others in same layer, 3 in layer above and 3 in layer below.
(D) each atom touches 3 others in same layer, 6 in layer above and 6 in layer below.

32. Which of the following is/are correct ?
(A) Schottky defect lowers the density
(B) Frenkel defect increases the dielectric constant of the crystals
(C) Stoichiometric defects make the crystals electrical conductors
(D) In the Schoottky defect, equal number of extra cations and electrons are present in the interstitial sites
33. A perfect crystal of silicon (Fig). is doped with some elements as given in the options. Which of these options
show n-type semiconductors?
(A) (B) (C) `(D)

1. Column I (Arrangement of the atoms/ions) Column II (Planes in fcc lattice)
(A) (p)
(B) (q)
(C) (r)
(D) (s)

2. Column I Column II
(A) ZnS crystal (p) fcc
(B) CaF2 crystal (q) hcp
3
(C) NaCl crystal (r) Distance between closest particles is a.
4
(D) Diamond crystal (s) Only one type of voids are occupied
Read the following comprehension carefully and answer the questions.
Comprehension # 1
Consider the figure given for solid XY. Answer the following questions
1. The site Y represents

(A) tetrahedral void (B) Octahedral void (C) triangular void (D) cubical void.
2. The number of XY units per unit cell is
(A) 4 (B) 3 (C) 3 (D) 8
3. Co-ordination number of Y is
(A) 3 (B) 4 (C) 6 (D) 8
Comprehension # 2
When an atom or an ion is missing from its normal lattice site, a lattice vacancy (Schottky defect) is created.
In stoichiometric ionic crystals, a vacancy of one ion has to be accompanied by the vacancy of the oppositely
charged ion in order to maintain electrical neutrality.
In a Frenkel defect an ion leaves its position in the lattice and occupies an interstitial void. This is the Frenkel
defect commonly found along with the Schottky defects and interstitials. In pure alkali halides, Frenkel defects
are not found since the ions cannot get into the interstitial sites. Frenkel defects are found in silver halides
because of the small size of the Ag+ ion. Unlike Schottky defects, Frenkel defects do not change the density of
the solids. In certain ionic solids (e.g. AgBr) both Schottky and Frenkel defects occur.
The defects discussed above do not disturb the stoichiometry of the crystalline material. There is large variety
of non-stoichiomertic inorganic solids which contain an excess or deficiency of one of the elements. Such
solids showing deviations from the ideal stoichiometric composition form an important group of solids. For
example in the vanadium oxide, VOx, x can be anywhere between 0.6 and 1.3. There are solids which are
difficult to prepare in the stoichiometric composition. Thus, the ideal composition in compounds such as FeO
is difficult to obtain (normally we get a composition of Fe0.95 O but it may range from Fe0.93 O to Fe0.96O). Non-
stoichiometric behaviour is most commonly found for transition metal compounds though is also known for
some lanthanoids and actinoids.
Zinc oxide loses oxygen reversibly at high temperatures and turns yellow in colour. The excess metal is
accommodated interstitially, giving rise to electrons trapped in the neighbourhood. the enhanced electrical
conductivity of the non-stoichiometric ZnO arises from these electrons.
Anion vacancies in alkali halides are produced by heating the alkali halide crystals in an atmosphere of the
alkali metal vapour. When the metal atoms deposit on the surface they diffuse into the crystal and after
ionisation the alkali metal ion occupies cationic vacancy whereas electron occupies anionic vacancy. Electrons
trapped in anion vacancies are referred to as F-centers ( from Farbe the German word for colour) that gives
rise to interesting colour in alkali halides. Thus, the excess of potassium in KCl makes the crystal appear violet
and the excess of lithium in LiCl makes it pink.

4. When LiCI is heated into the vapour of lithium, the crystal acquires pink colour. This is due to
(A) Schottkty defects (B) Frenkel defects
(C) Metal excess defect leading to F-centers (D) Electronic defect
5. Strongly heated ZnO crystal can conduct electricity. This is due to

(A) Movement of extra Zn2+ ions present in the interstitial sites
(B) Movement of electrons in the anion vacancies
(C) Movement of both Zn2+ ions and electrons
(D) None of these
6. AgCl is crystallized from molten AgCl containing a little CdCl2. The solid obtained will have
(A) cationic vacancies equal to number of Cd2+ ions incorporated
(B) cationic vacancies equal to double the number of Cd2+ ions
(C) anionic vacancies
(D) neither cationic nor anionic vacancies
7. Which of the following is most appropriate crystal to show Frenkel defect.

(A) CsCl (B) NaCl (C) AgBr (D) CaCl2
PART - I : IIT-JEE PROBLEMS (LAST 10 YEARS)

1. In the figures given below show the location of atoms in three crystallographic planes in a fcc lattice. Draw the
unit cell of the corresponding structure and identify these planes in your diagram. [JEE-2000, 3/100]
2. In a solid ' AB ' having the NaCl structure , ' A ' atoms occupy the corners of the cubic unit cell. If all the face
centered atoms along one of the axes are removed, then the resultant stoichiometry of the solid is :
[JEE-2001, 1/35]
(A) AB2 (B) A2B (C) A4B3 (D) A3B4
3. A substance Ax By crystallizes in a face centered cubic lattice in which atoms ‘A’ occupy each corner of the
cube and atoms ‘B’ occupy the centers of each face of the cube . Identify the correct composition of the
substance Ax By . [JEE-2002, 3/90]
(A) AB3 (B) A4 B3 (C) A3 B (D)composition cannot be specified
4. Marbles of diameter 10 mm each are to be arranged on a flat surface so that their centers lie within the area
enclosed by four lines of length each 40 mm. Sketch the arrangement that will give the maximum number of
marbles per unit area, that can be enclosed in this manner and deduce the expression to calculate it.
[JEE-2003, 2/60]
5. A binary salt AB (formula weight = 6.023 Y amu, where Y is an arbitrary number) has rock salt structure with
1 : 1 ratio of A to B. The shortest A-B distance in the unit cell is Y1/3 nm. [JEE-2004, 4/60]
(a) Calculate the density of the salt in kg m–3.
(b) Given that the measured density of the salt is 20 kg m–3, specify the type of point defect present in the
crystal.
6. In which of the following compounds the cations are present in alternate tetrahedral voids: [JEE-2005, 3/84]
(A) NaCl (B) ZnS (C) CaF2 (D) Na2O
7. In a FCC lattice of a metal edge length is 400 pm. Find the maximum diameter of an atom which can be
accommodated in an interstitial gap in this lattice without causing any distortion. [JEE-2005, 2/60]

8. For a unit cell edge length = 5Å, the element is of atomic mass 75, has density of 2gm/cc. Calculate atomic
radius of the element. [JEE-2006, 6/184]
9. Match the crystal system/unit cells mentioned in Column I with their characteristic features mentioned in
Column II. [JEE-2007, 6/162]
Column I Column II
(A) simple cubic and face-centerd cubic (p) have these cell parameters a = b = c and  =  = 
(B) cubic and rhombohedral (q) are two crystal systems
(C) cubic and tetragonal (r) have only two crystallographic angles of 90º
(D) hexagonal and monoclinic (s) belong to same crystal system
Comprehension :
In hexagonal systems of crystals, a frequently encountered arrangement of
atoms is described as a hexagonal prism. Here, the top and bottom of the
cell are regular hexagons and three atoms are sandwiched in between them.
A space-filling model of this structure, called hexagonal close-packed (HCP),
is constituted of a sphere on a flat surface surrounded in the same plane by
six identical spheres as closely as possible. There spheres are then placed
over the first layer so that they touch each other and represent the second
layer. Each one of these three spheres touches three spheres of the bottom
layer. Finally, the second layer is covered with third layer that
is identical to the bottom layer in relative position. Assume radius of every
sphere to be 'r'.
10. The number of atoms in the HCP unit cell is [JEE-2008, 4/163]
(A) 4 (B) 6 (C) 12 (D) 17
11. The volume of this HCP unit cell is [JEE-2008, 4/163]

64
(A) 24 2 r 3 (B) 16 2 r 3 (C) 12 2 r 3 (D) r3
3 3
12. The empty space in this HCP unit cell is [JEE-2008, 4/163]
(A) 74% (B) 47.6% (C) 32% (D) 26%
13. The correct statement(s) regarding defects in solids is(are) : [JEE-2009, 4/160]
(A) Frenkel defect is usually favoured by a very small difference in the sizes of cation and anion.
(B) Frenkel defect is a dislocation defect.
(C) Trapping of an electron in the lattice leads to the formation of F-center.
(D) Schottky defects have no effect on the physical properties of solids.
14. The packing efficiency of the two dimensional square unit cell shown below is :
[JEE-2010, 5/163]
(A) 39.27% (B) 68.02%
(C) 74.05% (D) 78.54%
15. The number of hexagonal faces that are present in a truncated octahedron is : [JEE-2011, 3/160]
16. A compound MP Xq has cubic close packing (ccp) arrangement of X. Its unit cell structure is shown below. The
empirical formula of the compound is : [JEE, 2012, 3/136]
(A) MX (B) MX2 (C) M2X (D) M5X14

PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)
1. Na and Mg crystallize in BCC and FCC type crystals respectively, then the number of atoms of Na and Mg
present in the unit cell of their respective crystal is [AIEEE-2002]
(1) 4 and 2 (2) 9 and 14 (3) 14 and 9 (4) 2 and 4
2. How many unit cells are present in a cube-shaped ideal crystal of NaCl of mass 1.00g?
[Atomic masses : Na = 23, Cl = 35.5] [AIEEE-2003]
(1) 2.57 × 1021 (2) 5.14 × 1021 (3) 1.28 × 1021 (4) 1.71 × 1021.
3. What type of crystal defect is indicated in the diagram below? [AIEEE-2004]

Na+ Cl– Na+ Cl– Na+ Cl–
Cl –
Cl–
Na +
Na+
Na+ Cl– Cl– Na+ Cl–
Cl –
Na +
Cl–
Na +
Na+
(1) Frenkel defect (2) Schottky defect
(3) interstitial defect (4) Frenkel and Schottky defects
4. An ionic compound has a unit cell consisting of A ions at the corners of a cube and B ions on the centers of the
faces of the cube. The empirical formula for this compound would be [AIEEE-2005]
(1) AB (2) A2B (3) AB3 (4) A3B
5. Total volume of atoms present in a face-center cubic unit cell of a metals (r is atomic radius)
[AIEEE-2006]
20 3 24 3 12 3 16 3
(1) r (2) r (3) r (4) r
3 3 3 3
6. In a compound, atoms of element Y form ccp lattice and those of element X occupy 2/3rd of tetrahedral voids.
The formula of the compound will be [AIEEE - 2008, 3/105]
(1) X2Y3 (2) X2Y (3) X3Y4 (4) X4Y3
7. Copper crystallises in fcc with a unit cell length of 361 pm. What is the radius of copper atom ?
[AIEEE - 2009, 8/144]
(1) 127 pm (2) 157 pm (3) 181 pm (4) 108 pm
8. The edge length of a face centred cubic cell of an ionic substance is 508 pm. If the radius of the cation is 110
pm, the radius of the anion is [AIEEE - 2010, 4/144]
(1) 288 pm (2) 398 pm (3) 618 pm (4) 144 pm
9. Percentages of free space in cubic close packed structure and in body centered packed structure are
respectively. [AIEEE - 2010, 4/144]
(1) 30% and 26% (2) 26% and 32% (3) 32% and 48% (4) 48% and 26%
10. In a face centred cubic lattice, atom A occupies the corner positions and atom B occupies the face centre
positions. If one atom of B is missing from one of the face centred points, the formula of the compound is:
[AIEEE-2011, 4/120]
(1) A2B (2) AB2 (3) A2B3 (4) A2B5
11. Copper crystallises in fcc lattice with a unit cell edge of 361 pm. The radius of copper atom is:
[AIEEE-2011, 4/120]
(1) 108 pm (2) 128 pm (3) 157 pm (4) 181 pm
12. Lithium forms body centred cubic structure. The length of the side of its unit cell is 351 pm. Atomic radius of the
lithium will be : [AIEEE-2012, 3/90]
(1) 75 pm (2) 300 pm (3) 240 pm (4) 152 pm

PART - III : CBSE PROBLEMS (PREVIOUS YEARS)
1. What are the properties of (i) Ferro magnetics and (ii) Ferroelectrics?
Given an example of each : [CBSE 2000, 2 M]
Ferro magnet
2. What is the difference between ferromagnetic and ferrimagnetic substances ? [Delhi 2001, 1 M]
3. Sodium crystallises in the cubic lattice and the edge of the unit cell is 430 pm. Calculate the number of
atoms in a unit cell. [Atomic mass of Na = 23.0 u, Density of sodium = 0.9623 g cm-3 NA= 6.023x 1023mol-l]
[AI 2001, 2 M]
4. An element A crystallises in fcc structure. 200 g of this element has 4.12 × 1024atoms. The density of A is
7.2 g cm-3. Calculate the edge length of the unit cell. [AI 2001, 2 M]
5. Mention one property which is caused due to the presence of F-centre in a solid. [DSB 03, AISB 06, 1 M]
6. An element occurs in bcc structure with cell edge 300 pm. The density of the element is 5.2 g cm-3
How many atoms of the element does 200 g of the element contain ? [Delhi 2003C, 2M]
7. What do you mean by coordination number? [CBSE 2004]
8. What makes alkali metal halides sometimes coloured, which are otherwise colourless ? [Delhi 2004, 1 M]
9. Define the term 'amorphous'. [AI 2004, 1 M]
10. What makes the crystal of KCl appears sometime violet

OR
Why is potassium chloride sometimes violet instead of pure white ? [AISB 2006]
11. What is the maximum possible coordination number of an atom in a hcp crystal structure of an element?
[DSB 2005, 1 M]
12. What is the effect of pressure on NaCl type crystals ? [DSB 2005, 1 M]
13. Name a salt that can be added to AgCl so as to produce cation vacancies. [AISB 2003, DSB 2005, 1 M]
14. Aluminium crystallies , in a cubic closed packed structure radius of the atom in the matel is 125 pm.
(i) What is the length of the unit cell ?
(ii) How many unit cells are present in 1cm3 of aluminium ? [Delhi 2005 3 M]
15. (a) Determine the type of cubic lattice to which a given crystal belongs if it has edge length of 290 pm and
density is 7.80 g cm-3. (Molecular mass = 56 g mol-1)
(b) Why does zinc oxide exhibit enhanced electrical conductivity on heating ? [Delhi 2005 3 M]
16. What is the effect of Schottky and Frenkel defects on the density of crystalline solids ? [AI 2006, 1 M]
17. A cubic solid is made of two elements X and Y. Atoms Y are at the corners of the cube and X at
the body centre. What is the formula of the compound ? [AISB 1997, Delhi 2006, 1 M]
18. Explain the following with suitable examples : An n-type semiconductor [Delhi 2006 2M]
19. Explain each of the following with a suitable example: [Delhi 2007 3M]
(i) Paramagnetism (ii) Piezoelectric effect (iii) Frenkel defect in crystals
20. What is the coordination number of each type of ions in a rock-salt type crystal structure? [Delhi 2008 1M]
21. What is the total number of atoms per unit cell in a face-centred cubic (fcc) structure?
[DSB SAT-II 2008, 1 M]

22. How many atoms can be assigned to its unit cell if an element forms (i) body-centred cubic cell (ii) a face-
centred cubic cell. [AISB 1999, 2000, 2005, 2007, 2008, 2009, 1 M]
23. Which point defect in crystals does not affect the density of the relevant solid? [DSB SAT-I 2009, 1M]
24. Describe the two main types of semiconductors and contrast their conduction mechanism.
[DSB SAT-I 2009, 2 M]
25. Iron has a body-centred cubic unit cell with a cell edge of 286.65 pm. The density of iron is 7.87 g cm– 3. Use
this information to calculate Avagadro’s number. (At. Mass of Fe = 56 g mol– 1)
[DSB SAT-I 2009, CBSE 2012 3M]
26. What type of interactions hold the molecules together in a polar molecular solid ? [AISB Set I 2010, 1 M]
27. What type of semiconductor is obtained when silicon is doped with arsenic? [AISB Set II 2010, 1 M]
28. Write a distinguishing feature of metallic solids. [AISB Set III 2010, 1 M]
29. Which point defect in crystals of a solid decreases the density of the solid? [DSB SAT-III 2010, 1 M]
30. Write a feature which will distinguish a metallic solid from an ionic solid. [DSB SAT-I 2010, 1 M]
31. The well known mineral fluorite is chemically calcium fluoride. It is known that in one unit cell of this mineral
there are 4Ca2+ ions and 8F– ions and that Ca2+ ions are arranged in a fcc lattice. The F– ions fill all tetrahedral
holes in the face centred cubic lattice of Ca2+ ions . The edge of the unit cell is 5.46× 10–8 cm in length. The
density of the solid is 3.18 g cm–3. Use this information to calculate Avogadro’s number. (Molar mass CaF2 =
78.08 g mol–1) [DSB SAT-I 2010, 3 M]
32. The density of copper metal is 8.95 g cm–3. If the radius of copper atom is 127.8 pm, is the copper unit cell a simple
cubic, a body -centrede cubic or a face-centred cubic structure? (Given : At mass of Cu = 63.54 g mol–1 and NA =
6.02 × 1023 mol–1). [DSB SAT-III AL SET-I 2010, 3 M]
33. ‘Crystalline solids are anisotropic in nature.’ What does this statement mean ? [DSB SAT-I 2011, 1 M]
34. Silver crystallizes in face-centered cubic unit cell. Each side of this unit cell has a length of 400 pm. Calculate
has radius of the silver atom. (Assume the atoms just touch each other on the diagonal across the face of the
unit cell. That is each face atom is touching the four corner atoms.) [DSB SAT-I 2011, 3 M]
35. Which stoichiometric defect in crystals increases the density of a solid? [DSB SAT-II 2011, 1 M]
36. How may the conductivity of an intrinsic semiconductor be increased ? [DSB 2012, 1 M]
37. Tungsten crystallizes in body centred cubic unit cell. If the edge of the unit cell is 316.5 pm, what is the radius
of tungsten atom? [CBSE 2012, 3 M]


1. Space latice is the three demensional regular arrangement of atoms, ions or molecules represented by points
called lattice points.
2. In body-centred cubic crystal free space is 32%.

3. There are 8 tetrahedral voids in a unit cell of ccp structure.
4. Packing efficiency in a simple cubic lattice = 52.4%.
5. The size of octahedral void is larger than tetrahedral void because cation can occupy octahedral void if size of
cation is 0.414 times as large as anion whereas in tetrahedral voids it should be 0.225 times as large as anion.
6. It is because their presence leads to excess of electrons or leads to formation of positive holes which increase
electrical conductivity.
7. Doping is a process of adding impurities in a crystal lattice. It is done by adding calculated amount of impurity.
Addition of one boron atom per 105 silicon atoms increases the conductivity of silicon by 103 at room tempera-
ture.
8. Dislocations: A dislocation extends along lines and result from the imperfect orientation of planes with respect
to one another in the crystal.
9. p-type semiconductor
10. MnO is antiferromagnetic solid.
11. Molecular solids – CO2, H2 ; Ionic solids – MgO, AgCl

Covalent solids – Si ; Metallic solids – Gd, Al, Pb
12. (i) Triclinic (ii) a  b  c, (iii)    90º, (iv) CuSO4.5H2O
13. (i) Unit cell is the smallest portion of a crystal lattice which, when repeated in different directions, generates the
entire lattice.
e.g., primitive unit cells : simple cubic
centred unit cells : bcc, fcc, ecc
(ii) The number of spheres which are touching a given sphere is called the coordination number.
e.g., In simple cubic arrangement coordination number is : 6.
In bcc arrangement coordination number is : 8.
In hcp or fcc arrangement coordination number is : 12.
14. Given : Density, edge length, Perameter of simple cubic unit cell [½ Mark]
Asked : Atomic mass
Z  M / N0
Formulae : Density = [½ Mark]
a3  10 30
Explanation : a pm = edge of the unit cell [½ Mark]
z = Number of atom present per unit cell
M = atomic mass
 Volume of the unit cell = (a pm)3 = a3 × 10–30 cm3.
D = Density
D  a 3  N0  10 30
Ans. M = amu [½ Mark]
Z

15. In a simple cubic unit cell : Suppose the edge length of the unit cell = a and radius of the sphere = r.
1
Number of spheres per unit cell = × 8 = 1.
8
4 3
Volume of the sphere = r
3
Volume of the cube = a3 = (2r)3 = 8r3
4 3
 r 
3  
Fraction occupied, i.e., packing fraction = 3 = = 0.524.
8r 6
% of occupied volume = 52.4%.
16. Given : a = 352 pm. [½ Mark]
Asked : r = ?
3
Formulae : r = a (for bcc unit cell) [½ Mark]
4
Explanation : r = radius of an atom
a = edge length
3  352 1.732  352

Substitution & Calculation : r = = [½ Mark]
4 4
Ans. 152.416 pm. [½ Mark]
17. Given : M = 60 g mol–1, Z = 4, a = 400 pm = 400 × 10–10 cm, NA = 6.023 × 1023 [½ Mark]
Asked : d = ?
Z M
Formulae : d= [½ Mark]
NA  a3
Explanation : d = density
a = edge length
M = atomic mass
NA = Avagadro number
4  60
Substitution & Calculation : d = [½ Mark]
6.023  10 23
 ( 400  10 10 )
Ans.: 6.23 g cm–3 [½ Mark]
Z M 4  63.5
18. Density (d) = 3 = = 8.96 g/cm3
a  NA (3.61) 10 – 24  6.023 10 23
3
19. (i) Schottky defect : It occurs when the equal number of vacant cation and anion sites are found in lattice
structure. It decreases the density of the substance.
(ii) Interstitial defect : When some constituent particles (atom or molecules) occupy an interstitial site, the
crystal is said to have interstitial defect. This defect increases the density of the substance. For example, non-
ionic solids.
20. O2– ions are arranged in hcp,  number of O2– ions are equal to = 6
Al3+ ions occupy 2/3 of the octahedral voids.
2
No. of Al3+ ions =  6  Al 2 O6 Al2/3O1 Formula of corundum is Al2O3.
3 3
6

21. Given : Z = 1 for simple cubic, M = 200 g, N = 24 × 10 atoms, d = 8 g cm , NA = 6.023 × 1023
23 –3
[½ Mark]
Asked : a = ? [½ Mark]
Z M ZM
Formulae : d= ; a3 = [1 Mark]
NA  a3 dN
a = edge length
M = atomic mass
Z = Effective number of atoms
1 200
Substitution & Calculation : a3 =
8  24  1023
a = 10.41 × 10 cm
3 –24 3
a = 2.18 × 10–8 cm = 2.18 × 10–8 × 1010 pm = 218 pm. [ 1 cm = 1010 pm] [1 Mark]
Ans.: 218 pm.
22. Given : Z = 4 for fcc, M = 200 g, N = 24 × 1023 atoms, a = 200 pm = 200 × 10–10 cm = 2 × 10–8 cm. [½ Mark]
Asked : d = ? [½ Mark]
Z M
NA  a3
a = edge length
M = atomic mass
Z = Effective number of atoms [½ Mark]
ZM 4  200
Substitution & Calculation :d = 
3
a N ( 200 )  10 30  24  10 23
3
4  200 1000
d=  24 23 = = 41.67 g cm–3 [1 Mark]
8  10  24  10 24
Ans.: 41.67 g cm–3
1 1
23. Cu forms sc  Cu = 8 × =1 Ag at edge centres = 12 × =3 Au at body centre = 1
8 4
Formula = Cu Ag3 Au
24. (a) It is due to strong covalent bonds in diamod whereas there are weak van der Waal’s forces of attraction in
S8 molecules. [1 M]
(b) Silicon is best conductor out of these because it is semiconductor whereas others are insulator in solid
state. [1 M]
(c) In bcc,4r = 3a [½ M]
3a 1.732  4.29Å 7.43

r=  ; r= Å = 1.857 Å
4 4 4
Body diagonal = 3a = 1.732 × 4.29 Å = 7.43 Å. [½ M]
25. (i) Frenkel defects have no effect on the density because number of atoms per unit cell remains the same.
Given : For fcc, Z = 4, Atomic weight of Ca = 40 g mol–1
a = 0.5506 nm = 0.556 × 10–7 cm, NA = 6.023 × 1023 [½ Mark]

Asked : d = ?
Z M
NA  a3
a = edge length
M = atomic mass
4  40 160 160
Substitution & Calculation : d = 7 3 23 =  [1 Mark]
(0.556  10 )  6.022  10 2 103.5
0.17  6.022  10
d = 1.5458 g cm–3
Ans.: 1.5458 g cm–3

(ii) Due to 0.2% Schottky defect, No. of atoms
0.2
– × 4 = 3.992 [½ Mark]
100
Z M 4  3.992
d= = = 1.5427 g cm–3. [½ Mark]
(0.556  10 7 )3  6.022  10 23
3
a  NA
26. (i) At 850 K ,Fe3O4 (magnetite) loses its alignment of magnetic moment is parallel and anti-parallel direction in
unequal numbers and become paramagnetic.
(ii) Zinc oxide is white in colour at room temperature. On heating it loses oxygen and turns yellow. (due to
formation of F - centre)
heating 1
ZnO  Zn2+ + O2 + 2e–
2
(iii) Due to Frenkel defect, no ions are missing from the crystal as a whole. Thus, there is no change in density.
27. Stoichiometric Defects :The compounds in which the number of positive and negative ions are exactly in the
ratios indicated by their chemical formulae are called stoichiometric compounds. The defects that do not
disturb the stoichiometry (the ratio of numbers of positive and negative ions) are called stoichiometric defects.
Non-Stoichiometric Defects :The defects which disturb the stoichiometry of the compound are called non-
stoichiometric defects. These defects are either due to the presence of excess metal ions or excess non-
metal ions.
28. (i) 12–16 Compound. A semiconductor formed by combination of group 12 and group 16 elements is called
12–16 compound e.g., ZnS, CdS, HgTe etc.
(ii) 13–15 Compound. A semiconductor formed by the combination of group 13 and group 15 elements is
called 13–15 compound e.g., AlP, InSb, GaAs etc.
29. In semiconductor, electrical resistivity decreases with increase in temperature. In metals, electrical resistivity
increases with increases in temperature and in insulators electrical resistivity decreases with increase in
temperature.
30. (i) Ferromagnetism : Materials which are strongly attracted by magnetic fields are called ferromagnetic
materials and the property thus exhibited is called ferromagnetism. only three elements (Fe, Co, Ni) show
ferromagnetism at room temperature.
(ii) Paramagnetism : Materials which are weakly attracted by magnetic fields are called paramagnetic materials
and the property thus exhibited is called paramagnetism. Paramagnetic substances contain unpaired electron.
e.g. TiO, CuO, O2 and VO2 etc.
31. (a) Coordination number : The number of nearest neighbours is a packing in a crystal structure is called
coordination number. [1 mark]
(b) Number of atoms in a unit cell of
(i) a face centred cubic structure is 4. (ii) a body centred cubic structure is 2. [½ + ½ = 1 marks]

(b) Given : Z = 4 for simple cubic, M = 207 g/mol, d = 11.35 g cm , NA = 6.023 × 10 –3 23
[½ Mark]
Asked : a = ?, r = ? [½ Mark]
Z M ZM a
Formulae : d= 3 ; a3 = ; for fcc 4r = 2a; r= [1 Mark]
NA  a dN 2 2
a = edge length
M = atomic mass
r = Radius of an atom
Z M
Substitution & Calculation : Density (d) = (For fcc(z) = 4) [½ Mark]
a3  NA
4  207 828
11.35 = 3 23 ; a3 =
a  6.02  10 11.35  6.023  10 23
1/ 3
 828  a
a=  23
 = 494.8 pm ; for fcc 4r = 2a; r=
 11.35  6.023  10  2 2
494.8
r= = 175 pm [1 Mark]
2 2
Ans.: 175 pm.
32. (a) Given : a = 287 pm. [½ Mark]
Asked : r = ? [½ Mark]
3
Formulae : For body centred cubic lattice, we have r = a [½ Mark]
4
Explanation : a = edge length
3 3 1.73  287 496 .51

Substitution & Calculation :r = a= × 287 = = = 124.1275 pm. [½ Mark]
4 4 4 4
Ans.: 124.1275 pm.
(b). Given : Z = 4, d = 10.5 g/cm3, a = 4.07 x 10–8 c.m, NA = 6.023 × 1023 [½ Mark]
Asked : M = ? [½ Mark]
Z M NA  a 3  d
Formulae : d = 3 ; M= [1 Mark]
NA  a Z
a = edge length
M = atomic mass
d  a 3  NA 10.5  ( 4.07)3  10 24  6.02  10 23

Substitution & Calculation : M = =
Z 4
4261 .564
= = 106.5391 g/mol [1 Mark]
40
Ans.: 106.5391 g/mol

33. (a) Given : Z = 4 for simple cubic, M = 60 g/mol, d = 6.23 g cm , NA = 6.023 × 10–3 23
[½ Mark]
Asked : a = ?
Z M ZM
Formulae : d = ; a3 = [½ Mark]
NA  a 3 dN
a = edge length
M = atomic mass
Z M 4  60 2400
Substitution & Calculation : a3 = N  d = 23 = ×10–24
A 6.023  10  6.23 37 .52
a3 = 64 × 10–24 cm3 ; a = (4 × 10–8 ×1010) pm = 400 pm [1 Mark]
Ans.: 400 pm.
(b) Given : M = 50 g mol–1, Z = 2, d = 5.91 g cm–3 , NA = 6.023 × 1023 [½ Mark]
Asked : V = a3 = ? [½ Mark]
Z M ZM
Formulae : d= ; Volume (V) = a3 = [1 Mark]
NA  a3 dN
a = edge length
M = atomic mass
ZM 2  50
Substitution & Calculation : d = 
3
NA  a a  6.023  10 23
3
2  50 100  10 23
a3 = = = 2.809 × 10–23 cm3 [1 Mark]
5.91 6.023  10 23 35.59
Volume = a3 = 2.809 × 10–23 cm3
Ans. 2.809 × 10–23cm3
34. (i) It is a hexagonal close packing
(ii) The coordination number is 12
(iii) Free space = 26%
(iv) Z = 6, There are six atoms in single unit cell having hexagonal close packing.
1 1
35. (a) Cations A = ×8=1 ; Cations B = ×4=2
8 2
1 1
O2– = 8 × +6× =4 [ O2– forms cubic close packed structure]
8 2
AB2O4 is formula of mixed oxide.
4r
(b) In bcc, 4r = 3a a=
3
4 3
Volume of sphere = r ; Z = 2
3
4 3
Total volume occupied by all spheres = 2 × r
3
3
 4r 
Volume of cube = a = 
3 

 3
4 3
2
r
3 8 3 3 3 22
Efficiency = 100 × 44 4 3
r
= 100 ×   = 100 ×  = 68%
3 3
3 4 4 4 8 7

36. (a) Point defects. The defects which are caused by missing or misplaced atoms or ions in the crystal.
(b) Given : Z = 4, d = 8.92 g cm–3, M = 63.5 g mol–1, NA = 6.023 × 1023 [½ Mark]
Asked : a = ?, r = ? [½ Mark]
Z M ZM a
Formulae : d= 3 ; a3 = ; for fcc 4r = 2a; r= [1 Mark]
NA  a dN 2 2
a = edge length
M = atomic mass
Z M 4  63.5
Substitution & Calculation : d3 = N  d =
A 6.022  10 23  8.92
254 .0
= × 10–23 = 4.728 × 10–23
53.716
d3 = 47.28 × 10–24
a = 3 47.28  10 8 x = (47.28)1/3
1 1
a = 3.616 × 10–8 × 1010 pm log x = log (47.28) = × 1.6746
3 3
a = 361.6 pm x = Antilog 0.558277
4r = 2a x = 3.616
a 361 .6 361.6
r= = r= = 127.86 pm [1 Mark]
2 2 2  1.414 2.828
Ans.: 127.86 pm
37. (a) (i) Schottky defect decreases the density of the crystal.
Frenkel defect does not change the density of the crystal.
(ii) Electrical conductivity of the crystal is increased in both Schottky and Frenkel defects.
(b) (i) In conductors the energy gap are very close or even overlapped by the conduction bands. Due to this
reason electron can flow very easily from valence to conduction band under an electronic field and shows
conductivity.
In insulator, the energy gap between the valence band and conduction band is too high so that electron can not
flow from valence band to conduction band. Therefore, no conduction is possible.
(ii) In semiconductor the energy gap between valence band and conductor band is small which make some
of the electron enable to jump from valence to conduction band and shows conductivity

EXERCISE - 1
PART-I
A-1. Ionic – LiBr , (NH4)3PO4 ; Metallic – Brass, Rb; Molecular – P4O10 , 2 , P4
Network – SiC, Graphite, Si, Amorphous – Plastic
A-2. (a)- (f), (l) ; (b)- (e), (k) ; (c) - (h) , (j) ; (d) - (g) , (i)
A-3. Ques. (a) (b) Total particles
(i) 1/4 1 2
(ii) 1/2 1/4 2
(iii) 1/6 1/2 2
(iv) 1/6 – 1/2
(v) 1/3 1/6 1
A-4. Crystal System Features Unit cell found Examples

Monoclinic abc S, EC Monoclinic sulphur, PbCrO4 ,
α = γ = 90°; Na2SO4.10H2O, Na2B4O7.10H2O.
β  120°,  90°,  60°
Hexagonal a=bc S Graphite, ZnO, CdS, Mg, PbI2, SiC.
α = β = 90°, γ = 120°
Triclinic abc S K2Cr2O7, CuSO4.5H2O, H3BO3.
α  β  γ  90°
B-1. Cube1 - 1/2 ; Cube2 - 1/4 ; Cube3 - 1 ; Cube4 - 1/8
B-2. r = 124 pm
B-3. BCC
B-4. 23/3 amu/ Å 3
B-5. 124.27 pm , density = 7.30 g cm -3
C-1. No, Rhombous: 2R, 60º, 120º ; Triangular voids; 2 voids, 0.155 R.
C-2. Octahedral void is present at the body center, which is formed by six face centered atoms and it consist at
triangle faces.
3 2
4 1
C-3. r –minmum = 102.45 , r –maximum = 333.3 pm
C-4. ABC-ABC-Arrangement (CCP unit cell).
1
C-5. O.V = 2 = 1 + ×4=2 : T.V = 4
4
D-1. Total number of atoms per unit cell in fcc structure = 4 atoms.

D-2. (i) 2r, 2r, 2 3r ; (ii) Square, side = 2r.. D-3. FCC, 2Å
a a
D-4. 4, 8, , E-1. ABAB............type arrangement (unit cell = HCP).
2 2
E-2. 1.72 × 10–23 cm3 , 1.60 Å
E-3. (i) b, f, g are identical; c, e are identical. (ii) da < [db = df = dg]< [dc = de]< dd
E-4. 12 and 6
F-1. (a) CsCl type (b) ZnS type (c) NaCl type (d) CsCl type
F-2. 12 F-3. 2.16 g/cm3
rZn2 
F-4. In case of ZnS radius ratio is r 2 – = 0.402.
S
That's why Zn2+ ion is present in tetrahedral void. If Zn2+ ion is present in octahedral void [For NaCl type
structure] then anion-anion contact is there and compound become unstable. That's why. ZnS not crystallize in
the NaCl structure.
F-5. (i) Zn2+ ions occupy alternate Tetrahedral holes ; (ii) Anti-Flourite: Anions in FCC and Cations in Tetrahedral
holes, Fluorite: Cations in FCC and Anions in Tetrahedral holes
F-6. (a) K+ ion = 4 & Br¯ ion = 4 (b) 6.56 Å (c) 2.80 g/cm3 (d) 0.414
F-7. B2A
F-8. Anti-Flourite: Anions in FCC and Cations in Tetrahedral holes, Fluorite: Cations in FCC and Anions in Tetrahedral
holes
F-9. 8
G-1. Imperfections in solids : Any deviation from the perfectly ordered arrangement constitutes a defect or
imperfection. These defect are sometimes called thermodynamic defects because the number of these defects
depends on the temperature.
(i) Stoichiometric point defects : Schottky Defects, Interstitial Defects, Frenkel Defects.
(ii) Non-Stoichiometric defects : Metal excess defects, Metal deficiency defects.
G-2. 6.02 × 1018
G-3. The reason of both is the presence of electron in anionic vacancies which is known as F– center.
G-4. Silicon doped with phosphorus forms n - type of semiconductor. Phosphorus contains one extra electron than
silicon which can move easily through the crystal and is responsible for semiconductor properties.
G-5. In semiconductor fairly small band gap is present between valence band (filled with electrons) and conduction
band (lowest unoccupied energy band). Increase in temperature gives thermal energy to some of the electrons
and they move to conduction band and change the conductivity of semiconductor (Increase).
PART - II
A-1. (C) A-2. (C) A-3. (D) A-4. (A) A-5. (A) B-1. (A) B-2. (B)
B-3. (A) B-4. (C) C-1. (A) C-2. (B) C-3. (C) D-1. (B) D-2. (C)
D-3. (A) D-4. (B) D-5. (A) D-6. (C) D-7. (A) E-1. (B) E-2. (A)
E-3. (A) E-4. (B) E-5. (C) F-1. (C) F-2. (D) F-3. (C) F-4. (B)
F-5. (B) F-6. (A) F-7. (A) F-8. (B) G-1. (C) G-2. (B) G-3. (A)
G-4. (A)
PART - III
1. (D) 2. (B) 3. (B)

EXERCISE - 2
PART-I
1. Ionic – NaCl , ZnSO4 Metallic – Bronze, Fe Molecular – S8 , 2
Network – SiO2, Diamond, Si Amorphous – Rubber, Glass
2. (a) 3, (b) 60 % 3. (i) r 2 3 ; (ii) 2r 2 / 3 ; (iii) Yes, of course 4. 16
11
5. n=8,p= 6. 9 × 1024
21
7. (a) 4.50 Å, (b) 5.20 Å, (c) 12, (d) 6, (e) 0.925 g/cm3
8. It is formed by four spheres the centres of which form a regular tetrahedron.
9. (i) Octahedral void Tetrahedral void

HCP 6 12
FCC 4 8
(ii) False
10. (a) 2.878 Å, (b) 12, (c) 19.4 g/cm3, (d) 0.7405 11. 6.038 × 1023 atoms mol–1.
C a
12. (a) XY3 (b) (i) X7Y24 (ii) XY4 (iii) X7Y24Z 13. h= =2 2 × = 2 2 r..
2 3 2 3
14. d = 4.43 g/cm3 15. (a) Fe2O3, (b) CdI2 16. NA = 6.04 × 1023
17. (i) 100% (iii) 50% 18. 4 Fe2+ & 4 O2  19. 64.5 g/cm3
20. When the atoms or ions are missed or misplaced in the crystal, the defects are called point defects.
21. (i) 0.007  6.02  1023 vacancies, (ii) 0.0465  6.02  1023 vacancies
22. In ferromagnetic substance the magnetic moment is aligned spontaneously in one direction under the influence
of external magnetic field and they become permanently magnetised. When magnetic moments are aligned in
parallel and antiparallel directions in unequal numbers resulting net magnetic moment it is called ferrimagnetism.
23. In Silicon, electrons are fixed in covalent bonds and are not free for conduction, hence it is an insulator. On
heating some of covalent bonds break and released excited electrons which can move under the electric field,
and thus make the silicon, semiconductor.
PART - II
1. (C) 2. (A) 3. (C) 4. (B) 5. (D) 6. (B) 7. (C)
8. (D) 9. (A) 10. (A) 11. (C) 12. (B) 13. (C) 14. (B)
15. (B) 16. (A) 17. (B) 18. (D) 19. (A) 20. (A) 21. (D)
22. (B) 23. (A) 24. (C) 25. (D) 26. (B) 27. (A) 28. (C)
29. (A,B,C) 30. (A,B,C) 31. (B,C) 32. (A,B,C) 33. (A,C)
PART - III
1. (A - r,s) ; (B - r,s) ; (C - p) ; (D - q) 2. (A - p,q,r,s) ; (B - p,r,s) ; (C - p,s) ; (D - p,r,s)
PART - IV
1. (B) 2. (A) 3. (C) 4. (C) 5. (B) 6. (A) 7. (C)

EXERCISE - 3
PART - I
1.
In the figures given below draw the unit cell of the corresponding structure and identify these plane in your
diagram (out of fcc and simple cubic).
(i) Face plane (ii) Body diagonal plane (iii) Plane passing through the face diagonals.
2. (D) 3. (A) 4. 25, 1.804 marbles/cm2
5. (a) 5 kg m–3 (b) Cancelled (Full marks given in part a) 6. (B)

7. 117.08 pm
ZM
8. d=  Z = 20 × 10–1 = 2
NA a3
3
So its is a bcc unit cell. Hence 3 a = 4R so R= × 5Å = 216.5 pm.
4
9. [A – p, s] ; [B – q & p] ; [C – q] ; [D – q, r]. 10. (B) 11. (A)
12. (D) 13. (B,C) 14. (D) 15. 8 16. (B)

PART - II
1. (4) 2. (1) 3. (2) 4. (3) 5. (4) 6. (4) 7. (1)
8. (4) 9. (2) 10. (4) 11. (3) 12. (4)
PART - III
1. (i) Ferromagnetics : substances which show magnetism even in the absence of magnetic field, are known as
ferromagnetic substances. In ferromagnetics the magnetic moment is aligned spontaneously in one direction
under the influence of external magnetic field and they are magnetized permanently. Example : Fe and Co.
(ii) Ferroelectrics : In certain piezoelectric crystals the dipoles are permanently lined up in the absence of
electric field too. On applying the electric field the direction of polarisation can be changed. Such crystals are
known as ferroelectric crystals and this phenomenon is known as Ferroelectrics. Example : Bariumtitanate
(BaTiO3).
2. Ferromagnetic substances have large number of unpaired electrons. They remain magnetised even in ab-
sence of magnetic field. Ferrimagnetic substances have magnetic dipoles parallel and anti parallel unequal in
number such that there is net magnetic moment.
3. 2.004 atoms/unit cell.
4. 299.8 pm
5. F-centre is responsible for the colour and paramagnetic behaviour of the solid.
6. 2.85 ×1024 atoms
7. Number of nearest neighbours (atoms or ions) of any atom or ion is known as it’s coordination number in
crystal lattice.
8. Metal halides become coloured due to excess of metal ions which attract halide ions forming
F-centres which absorb light from visible region and radiate complementary colour.

9. Amorphous substances are those which do not have well defined geometrical shape. They have short
range order.
10. In presence of excess of potassium, Cl– ions leave their lattice sites creating anion vacancies which are
occupied by electrons given out by potassium. These are called F-centres and are reponsible for colour.
11. 12
12. On increasing pressure, the coordination number of NaCl type crystals increase from 6 : 6 to 8 : 8.
13. CdCl2 or SrCl2..
14. (i) a = 354 pm, (ii) 2.261 × 1022 unit cells
15. (a) 2.04  2.00 b cc
(b) On heating it is because electrons are trapped in place of O2–.which increases electrical conductivity. On
hating O2– changes to O2which is lost to atmospheres. [1 Mark]
16. The density decreases in case of Schottky defects whereas it remains the same in case of Frenkel defect.
17. XY
18. W hen group 14 element is doped with group I5 element, we get n-type semiconductor e.g.,
Silicon doped with Arsenic.
19. (i) Paramagnetism : When substances which are attracted by the external magnetic field are called paramagnetic
substances and the phenomenon is called as paramagnetism. Atoms ion or molecules containing unpaired electron
show this property, eg. O2 Cu2+, Fe3+ etc. these substances lost their magnetism in the absence of magnetic field.
Piezoelectricity : A dielectic crystal which has a resultant dipole moment can produce electricity or show
electrical property when external pressure is applied. Such a crystal is known as piezoelectric crystal and
this property is called piezoelectricity.The mechanical stress caused by the applied pressure results in
electric current because of the displacement of the ions in the crystals.
Such piezoelectric crystals find applications as pick-ups in record players since electric signals are produced
on applying pressure. Some piezoelectric materials are lead-zirconate (PbZrO3), ammonium dihydrogen
phosphate (NH4H2PO4), quartz, etc.
(iii)Frenkel Defects : This type of defect is created when an ion leaves its correct lattice site and occupies an
interstitial site. Frenkel defects are common in ionic compounds which have low coordination number and in
which there is large difference in size between positive and negative ions. Example ZnS, AgCl, AgBr and AgI.
20. In rock salt or common salt, every Na+ ion is surrounded by 6 Cl– ions and each Cl– ion is surrounded by
6 Na+ ions. Thus, the coordination number of each type of ion in rock salt is 6.
21. Total number of atoms per unit cell in fcc structure = 4 atoms.
22. (i) 2, (ii) 4
23. Frenkel defect in crystals does not affect the density of the relevant solid.
24. The solids which have intermediate conductivities generally between 10 –6 to 10 4  –1 m –1 are called
semiconductors. For example, germanium and silicon. The two main types of semiconductors are as
follows :
(i) n-type semiconductors : When a silicon crystal is doped
with atoms of group-15 elements, such as P, As, Sb or Bi ;
then only four of the five valence electrons of each impurity
atoms participate in forming covalent bond and fifth electron
is almost free to conduct electricity. Silicon that has been
doped with a group-15 element is called n-type
semiconductor.

(ii) p-type semiconductor : When a silicon crystal is dope with atoms of group-13 elements, such as B, Al,
Ga or In; each impurity atoms forms only three covalent bonds with the host atoms. The place where the fourth
electron is missing is called a hole which moves through the crystal like a positive charge and hence increases
its conductivity. Silicon that has been doped with group-13 element is called p-type semiconductor.
25. 6.022 × 1023
26. Dipole-dipole attractions
27. n-type semiconductor
28. Metallic solids are malleable and ductile and good conductors of electricity.
29. Vacancy defect decreases the density of a substance. Vacancy defect in ionic solids is known as Schottky
defect.
30. Metallic solids conduct electricity in solid state through free electrons while ionic solids conduct electricity in
molten state or in aqueous electricity in molten state or in aqueous solution through free ions. Metals are
malleable and ductile whereas ionic solids are hard and brittle.
31. NA = 6.022 × 1023

32. Let us assume Z = 4 (copper has fcc)
Z M 4  63.54
d= : 8.95 =
a3  NA a  6.023  10 23
3
4  63.54 254.16
a3 =  × 10–23  4.7 145 × 10–23 cm3
8.95  6.023  10 23 53.91
a3 = 47.145 × 10–24 cm3
a= 3
47.145 × 10–8 cm3 = 3.612 × 10–8 cm = 361 .2 pm
a 361 .2
For Fcc 4r = 2a : r= = = 127.7 pm
2 2 2  1.414
It shows 'Cu' has fcc structure
33. Crystalline solids are anisotropic in nature, that is some of their physical properties like electrical resistance or
refractive index, show different values, when measured along different direction in the same crystals.
34. 141.84 pm
35. Point defects due to the presence of foreign atoms or impurities (Impurity defects) :
When some small foreign atoms are trapped in interstitial voids of the lattice without any chemical reaction.
Formula remains the same, but exp > theortical
Cation Anion Interstitial entity
Interstitial defec t
36. Conductivity can be increased by adding appropriate amount of suitable impurity in intrinsic semiconductor.
This process is called doping.
37. 137.04 pm.


Single choice type
1. In a square close packing pattern, one atom is in contact with how many atoms in the 2-D plane base?
(A) 2 (B) 4 (C) 6 (D) 8
2. In a cubic structure of compound which is made from X and Y, where X atoms are at the corners of the cube
and Y at the face centers of the cube. The molecular formula of compound is
(A) X2Y (B) X3Y (C) XY2 (D) XY3.
3. In a face centerd lattice of X and Y, X atoms are present at the corners while Y atoms are at face centers. Then
the formula of the compound would be if one of the X atoms is missing from a corner in each unit cell
(A) X7Y24 (B) X24Y7 (C) XY24 (D) X24Y
4. A solid has a structure in which W atoms are located at the corners of a cubic lattice. O atom at the center of
the edges and Na atom at center of the cube. The formula for the compound is
(A) NaWO2 (B) NaWO3 (C) Na2WO3 (D) NaWO4
5. A certain metal fluoride crystallises in such a way that F atoms occupy simple cubic lattice corner sites, while
metal atoms occupy the body centre of the cubes. The formula of metal fluoride is :
(A) M2F (B) MF (C) MF2 (D) MF8
6. CsBr has b.c.c. structure with edge length 4.3 A. The shortest inter ionic distance in between Cs+ and Br–
is:
(A) 3.72 (B) 1.86 (C) 7.44 (D) 4.3
7. Space lattice of CsCl is :

(A) Face centered cubic (B) Body centered cubic
(C) Simple cubic (D) Hexagonal close packing
8. The density of crystalline CsCl is 3.988 g/cc. The volume effectively occupied by a single CsCl ion pair in the
crystal is :
(A) 7.014 × 10–23cc (C) 2.81 × 10–22cc (C) 6.022 × 1023cc (D) 3.004 × 10–23cc
9. Match list- with list-II and select the correct answer by using the codes given below:
List I List II
(Shapes) (Radius ratio)
(A) Planar triangle 1. 0.732
(B) Square planar 2. 0.225
(C) Body centered cubic 3. 0.155
(D) Tetrahedral 4. 0.414
Code
A B C D A B C D
(A) 3 4 1 2 (B) 3 2 1 4
(C) 2 1 4 3 (D) 1 3 4 2
10. In the closest packing of atoms,

(A) the size of tetrahedral void is greater than that of octahedral void
(B) the size of tetrahedral void is smaller than that of octahedral void
(C) the size of tetrahedral void is equal to that of octahedral void
(D) the size of tetrahedral void may be greater or smaller or equal to that of octahedral void depending upon
the size of atoms.

11. Figure shows a cube of unit cell of CCP arrangement with face centered atoms marked 1, 2, 3.Which of the
following statements is true.
(A) Atom 3 is twice as far from 1 as from 2 (B) Atom 2 is equidistant from atoms 1 & 3.
(C) Atom 2 is nearer to 1 than to 3. (D) All atoms lie on a right angled triangle.
12. The following diagram shows arrangement of lattice point with a = b = c

and  =  =  = 90º.
Choose the correct options.
(A) The arrangement is SC with each lattice point surrounded by 6 nearest neighbours.
(B) The arrangement is SC with each lattice point surrounded by 8 nearest neighbours.
(C) The arrangement is FCC with each lattice point surrounded by 12 nearest
neighbours.
(D) The arrangement in BCC with each lattice point surrounded by 8 nearest
neighbours
13. If the radius of a metal atom is 2.00 Å and its crystal structure in cubic close packed (fcc lattice), what is the
volume (in cm3) of one unit cell ?
(A) 8.00 × 10–24 (B) 1.60 × 10–23 (C) 1.80 × 10–22 (D) 2.26 × 10–23
14. A crystal is made of particle X, Y & Z. X forms FCC packing, Y occupies all octahedral voids of X and Z
occupies all tetrahedral voids of X, if all the particles along one body diagonal are removed then the formula of
the crystal would be -
(A) XYZ2 (B) X2YZ2 (C) X8Y4Z5 (D) X5Y4Z8
15. A crystal is made of particles A and B. A forms FCC packing and B occupies all the octahedral voids. If all the
particles along the plane as shown in figure are removed, then, the formula of the crystal would be :
(A) AB (B) A5B7 (C) A7B5 (D) None of these.
16. Calculate the perimeter of given plane in HCP unit cell (Given that radius of atoms = R Å).
(A) 6.437 R (B) 15.32 R (C) 16 R (D) 8 R
17. For an Ionic solid of the general formula AB and coordination number 6, the value of the radius ratio will be
(A) less than 0.225 (B) in between 0.225 and 0.414
(C) between 0.414 and 0.732 (D) greater than 0.732
18. In the zinc blende structure, zinc ions occupy alternate tetrahedral voids and S2– ions exist as ccp. The radii of
Zn2+ and S2– ions are 0.83 Å and 1.74 Å respectively. The edge length of the ZnS unit cell is
(A) 2.57 Å (B) 5.14 Å (C) 5.93 Å (D) 4.86 Å

19. An ionic solid of XY type having anions in CCP lattice and cations in the octahedral voids.Let a be the edge
length of an FCC cube.The radius ratio of cation(R+) to that of anion(R–)is greater than 0.415.Then which of
the following is false:
a a
(A) R+ = (B) R+ + R- =
2 2 2
(C) Anions will not be in contact with each other. (D) Cations will not be in contact with each other.
20. How many units cells are there in 1.00 g cube shaped ideal crystal of AB (Mw = 60) which has a NaCl type
lattice
(A) 6.02 × 1023 (B) 1.00 × 2022 (C) 2.50 × 1021 (D) 6.02 × 1024
21. MgAl2O4, is found in the Spinal structure in which O 2  ions constitute CCP lattice, Mg2+ ions occupy 1/8th of
the Tetrahedral voids and Al3 ions occupy 1/2 of the Octahedral voids.
Find the total +ve charge contained in one unit cell.
(A) +7/4 electronic charge (B) +6 electronic charge
(C) +2 electronic charge (D) +8 electronic charge
22. Statement-1 : The apparent ionic radius increases 3% if the co-ordination number is changed from 6 to 8 and
decreases 6% when the co-ordination number is decreased from 6 to 4.
Statement-2 : Ionic radii can not be measured absolutely, but are estimated, and since they vary with the co-
ordination number , conclusions based on them are not very rigorous.
23. Which of the following statements is not true?
(A) Paramagnetic substances are weakly attracted by magnetic field.
(B) Ferromagnetic substances cannot be magnetised permanently.
(C) The domains in antiferromagnetic substances are oppositely oriented with respect to each other.
(D) Pairing of electrons cancels their magnetic moment in the diamagnetic substances.
24. Statement-1 : In Frenkel defect in an ionic crystal, an ion is displaced from its normal site to an interstitial site.
Statement-2 : There is both a vacancy and an interstitial ion.
25. Statement-1 : Stoichiometric compounds obey the law of constant composition.
Statement-2 : Schottky and Frenkel defects are observed in stoichiometric compounds
26. Statement-1 : In point defect density of solid may decrease and increase
Statement-2 : Formation Fe0.93 O is called non–stoichiometric defects.

27. Lead metal has a density of 11.34 g/cm3 and crystallizes in a face–centered lattice. Choose the correct
alternatives
(A) the volume of one unit cell is 1.214 × 10–22 cm3
(B) the volume of one unit cell is 1.214 × 10–19 cm3
(C) the atomic radius of lead is 175 pm
(D) the atomic radius of lead is 155.1 pm
28-* Given that interionic distance in Na+ F– crystal is 2.31Å and rF = 1.36Å, which of the following predictions will
be right
(A) rNa rF   0.7
(B) coordination number of Na+ = coordination nunber of F– = 6
(C) Na+ F– will have rock salt type crystal structure
(D) effective nuclear charge for Na+ and F– are equal
29.* Which of the following statement(s) for crystal having schottky defect is/are correct.
(A) Schottky defect arises due to absence of cations & anion from positions which they are expected to
occupy.
(B) The density of crystal having shottky defect is smaller than that of perfect crystal.
(C) Schottky defect are more common in co-valent compound with higher co-ordination number.
(D) The crystal having shottky defect is electrically neutral as a whole.
30.* Which of the following statements are correct?

(A) Ferrimagnetic substances lose ferrimagnetism on heating and become paramagnetic.
(B) Ferrimagnetic substances do not lose ferrimagnetism on heating and remain ferrimagnetic.
(C) Antiferromagnetic substances have domain structures similar to ferromagnetic substances and their
magnetic moments are not cancelled by each other.
(D) In ferromagnetic substances all the domains get oriented in the direction of magnetic field and remain
as such even after removing magnetic field.

1. In the orthorhombic lattice of sulphur a = 10.46 Å, b = 12.87 Å, c = 24.49 Å. This unit cell contains 128 atoms
of sulphur (atomic weight = 32). Calculate the theoretical density.
2. For each of the following substances, identify the intermolecular force or forces that predominate. Using your
knowledge of the relative strengths of the various forces, rank the substances in order of their normal boiling
points. Al2O3 , F2, H2O, Br2, Cl, NaCl
3. An organic compound crystallizes in an orthorhombic pattern with two molecules per unit cell. The unit cell
dimensions are 12.05, 15.05 and 2.69 Å. If the density of the crystal is 1.419 gm cm-3, calculate the molecular
weight of the organic compound.
4. (a) If the density of crystalline CsCI is 3.988 g/cm3, calculate the volume occupied by a single unit cell in
the crystal.
(b) Calculate the smallest Cs-to-Cs internuclear distance which is equal to the length of the side of a cube
corresponding to the volume of one CsCI ion pair.
(c) Calculate the smallest Cs-to-Cl internuclear distance in the crystal, assuming each Cs+ ion to be
located in the center of a cube with Cl– ions at each corner of the cube.
5. A small sphere of radius 10Å was found to fit perfectly in the largest void of Simple Cubic arrangement.Find
the location of the sphere and the volume of the unit cell.
6. An element has a body centered cubic structure with a cell edge of 288 pm. The density of the element is
7.2 g/cc. How many atoms are present in 208 gms of the element ?
7. A metal crystallises with a b.c.c. structure with a density of 19.3 g.cm–3. Calculate the length of the body
diagonal of the unit cell. (Atomic weight of metal = 183.9)

3
8. The density of solid argon is 2/3 (amu/ Å 3) at 40K.If the Argon atom is assumed to be sphere of radius
1/ 3
Å, what percentage of solid Argon is apparently without anything.
9. A mineral of iron contains an oxide containing 72.36% iron by mass and has a density of 5.2 g/cc. Its unit cell
is cubic with edge length of 839 pm. What is the total number of atoms (ions) present in each unit cell ?
(Fe - 56, O-16)
10. Illustrate an octahedral void in the close packing of spheres. Why is it so called ?
11. Consider the arrangement of circles of equal radii with their centers arranged as per the 2-dimensional lattice
defined by a = b,  = 60° such that each circle is touching all its nearest neighbours. If all the void areas present
are additionally occupied by smaller circles of relevant size so that the void circles are just contacting their
neighbours find the packing efficiency of the configuration in percent.
12. Titanium crystallizes in a face-centered cubic lattice. It reacts with carbon or hydrogen interstitially, by allowing
atoms of these elements to occupy holes in the host lattice. Hydrogen occupies tetrahedral holes, but carbon
occupies octahedral holes.
(a) Predict the formulas of titanium hydride and titanium carbide formed by saturating the titanium
lattice with either "foreign" element.
(b) What is the maximum ratio of "foreign" atom radius to host atom radius that can be tolerated in a
tetrahedral hole without causing a strain in the host lattice?
(c) What is the maximum allowable radius ratio in an octahedral hole?
(d) Account for the fact that hydrogen occupies tetrahedral holes while carbon occupies
octahedral holes.
13. In Rock Salt type structure cations(radius r) occupy Octahedral holes in the FCC of anions(radius R) such that
there is no distortion in the FCC lattice. Find the perimeter of the shaded region.
Face centres
Rock salt type
14. An alloy of gold and cadmium crystallises with a cubic structure in which gold atoms occupy the corners and
cadmium atoms fit into face centres. What formula would you assign to the alloy?
15. Iron crystallizes in several modifications. At about 910°C, the body-centered cubic ‘’ form undergoes a transition
to the face-centered cubic ’’ form. Assuming that the distance between nearest neighbours is the same in the
two forms at the transition temperature, calculate the ratio of the density of  iron to that of  iron at the
transition temperature.
16. Volatile compound (A) crystallizes in fcc manner. It’s density in solid state is 2.3 g/cc.
25.45 g of compound (A) along with 39.6g of CO2 at 100ºC and 3.2 atmospheric pressure occupied 9.56 L
volume. Calculate the value of Vander Walls constant ‘b’ for compound (A). Compound (A) exists in gaseous
state at 100ºC.
17. A metal (M), shows ABAB arrangement of atoms in solid state, then what is the relation between radius of
atom (r) and edge length (a) and height (c) of HCP unit cell.
18. Ice crystallizes in a hexagonal lattice. At the low temperature at which the
structure was determined, the lattice constants were a = 4.53 Å and c = 7.41
Å (as shown in fig.). How many H2O molecules are contained in a unit cell?
(Density of ice = 0.92 gm/cc)

19. The ZnS zinc blende structure is cubic. The unit cell may be described as a face-centered sulfide ion sublattice
with zinc ions in the centers of alternating minicubes made by partitioning the main cube into 8 equal parts (as
shown in fig.)
(a) How many nearest neighbors does each Zn2+ have?
(b) How many nearest neighbors does each S2– have?

(c) What angle is made by the lines connecting any Zn2+ to any two of its nearest neighbors?
(d) What minimum r+/r_ ratio is needed to avoid anion-anion contact, if closest cation-anion pairs are
assumed to touch ?
r 1
20. Percentage of void space in AB solid having rock salt structure if r = having cation anion contact. Given
– 2
 = 3.15.
21. In an ionic solid r(+) = 1.6 Å and r(–) = 1.864 Å. Use the radius ratio rule to determine the edge length of the cubic
unit cell in Å.
22. NH4Cl crystallizes in a body-centered cubic lattice with a unit cell distance of 387 pm. Calculate
(a) the distance between the oppositely charged ions in the lattice and
(b) the radius for the NH4+ ion, if the radius for the Cl– ion being 181 pm.
23. The edge length of the unit cube of diamond is 356.7 pm and this cube contains 8 carbon atoms. Calculate:
(a) the distance dC–C between carbon atoms, assuming them to be spheres in contact;
(b) the fraction of the total volume that is occupied by carbon atoms.
24. A spinal is an important class of oxides consisting of two types of metal ions with the oxides ions arranged in
CCP layers. The normal spinal has one-eighth of the tetrahedral holes occupied by one type of metal ion and
one-half of the octahedral holes occupied by another type of metal ion. Such a spinal is formed by Zn2+, Al3+
and O2– with Zn2+ in the tetrahedral holes. Give formula of the spinal.
25. Strontium titanate, SrTiO3, has a cubic unit cell with a titanium at the cube center, and oxygen at each face
center, and a strontium at each corner. The length of the edge of the unit cell is 391 pm at 25°C. (a) What is the
coordination number of the titanium atom ? (b) what is the coordination number of the strontium atom ? (c)
what is the density of SrTiO3 at 25°C? (d) How far is each Sr atom from its nearest neighbours?
26. Given that  is the ratio of the observed to the theoretical densities of a solid.Can one give the idea about the
value of  for the following.
(i) Schottky defects are present in the solid.Find fraction of the missing units.
(ii) Interstitial defects are present in the solid.
(iii) Frenkel defects are present.
27. A transition metal M can exist in two oxidation states +2 and +3. It forms an oxide whose experimental formula
is given by MxO where x < 1.Then the ratio of metal ions in +3 state to those in +2 state is (in terms of x) :

PART-I
1. (B) 2. (D) 3. (A) 4. (B) 5. (B)
6. (A) 7. (B) 8. (A) 9. (A) 10. (B)
11. (B) 12. (A) 13. (C) 14. (D) 15. (A)
16. (A) 17. (C) 18. (C) 19. (A) 20. (C)
21. (D) 22. (B) 23. (B) 24. (A) 25. (B)
26. (B) 27. (A,C) 28-* (A,B,C) 29.* (A,B,D) 30.* (A,D)
PART-II
1. 2.075 gm/cm3 2. XY3 3. 208.4 gm mol-1.
4. (a) 7.014 × 10–23 cm3 (b) 4.125 Å (c) 3.572 Å
5. At the center of the cube, Volume = 1000( 3  1)3 Å 3
6. 24.16 × 1024 7. 5.48 Å 8. 40% 9. 56
10. Octahedral void is present at the body center, which is formed by six face centered atoms.
11. 95. 12. (a) TiH2 , TiC. (b) 0.225 (c) 0.414 (d) H-atom is small
13. 4( r + 2R ) 14. The formula the alloy will be AuCd3.
2 2
15. 1.09. 16. 327. 6 cm3 mol–1 17. a = 2R, c = 2a = 4r
3 3
18. 4 water molecules
19. (a) 4 (b) 4 (c) Tetrahedral angle, 109º28’ (d) 0.225

20. 30% 21. 4 22. (a) 335.15 pm (b) 154.15 pm
23. (a) 154.4 pm (b) 0.34 24. ZnAl2O4
25. 6, 12, 5.1 g/cc, 276 pm (Atomic mass : Ti = 48 ; Sr = 88 and O = 16)
26. (i)  < 1, fraction = ( 1 -  ); (ii)  > 1 ;(iii)  = 1. 27. 2(1 - x) / (3x - 2)

SOLID STATE
EXERCISE # 1
PART - I
A-2. Covalent  Diamond ; Ionic  NaCl
Dipole-dipole  HCl ; Metallic  Al
B-1. Contribution of atom

1
At face center = ; At body center = 1
2
3a 1.732  286
B-2. For bcc structure 3 a = 4r,, r= = = 123.8  124 pm.
4 4
B-5. We know for B.C.C. 4R = a 3

287  3
R= = 124.27 pm.
4
2  52
density =
6.023  10 23
287  10 
—10 3 = 7.30 gm / cm3.
C-1. Rhombous. 60o and 120o

Whole available space not occupy.
No. of void = 2
Type of void = Triangular
3 R
Sin 60 = = R  r   r = 0.155 R
2
C-3. For close packed structure of AB type solid

r+ / r– = 0.225 – 0.7342
Minimum value of r– = r+ / 0.732 = 75 / 0.732 = 102.5 pm
Maximum value r– = r+ / 0.225 = 75 / 0.225 = 333.3 pm
C C C
A A
B B B
C-5. A A Octahedral void, at edge center & body center..
C C C
 Tetrahedral voids on body diagonal.
D-2. (i) distance between 1 and 2 = 2r

2 and 3 = 2r
1 and 3 = 2 2r   2r
2 2 = (2 3 ) r
(ii) Shape = square and length of square = 2r

ZM 27 Z  27amu
D-3. We know d = (a )3 =
16
=
4.0 Å3

Z = 4 Then unit cell f.c.c. and
we know for f.c.c. 4r = a 2
4
r= 2 = 2 Å.
4
D-4. Number of octahedral voids in fcc = 4.

Number of tetrahedral voids in fcc = 8.
a
Distance between two octahedral voids =
2
a
Distance between two tetrahedral voids =
2
E-1.
ABAB............type arrangement (unit cell = HCP).
6  vol. of 1 atom
E-2. Packing efficiency of hcp = Vol. of unit cell
Z M 6  24.31
Volume of unit cell = N  d = = 13.9179 × 10–23 cm3.
A 6.023  1023  1.74
Packing fraction  Vol. of unit cell 0.741  13 .9179  10 23

So, volume of 1 atom = = = 1.718 × 10–23 cm3.
6 6
4 3
Volume of 1 atom = r .
3
1/ 3
 Volume of 1 atom  3 
Radius of 1 atom = (r) =   = (0.41055 × 10–23)1/3 = 1.60 Å.
 4 
F-2. In NaCl nearest neighbour of Na+ is 6Cl– and next nearest is 12 Na+.
4  58.5
F-3. d=

6.023  10 23 .564  10 — 7 
3 = 2.16 g/cm3.
F-6. (a) KBr is NaCl type, so no. of K+ & Br– are 4 each. (b) a = 2rK   rBr   = 2(1.33 + 1.95) = 6.56 Å
4  119 r
(c) Density = 23 8 3 = 2.80 g/cm3 (d) For octahedral voids, r = 0.414
6.02  10  ( 6.65  10 ) 
F-9. In diamond structure C atoms forms fcc structure and C atom also occupied in alternet tetrahedral void. So
1 1
number of C atom in (also same in Si)  ×8+ × 6 + 1 × 4 = 8 atom (in diamond)
8 2

G-2. In 100 mole of NaCl 10–3 mole of Sr2+ is doped
 No. of hole in 100 mole of NaCl due to 10–3 mole of SrCl2 = 10–3 mole
10 3 mole vacancies mole vacancies

 1 mole of NaCl have vacancies = 1 mole of NaCl = 10–5 1 mole of NaCl = 10–5  6.02  1023
100
vacancies
= 6.02  10+18 mole of NaCl
PART - II
A-2. Unit cell : Unit cell is the smallest portion of a crystal lattice which, when repeated in different directions,
generates the entire lattice.
A-4. For rhombohedral system, axial distance and axial angles are a = b = c,  =  =  900
A-5. In Bravais lattices, each point has identical surroundings.
3a 3 2 1.732  2
B-2. Distance between two nearest neighbours in bcc = = = = 4.503 Å.
2 2 2
B-4. de = a
dfd = 2a
3a
dbd =  dfd > de > dbd
2
C-1.
C-3. In ABB AABB A, there is no close packing as there are repeated planes adjacent to each other.
D-1.
D-4. 4r = a 2
4r 4  1.28
a  Å = 3.62 Å
2 2
1
D-7. No. of tetrahedral voids = 8 × =1
8
No. of Octahedral voids = 1×1 = 1 (at body center).

E-3. Volume of hexagon :
a  1a 3 a 2
a 3 3    = 6 3a
tan30º = 2  y So y= = a and Area of hexagonal surface = 6
2 1 2  2 2  4
volume of hexagon = area of base × height
6. 3 2 6. 3 2
= × a2 × 2 a = × (2r)2 + 2 × (2r) = 24 2 r3
4 3 4 3
E-5. No. of A atoms = 6.

2
No. of C atoms = 6× = 4.  Formula = C4A6 or C2A3.
3
F-2. In rock salt structure, Cl– forms fcc (ccp) lattice & Na+ occupies octahedral voids, So tetrahedral voids are
vacant.
F-4. Coordination number of Zn2+ ion in Zinc blende = 4.

Zn2+ ion present in half of tetrahedral void formed by S2– in fcc unit cells.
1 1
F-6. A ×8=1,B4 = 2 and O2– = 4 so formula of spinal = AB2O4
8 2
F-8. On increasing tempr C.N. decreases.

 CsCl (8 : 8) structure changes into (6 : 6) NaCl type structure.
G-2. Since Ag+ (cation) is smaller than Cl– (anion) & hence cation is present in voids.
–
In CaF2 , Fanion is smaller..
G-4. p-type semiconductors acquired positive charge because p-type semiconductor have holes due to presence
of 13 group elements in 14 group elements.
PART - III
 1
1. In HCP structure corner atom contribution is  6  .
 
3. Zinc oxide losses oxygen reversible at high temperature and turn yellow.
EXERCISE # 2
PART - I
1
2. (a) Number of atoms in 2D unit cells = × 6 + 1 × 1 = 3.
3
Number of atoms  Volume of 1 atom
(b) Packing efficiency (of 2 layers) = Total volume of 2 layers of unit cells × 100
4 3 4 3
3
r 3 r
3 3
Packing efficiency = area of hexagon  height × 100 = 3
× 100 = 60.43%.
6  ( 2r )2  (2r )
4

4. Number of atom effectively present in a cubic unit formed by
arrangement of eight B.C.C unit cell =
1 1 1
8× + 12 × +6× + 1 + 8 = 16.
8 4 2
2M
6. Density (d) = 2 = M = 27 amu
33
Then No. of atoms present in 243×1024 amu is
243  10 24
 = 9×1024
27
11. Edge length a = 500 pm = 500 × 10–10 cm

Volume, a3 = (500 pm = 500 × 10–10 cm)3 = 12.5 × 10–23 cm3.
For fcc structure, number of atoms per unit cell, Z = 4
Atomic mass, M = 98.5 g
density, r = 5.22 g cm–3
We know that :
M Z 98.5  4
Avogadro constant, N0 = = = 6.038 × 1023 atoms mol–1.
12.5  10 23  5.22
3
a p
13. Calculation of c.
a 2a a
cos30º = so x= =
2 x 2 3 3
Applying pythogoras theorem : x + h = a22 2
a2 2 2 2 r..
so h2 = a2 – x2 = a2 – = a2 and h= a=2
3 3 3
3
2
so height of hexagon c = 2h = 2 a.
3
ZM
14. Density of hcp = N  ( Volume of unit cell)
A
3 2 6  1.732
Volume of unit cell = 6 × a ×C= × 295.5 × 295.5 × 472.9 × 10–30 = 107.281 × 10–24 cm3.
4 4
6  47.8
density = = 4.438 g/cm3.
6.023  10 23  107.281 10  24

17. Number of octahedral void in ccp = Z ; Number of tetrahedral void in ccp = 2Z.
For A2B, Number of anion B = 4.
Cataion (A) present in all octahedral void (100% occupied) and half tetrahedral void (50% occupied), then
1
number of cation (A) in unit cell = 4+8× = 8.
2
So, formula of compound = A2B.
1
19. No. of Mg2+ per unit cell = 8 [At corners]  =1
8
1
No. of Ti per unit cell = 1 [body center]  =1
1
1
No of O per unit cell = 6 [Face center]  =3
2
so formula = MgTiO3
atom are removed along face diagonal
1 6 3
No. of Mg2+ = 6[At corner]  = =
8 8 4
1
No. of Ti per unit cell = 1 [Body center]  =1
1
1 5
No. of O per unit cell = 5 [Face center]  =
2 2
So formula of compound = Mg 3 TiO 5
4 2
3 5
Formula mass = 24  + 48 + 16  = 18 + 48 + 40 = 106 amu
4 2
As corner ion are touching so = a = 2 rMg2 = 2  0.7 = 1.4 Å
mass 106  1.67  10 24

d= = g/cm3 = 64.5 g/cm3
Volume (1.4)3  10 24
21. (i)
by charge balancing
2x + 3 [0.93 - x] = x
x = 2.79 so Fe3+ = 0.14
In 0.1 mole compound Fe2+ = 0.279 & Fe3+ 0.014
No. of vacancies = 0.007 mole
= 0.007  6.02  1023 vacancies.
(ii) No. of Fe ion = 0.079 mole which are replaced by Sn4+ with each replacement one vacancies is created.
2+
0.079 0.079
So no. of vacancies due to replacement of Fe2+ by Sn4+ = mole = = 0.0395 mole
2 2
Total vacancies = [0.007 + 0.0395] mole = 0.0465  6.02  1023 vacancies

PART - II
2.
2 Square Voids (4)
1 7 1 1
4. X = 7x = ; Y= x 6 = 3. ; Z= .  X7/8 Y3 Z1/8 = X7 Y24 Z
8 8 2 8
2(r   r  )
7. For (bcc) = r+/r– = 0.732 and a =
3
and diameter of cubical void (2r+) = a( 3 –1) = 2.888 × 0.732 = 2.108 Å.
8. no. of oxide ions = 4

1 4
no. of A particles = 8 =
6 3
1 4
no. of B particles =  4 =
3 3
so formula is A4/3 B4/3O4 or ABO3.
9.
a 2
11. Distance between nearest neighbours is along the face diagonal = .
2
ZM 4  195
12. Density = N  a3  6.02  1023  (3.9231 108 )3 = 21.86 g/cm3
A
for fcc lattice, 4r = a 2
a 2 3.9231 2
so, r= = Å = 1.387 Å.
4 4
14. Cu4 Ag3 Au

  
3 1
Froms c.c.p. , th
of tetrahedral voids , of Octahedral voids [ No. of O- voids = 4]
8 4
z=4 , [ No. of T- voids = 8].
17. Number of nearest neighbours in hcp pattern in its own layer = 6.
21. r
Rb 

 rCl  rK   rBr   r K   
 rCl  rRb   rBr  
3.285 + 3.293 – 3.139 = 3.439.

23. It is fluorite (CaF2) structure. Since formula is AB2
 No. of B atoms is twice the no. of A atoms. Hence B occupies all the tetrahedral voids (100%).
AB2 is (8 : 4) compound (Fluorite Structure Compound)

C.N. of A C.N. of B.
28. Some of O2– combine with each other forming O2 gas which is liberated learning behind electrons at the site
vacated by oxide ions.
29. Randomness (entropy) in amorphous solids is more than that in crystalline solids.
31. Fcc can be viewed in two following ways -

(i) Planes along the faces (and parallel to it) of the unit cell.
 Each atom touches 4 in same layer, 4 in layer above and 4 in layer bellow it.
(ii) Planes along closest packed spheres  each atom touches 6 atom in same layer, 3 in layer above and 3
in layer below it.
33. When silcon is doped with some group-15 element, the some of the positions in the lattice are substituted by
atoms fo groups -15 elements have five valence electrons. After forming the four covalent bonds with silicon
(or anyother group-14 element such as germanium). one excess electron is left on them.
Since this electron is not involed in bonding it becomes delocalized and contributre to electrical conduction.
Silicon dped with group 15 element behaves as a n-type semconductor.
PART - III
2. (A) ZnS crystal
S2– ion are present in fcc lattice & Zn2+ ion occupy all the tetrahedral voids distance of tetrahedral voids from
3a
corner =
4
(B) CaF2  Fluorite structure
Ca2+ ion are present in ccp lattice & F– ion are present in all tetrahedral voids.
(C) NaCl  Rock salt Type structure
Cl– ion are present in ccp lattice & Na+ ion occupy all the octahedral voids.
(D) Diamond crystal  C atom present in fcc lattice in which alternate tetrahedral voids are occupied by C
atom.

PART - IV
1 1
2. No. of X = 8 × +6× =4  4 XY unit per cell.
8 2
1
No. of Y = 1 + 12 × =4
4
3. At edge center , there is octahedral void in f.c.c. lattice.

 C.N. of Y = 6
(6 : 6) C.N.  NaCl Structure.
1
5. On heating, ZnO(s) dissociates reversibly as ZnO Zn2+ + O + 2e–
2 2
Zn2+ ions occupy certain interstitial sites whereas the electrons released are present at the neighbouring sites,
which act as F-centers.
6. In the crystallization, some Ag+ ions will get replaced by as many half of Cd2+ ions. Thus the cation vacancies
will be the same as the number of Cd2+ is ions incorporated.
EXERCISE # 3
PART - I
1. In the figures given below draw the unit cell of the corresponding structure and identify these plane in your
diagram (out of fcc and simple cubic).
(i) Face plane (ii) Body diagonal plane (iii) Plane passing through the face diagonals.
1 1
2. The No. of atom of A for unit cell =  8  8  4  2  = 3
 
Then formula = A3B4.
3. Calculate no. of atoms of A & B per unit cell.

1
No. of atoms of A/ unit cell = 8 × = 1.
8
1
No. of atoms of B/ unit cell = 6 × = 3.
2
 Formula is AB3 .
4. Again to have the maximum number of spheres the packing must be hcp.
Maximum number of spheres = 25
Area of the figure = 2 × Area of equiletral tringle of side = 4 cm

3
=2× × (4)2 = 13.856
4

25 marbel
= 1.804 marbles/cm2
13 .856 cm2
1
a
5. (a)  Y3
2
1
a = 2Y 3
4  6.023  Y  10 —3
density (d) =

6.023  10 23 2Y1/ 3  10 — 9 
3 = 5.0 Kg/M3
(b) Observed density of AB is 20 Kg/M3

Which is Higher then calculate density 5kg/m3 thus AB has either interstitial impurity defect or substitutional
impurity defect.
6. In cubic close packing no. of tetrahedral void = 2 × no of atom. As there are 4 S2– ions at lattice point and they
r
need 4 Zn+2, which adjusted in alternate tetrahedral void (0.225 < < 0.414).
r

r1 
7. For f.c.c.  r  0.414  octahedral void
 2 
r1
r2 = 0.225 Tetrahedral void
a 2
We know along face diagonal for f.c.c. 4r2 = a 2  r2 =
4
required diameter of interstitial sites = 2r1 = 2 × 0.414r2
2  .414  2  a 2  .414  2  400
Diameter = = = 117.1 pm.
4 4
ZM
8. d=  Z = 20 × 10–1 = 2
NA a3
3
So its is a bcc unit cell. Hence 3 a = 4R so R= × 5Å = 216.5 pm.
4
9. (A) Simple cubics and fcc (i) have the cell parameters a = b = c &  =  =  (choice P) and belong to the same
crystal system (choice (s)).
(B) Cubic & rhombohedral (i) have the cell parameters a = b = c and  =  =  (choice P) and (ii) are two crystal
systems (choice (q)).
(C) Cubic and tetragonal are two crystal system (q).
(D) Hexagonal & monocubic (i) two crystal system choice (q) p (ii) have only two crystallographite angles of
90º choices.
 1  1
10. Total no. of atoms in 1 unit cell = 12 x  + 3 +  2 x  = 6
 6  2
2
11. C= 4r = Height of the unit cell.
3
3
Base area = 6 × (2r)2 .
4
2 2 2 2
Volume of the hexagon = Area of base x Height = 6 . a × c = 4r  4r = 24 2.r
3
3 3

4 3
6 r 
13. Packing fraction = = 3  = 0.74 = 74%
24 2 r 2 3 2
 empty space = 100 – 74 = 26%.
14. Frenkel defect is a dislocation defect.

Trapping of an electron in the lattice leads to the formation of F-center.
15.
4R = L 2
so, L = 2 2 R
Area of square unit cell = ( 2 2 R)2 = 8R2
 R 2 
 
Area of atoms present in one unit cell = R2 + 4 4  = 2R2
 
2R 2
so, packing efficiency = × 100
8R2

= × 100 = 78.54%
4
16.
1
17. No. of M atoms = ×4+1=1+1=2
4
1 1
No. of X atoms = ×6+ ×8=3+1=4
2 8
so formula = M2X4 = MX2
PART - II
1. BCC - points are at corners and one in the center of the unit cell.
1
Number of atoms per unit cell = 8 × 1 2 .
8
FCC - Points are at the corners and also center of the six faces of each cell.

1 1
Number of atoms per unit cell = 8 ×  6  = 4.
8 2
2. mass (m) = density × volume = 1.00 g

Mol. wt. (M) of NaCl = 23 + 15.5 = 58.5
Number of unit cells present in a cube shaped crystal of NaCl of
  a 3  NA m  N A 1 6.023  10 23
mass 1.00 g =  
M Z M Z 58.5  4
(In NaCl each unit cells has 4 NaCl units. Hence Z = 4)
 Number of unit cells = 0.02573 × 1023 = 2.57 × 1021 unit cells.
3. When an atom or ion is missing from its normal lattice site, a lattice vacancy is created. This defect is known
as Schottky defect . Here equal number of Na+ and Cl– ions are missing from their regular lattice position in the
crystal. So it is Schottky defect.
1 1
4. Number of A ions per unit cell = × 8 = 1 ; Number of B ions per unit cell = × 6 = 3
8 2
Empirical formula = AB3.
5. In case of a face-centerd cubic structure, since four atoms are present in a unit cell, hence volume.
 4 3  16 3
V = 4  r   r
3  3
6. According to question : Number of Y atom in ccp unit cell = 4

2 16
Number of X atom in ccp unit cell = 8 × =
3 13
Formula of compound = X16/3Y4 = X16 Y12 = X4 Y3
7. In fcc unit cell 4r = 2a [r = radius of Cu atom, a = edge length]
2a
So r =
4
2  361
r= = 127 pm.
4
8.
2 × 110 + 2 × r– = 508
2r– = 288
r– = 144 pm

9. Packing fraction of CCP = = 0.74  74%
3 2
 Percentage of free space in CCP = 100 – 74 = 26%
 3
Packing fraction of BCC = = 0.68  68%
8
 Percentage of free space in BCC = 100 – 68 = 32%
A 1 B 1
10. 8 5
8 2
Formula of compound A2B5.

11. FCC lattice
a = 361 pm
a 2 = 4r
361 2
r= = 127.6  128 pm.
4
3 3
12. For BCC structure 3 a = 4r r= a =  351 = 152 pm.
4 4
PART - III
3. Given : a = 430 pm, M = 23.0 u, d = 0.9623 g cm-3 NA= 6.023x 1023mol-l] [½ Mark]
Asked : Z = ? [½ Mark]
Z M NA  a 3  d
Formulae : d = 3 ; z= [½ Mark]
NA  a M
Explanation : d = density, a = edge length, M = atomic mass, NA = Avagadro number,
0.9623 g cm –3  6.023  10 23  ( 430 )3  (10 –10 )3 cm3

Substitution & Calculation : Z =
23
0.9623  6.023  43  43  10 –4
Z= = 2.004 atoms/unit cell. [1 Mark]
23
Ans.: 2.004 atoms/unit cell.
4. Given : Z = 4, w = 200 g, N = 4.12 × 1024,d= 7.2 g cm-3 [½ Mark]

Asked : a = ? [½ Mark]
Z M Z w w N
Formulae : d= ; a3 = ;  [½ Mark]
NA  a3 dN M NA
Explanation : d = density, a = edge length, M = atomic mass, NA = Avagadro number
Z = Effective number of atoms, w = Weight of element
N = Number of atoms of element
Z M 4  200 800
Substitution & Calculation : a3 d  N = 24 = ×10–24
7.2  4.12  10 29.664
a3 = 26.968 × 10–24 cm3 = 26.968 × 10–6 cm : a = 299.8 pm [1 Mark]
Ans.: 299.8 pm
ZM
6. d = a3  N
Z M 2  200
N = a3  d = (300 )3  (10 –10 cm3 )  5.2 cm – 3
400 400  10 24
N= = = 2.85 ×1024 atoms
27 10 – 24  5.2 140.4
14. (i) r = 125 × 10–12 m , 4r = 2a [1 Mark]
4r
a= = r × 2 2 = 125 × 10–12 × 2 2
2
= 250 × 1.414 × 10–12 m = 354 pm [1 Mark]

(ii) Number of unit cell in 1 cm 3
Total volume 10 –6 m 3
= Volume of one unit cell = = 2.261 × 1022 unit cells [1 Mark]
44.2110 – 30 m 3
ZM
15. (a) d = [1 Mark]
a3  NA
Z  56
7.80 =
( 290 )  10 – 30  6.02  10 23
3
7.80(290 )3  10 –30  6.02  10 23 114 .52

Z= = = 2.04  2.00 b cc [1 Mark]
56 56
(b) On heating it is because electrons are trapped in place of O2–.which increases electrical conductivity. On
hating O2– changes to O2which is lost to atmospheres. [1 Mark]
1
22. (i) Atoms per unit cell in a body centred cubic cell = 8 × (from corners) + 1 (from body centre) = 2 [½ M]
8
1 1
(ii) Atoms per unit cell in a face- centred cubic cell = 8 × (from corners) + 6 × (from face centres) = 4
8 2
[½ M]
25. Given : Z = 2 for bcc unit cell, M = 56 g mol– 1, d = 7.87 g cm– 3, [½ Mark]
Asked : NA = ? [½ Mark]
Z M Z M
Formulae : d= 3 ; NA = [1 Mark]
NA  a d  a3
Explanation : d = density, a = edge length, M = atomic mass, NA = Avagadro’s number
Substitution & Calculation : Mass of iron (w) = 7.87 × Volume
Volume = (a)3 = (286.65)3 pm = 2.34 × 10– 23 cm
Mass = 7.87 × 2.34 × 10– 23 g
ZM 2  56
NA = 
w 7.87  2.34  10 – 23
 NA = 6.022 × 1023 [1 Mark]
Ans.: NA = 6.022 × 10 23
31. Given :4Ca2+ and 8F– ions means, numbers of formula units = 4CaF2
Z=4
M = 78.08 g mol–1, d = 3.18 g cm– 3, a = 5.46 × 10–8 cm [½ Mark]
Asked : NA = ? [½ Mark]
Z M Z M
Formulae : d= ; NA = [1 Mark]
NA  a3 d  a3
Explanation : d = density, a = edge length, M = Molar mass, NA = Avagadro’s number
Substitution & Calculation :
Z M 4  78.08g mol 1 312.32  10 24 3123 .2

NA = = = = × 1023
d  a3 3.18g cm 3  (5.46 )3  10 24 cm3 3.18  (5.46)3 517 .61
NA = 6.0338 × 1023 mol–1 [1 Mark]
Ans.: NA = 6.022 × 1023

32. Let us assume Z = 4 (copper has fcc)
Z M 4  63.54
d= 3 : 8.95 =
a  NA a  6.023  10 23
3
4  63.54 254.16
a3 = 23  × 10–23  4.7 145 × 10–23 cm3
8.95  6.023  10 53.91
a = 47.145 × 10–24 cm3
3
a= 3
47.145 × 10–8 cm3 = 3.612 × 10–8 cm = 361 .2 pm
a 361 .2
For Fcc 4r = 2a : r= = = 127.7 pm
2 2 2  1.414
It shows 'Cu' has fcc structure
34. Given : a = 400 pm, face-centred cubic unit cell. [½ Mark]

a
Formulae : Radius for face-centred cubic unit cell is r = [1 Mark]
2 2
Explanation : r = Radius of atom, a = edge length
a 400 400 400
Substitution & Calculation : r = = = = = 141.84 [1 Mark]
2 2 2 2 2  1.41 2.82
Ans.: 141.84 pm.
37. Given : a = 316.5 pm, BCC,unit cell [½ Mark]

3a
Formulae : Radius of atom for BCC, unit cell is r = [1 Mark]
4
Explanation : r = Radius of atom, a = edge length
3a 1.732  316 .5 pm 548 .178

Substitution & Calculation : 4r = 3a : r = = =
4 4 4
r = 137.04 pm. [1 Mark]
Ans.: 137.04 pm.
PART-I
1. Coordination number of square packing pattern is 4.
1 1
2. for X, 8 × =1; for Y, 6 × =3
8 2
so, XY3
1 7
3. No. of X atom per unit cell = 7 × =
8 8
1
No. of Y atom per unit cell = 6 × =3
2
 Formula = X7/8 Y3 or X7 Y24.

4. Na = 1×1 = 1
1
W = 8× =1  NaWO3
8
1
O = 12× = 3.
4
1
5. Number of F atom in metal fluoride = × 8 = 1.
8
Number of M atom in metal fluoride = 1 × 1 = 1.
So formula of metal fluoride = MF.
3a 3  4. 3
6. r+ + r– = = = 3.72 Å
2 2
– +
7. CsCl compound has bcc arrangement. Cl ion forms cubic lattice and Cs ion occupied at body center of unit
cell.
d  MCsCl
8. Density of crystalline CsCl = 3.988 g/cc then, d = N  (a)3
A
Z  MCsCl 1 (132.9  35.5)

Volume of unit cell (a)3 = NA  d = 6.023  1023  3.988 = 7.01 × 10
–23 cm 3.
9. Radius ratio Types of structure Coordination No.

r+/r– < 0.155 linear void 2
0.155  r+/r– < 0.225 triangular void 3
0.225  r+/r– < 0.414 tetrahedral void 4
0.414  r+/r– < 0.732 octahedral void 6
0.732  r+/r– < 1 cubical void 8
r r
10. for tetrahedral voids = 0.225  for octahedral voids = 0.414
R R
2 2
2a a a a a
11. d1–2 = = ; d2–3 =     =
2 2 2 2 2
Hence d1–2 = d2–3.

12. According to figure, it shows a simple cubic lattice. Now observe the center atom , its has 6 nearest neighbours
13. a= 2 2r
 v = a3 = 16 2 r3 = 16× 2 × (2 × 10–8)3 = 1.8×10–22 cm3
14. When all particle along one body diagonal are removed, these 2 X particles from corner are removed, one Y
particle removed & 2 Z particle removed.
1 1 15
Hence new arrangement, X particle = 6 6  ; Y particle = 3 ; Z particle = 6
8 2 4
Hence formula = X15 / 4 Y3 Z 6  X 5 / 4 YZ 2 = X5Y4Z8
1 1  1 1  5
15. In new arrangement, A particles =   8   6  –   4   2  =
 8 2   8 2  2
1   1  5
& B particles =   12  1 – 1   2  =
4   4  2
So, formula is AB.

2  4 2R
16. Perimater of plane is = 2C + 8R = + 8R = 6.437 R
3
17. Ionic solid having C.N. = 6 cation in octahedral holes.
r
Hence, 0.414 <  r –  < 0.732.
 
18. For ZnS  4 (rZn2+ + rS2–) = 3 a.
4(r  r 2– )
Zn2 S (0.83  1.74 )
a=  a=4 = 5.93 Å.
3 1.732
19. Refer NaCl (Rock salt structure).

20. Z = 4, M = 60
60 × 4 gram –––––––––––––––––––– 6.023 × 1023 unit cells
6.02  10 23
1 gram –––––––––––––––––––– = 2.5 × 1021
60  4
1 1
21. Total positive charge = Charge on Mg2+ + Charge on Al3+ = ×8×2 + ×4×3 = 8 electronic charge.
8 2
22. Based on radius ratio.

23. Ferromagnetic substances can be magnetised permanently.
24. There is both a vacancy and an interstitial ion.
25. In these defects stoichiometry of compound maintained.
26. In schottky defect density decreases while interstitial defect density increases.
ZM 4  207
27. Density = N  volume so, Volume = = 1.213 × 10–22 cm3 4r = a 2
6.02  1023  11.34
;
A
4.95  10 8  2
r= = 175 pm
4
Volume = a3 = 1.213 × 10–22
so, a = (1.213 × 10–24)1/3
a = 4.95 × 10–8 cm.
28-* Na+ & F– are isoelectronic hence they will have same screening const (s) but not the effective nuclear charge.
and rNa  rF  = 2.31 Å and rF = 1.36Å
 rNa rF   0.7 (coordination = 6, rock salt structure)
29.* Schottky defect is only observed in ionic compound.
30.* Ferrimagnetic substances lose ferrimagnetism on heating and become paramagnetic. In ferromagnetic
substances all the domains get oriented in the direction of magnetic field and remain as such even after
removing magnetic field.
PART-II
mass
1. d=
volume
For orthorhombic volume = (a × b × c)
128  32  1.67  1024

= gram/cm3 = 2.075 gram/cm3
[10.46  12.87  24.49]  1024

2. Al2O3 – ionic Br2 – vanderwaal F2 – vanderwaal
Cl – dipole dipole H2O – dipole - dipole (H–bonding) NaCl – ionic,
F2 < Br2 < Cl < H2O < NaCl < Al2O3
ZM
3. d=
6.02  10 23  [a  b  c ]
2M
1.419 = gram/cm3  M = 208.4 gram/mol.
6.02  1023  [12.05  15.05  2.69]  10  24
mass of NA unit cells 168.5

4. (a) volume occupied by NA unit cells = density = = 42.25 cm3
3.988
42.25
so volume of one unit cell = = 7.014 ×10–23 cm3
6.02  1023
(b) smallest Cs – Cs distance = a = (volume)1/3
= (7.014 × 10–23)1/3 = 4.125 Å
a 3 4.125 3
(c) smallest Cs – Cl distance = = 3.572 Å.
2 2
5. For simple cubic lattice

2(R + r) = a 3 = 2R 3 [for simple cubic lattice a= 2R]
r 10
R=  3 —1
=   3 — 1 Å
3
 2  10 
Then volume = a3 = (2R)3 =  
 3 —1 
   = 1000 ( 3 +1) Å3
6. Volume of one unit cell = a3 = (288 × 10–10)3 cm3

mass 208
Volume of 208 g of element = density  7.2 = 28.88 cm3
28.88
so no. of unit cells in this volume = = 12.09 × 1023 unit cells
[ 2.88  10 8 ]3
Since Z = 2
so Total no. of atoms = 2 × 12.09 × 1023 = 24.18 ×1023.
ZM 2  183.9
7. a3 = N  d 
A 6.02  1023  19.3
so a = 3.16 Å
now length of the body diagonal = a 3 = 5.48 Å.
2
8. Actual given density = amu / Å3
3
40 40
Density when 100% solid Ar filled = 3 = amu / Å3
4  3  36
   
3  1 / 3 
 40 2 
  
then % of solid Ar without anything =  36 3   100 = 40% Ans.
 40 
   
  36  

72.36 27.64
9. ‘Fe’, ‘O’  1.292 ‘Fe’, 1.7275 ‘O’
56 16
Hence proportion is 1 : 1.33 ; So Empirical formula is Fe3O4 , Empirical formula mass = 232 amu
Now if there are x formula units in the unit cell
x (232 )
6.02  10 23
5.2 =  x = 7.968  8
(8.39  10 8 )3
Hence number of ions in the unit cell = 56
1
R 2   (0.155R )2
11. Packing fraction = 2 × 100 = 95%
1 2 3
(2R )
2 2
12. (a) For titanium hydride

No. of Ti atom per unit cell = 4
No. of H atom = 8 [in tetrahedral voids] × 1 = 8.
So formula of compound = Ti4H8 or TiH2
For titanium carbide
No. of Ti atom per unit cell = 4
No. of C atom per unit cell = 4 [in octahedral voids] × 1 = 4.
So formula of compound = Ti4C4 = TiC4
rH
(b) For tetrahedral void. rTi = 0.225
rC
(c) For octahedral void rTi = 0.414
(d) The void occupied by small size particle is depends on radius ratio. As per radius ratio H atom
occupy tetrahedral void not octahedral void.
13. Perimeter = 2a + 2a
= 2[2(R + r)] + 4R = 4 [r + 2R]
1
14. Number of Au atoms in unit cell = ×8=1
8
1
Number of Cd atoms in unit cell = ×6=3
2
The formula the alloy will be AuCd3.
Zfcc  M 4M ZBCC  M 2M

15. dfcc = N  (a )3 = N  (a )3  dBCC = N  (a )3 = N  (a )3
0 fcc 0 fcc 0 bcc 0 bcc
3
dfcc  abcc 
dBCC = 2  a fcc 
According to question 2 afcc = 3 abcc

3
 abcc   2 dfcc  2
=  a  =  
  
 fcc

  3
  dBCC = 2  3  = 1.09.
 

 39.6 
16. PCO2 × 9.56 =   × 0.082 × 373
 44 
PCO2 = 2.88
(PA)gas = 0.32
For A- gas  PA × V = nRT
= 0.32 × 9.56 = nA × 0.082 × 373
ngas = 0.1 mole.
so molar mass of A = 254.5
ZM
Again dA = N  a3
0
4  254.5
a3 =
6.02  1023  2.3
a3 = 735.2 × 10–24
a = 9 × 10–8
4r = 2a
For FCC lattice
2
r= a = 3.19 × 10–8 cm.
4
4 3 4
b = 4  r  × NA = 4 × × 3.14 [3.19]3 × 10–24 ×6.02 ×1023
3  3
= 327.26 cm3/mole.
2 2
17. a = 2R, c = 2a = 4r
3 3
ZM Z  18
18. d = N  Volume  0.92 =
0  6 3 a2 
6.02  1023   c
4
 
Z  18
 0.92 =  Z = 4.
 6 3 
6.02  1023   ( 4.53)2  7.41 1024 
 4 
19. (a) As each Zn2+ ion is present in tetrahedral void. So it is coordination number is = 4.
(b) Similarly S2– ion have coordination number = 4.
(c) As Zn2+ ion is present in tetrahedral void that's why line's connecting any two nearest neighbour and Zn2+
have angle = 109º28'.
rZn 2 
(d) For tetrahedral voids radius ratio is r 2  = 0.225.
S
a 3r– a a a
20. r+ + r– =  = ; r– = and r+ =
2 2 2 3 6
4  a  a 
3 3
4 3 3 4       
4  (r  r– ) 3  6   3  
3 
Packing fraction = = = 0.7.
a3 a3
Percentage void = 30%.

r 1 .6
21. r = 1.864 = 0.858
So, it is CsCl type unit cell
So 3 a = 2(r+ + r–)
2(1.864  1.6)
So a = Å = 2 x 2Å = 4Å
3
a 3 387  3
22. (a) Distance =  = 335.15 pm (b) rNH4  = 335.15 – 181 = 154.15 pm.
2 2
3
4  dc  c 
8x  
1 a fcc 3  2 
23. (a) dc–c = x 3 . = 154.4 pm (b) fraction = = 0.34
2 2 a3
24. O 4 Zn 1 Al 1
8 4
8 2
So, formula is ZnAl2O4.
1
25. No. of Sr atom per unit cell = 8 [corner] × =1
8
No. of Ti atom per unit cell = 1 [center] × 1 = 1
1
No. of O atom per unit cell = 6 [face center] × =3
2
So formula of compound SrTiO3
Edge length = 391 pm.
(a) Ti atom is present at body center of fcc lattice which act as octahedral voids. Which has coordination
number = 6.
(b) Sr atom is present at corner of fcc lattice with has coordination number = 12.
ZM 184
(c) density = d = N  a3 = = 5.1 gram/cc.
0 6.02  10 23  (3.91 10 8 )3
2a a
(d) In fcc lattice distance of nearest neighbour of Sr atom = = = 276.5 pm.
2 2
26. (i) In shottky defects density decreases.
(ii) In interstitial defects density increases.
(iii) In frenkel defects density remain same.
27. 2 (1 – x) / (3x – 2)
 Applying charge balance , 2y + 3(x – y) – 2 = 0

 y = 3x – 2
M3  x–y x – ( 3 x – 2) (2x  2) 2(1  x )

 = y = = =
M2 3x – 2 3x – 2 3x – 2

IUPAC NOMENCLATURE & STRUCTURAL
ISOMERISM
189 IUPAC NOMENCLATURE & STRUCTURAL ISOMERISM Chemistry
IUPAC Nomenclature
1. Historical introduction of organic compounds :
It was observed that initially compounds were found from two sources living organism and non living matter. The
compounds which were derived from living organism were called as organic compounds while those from non
living matter were named as inorganic compounds. Berzilius thought that organic compounds were produced
• i
from their element by laws different from those governing the formation of inorganic compounds. This led him to
the belief that organic compounds are formed under the influence of a vital force and they couldn't be prepared
artificially.This myth continued till Wohler converted inorganic compound ammonium cyanate found from non
living matters into urea an organic compound.
heat
NH4CNO   NH2CONH2
ammonium cyanate urea
The myth of vital force theory was completely ended with the synthesis of acetic acid from its elements by Kolbe
in 1845,and the synthesis of methane by Berthelot in 1856.
Since then millions of compounds have been produced in laboratory. Basically organic compounds are made of
essentially carbon and other elements like Hydrogen, Oxygen, Nitrogen Phosphorus, Sulphur etc..
2. Some important definitions :

(i) Catenation : The property of atoms of an element to link with one another forming chains of identical atoms
is called catenation.
(ii) Homologous series : Homologous series may be defined as a series of similarly constituted compounds in
which the members possess the same functional group, have similar chemical characteristics and have a
regular gradation in their physical properties. The two consecutive members differ in their molecular formula by
CH2.
(iii) Isomerism : Compounds which have the same molecular formula but differ in physical and chemical
properties are called isomers and the phenomena is called isomerism.
Isomerism can be broadly classified into two categories
(1) Structural Isomerism
(2) Stereoisomerism
3. Classification of organic compounds

If we look at the vast number of organic compounds, two things will strike our mind –the skeleton is either open or
closed. Based on this, organic compounds are classified as acyclic (open–chain) or cyclic (closed–chain)

1. Alkanes (Saturated hydrocarbon) CH3 – CH2 – CH3 Propane

2. Alkenes (Unsaturated hydrocarbon) CH3 – CH = CH2 Propene
3. Alkynes (Unsaturated hydrocarbon) HC  CH Ethyne
4. Aliphatic compounds with other functional groups CH3–CH2–OH Ethanol (absolute alcohol)
• CH3–CH2–COOH Propanoic acid i
5. Homo alicyclic compound Cyclohexane
6. Heteroalicyclic compound Tetrahydropyran

O
7. Heterocyclic aromatic compound Pyridine
OH
8. Homo cyclic benzenoid aromatic compounds Phenol
Napthalene
9. Homo cyclic Non-benzenoid aromatic compound [18] annulene
4. Organic compounds and functional groups

Number of known organic compounds is much more than inorganic compounds but, it has been possible to
group them into classes or families based on their structural features. This has given organic chemistry a logical
and systematic shape. Examples are as follows :
4.1 Alkanes
These are open–chain aliphatic saturated compounds which have no functional groups. These are also called
paraffins. These are represented by the general formula, CnH2n + 2 where n = 1, 2, 3, ............
The names of the alkanes for n = 1, 2, ..........., 10 must be committed to memory since all organic nomenclature
is related directly or indirectly to the name of alkane CnH2n + 2
n = 1 means CH4 – Methane
n = 2 means C2H6 – Ethane
n = 3 means C3H8 – Propane
n = 4 means C4H10 – Butane
n = 5 means C5H12 – Pentane
n = 6 means C6H14 – Hexane
n = 7 means C7H16 – Heptane
n = 8 means C8H18 – Octane
n = 9 means C9H20 – Nonane
n = 10 means C10H22 – Decane

4.2 Alkyl groups
When we remove a hydrogen from alkane, we get an alkyl group :
 – ane 
General formula
–H
CnH2n  2 
 CnH2n  1  alkane   alkyl 
  yl 
– ane  CH 
methane   methyl   CH3 
–H
• e.g.  yl  4
 i
– ane  C H   C 3H7 

propane   propyl –H
e.g.  yl  3 8 
4.3 Alkenes
Alkenes are open chain unsaturated hydrocarbons and having carbon–carbon double bonds (C = C). They have
the general formula CnH2n where n = 2, 3, 4 ... etc. These are also called alkylenes or olefins. The first three
members are generally named by their common names.
CH3
|
e.g. CH2 = CH2 CH3 – CH = CH2 CH3 – CH2 – CH = CH2 CH3  C  CH2
ethylene propylene butylene Isobutylene
4.4 Alkenyl groups

Like alkyl groups (alkane – H), there are three commonly encountered alkenyl groups which are given common
names.
remove H
e.g. CH2 = CH2    CH2 = CH –
vinyl group
4.5 Alkynes
Unsaturated aliphatic hydrocarbons containing a carbon–carbon triple bond are called alkynes. In the common
system, they are called acetylenes, after the name of the first member of this family. (i.e. acetylene)
General formula : CnH2n-2
where n = 2, 3, 4....... etc.
Common Names : Acetylene and its alkyl derivatives.
IUPAC names : Alkane – ane + yne = Alkyne
The position of the triple bond on the parent chain is designated by lowest possible arabic numerals
The common names of a few simple alkynes are given below.
n = 2  CH  CH Acetylene
n = 3  CH3–CCH Methyl acetylene
n = 4  CH3 – CH2 – C  CH Ethylacetylene
CH3
n = 6  CH3 – C  C – CH Methyl isopropyl acetylene
CH3
4.6 Alkynyl groups
HC  CH 
H
 HC  C –
(-e + yl = Ethynyl)
H3C – C  CH 
H
 H3C – C  C –
(-e + yl = propynyl)

4.7 Functional group and residue
The characteristic group of atom which decided the physical and chemical properties of an organic molecule is
called functional group.
Functional group is that portion of molecule which is highly reactive and takes part in chemical reactions. Rest
of the molecule is called Residue.
e.g. CH3CH2CH2CH2 – COOH
• i
Residue Functional
Group
Examples of Compound containing different functional groups with common / trival names.
No. of
carbon Prefix –CHO (Aldehyde) –COOH(–ic acid) –COCl.(–yl chloride) –CONH2 (Amide)
atoms
HCHO HCOOH HCOCl HCONH2

1 Form
Formaldehyde Formic acid Formyl chloride Formamide
CH3CHO CH3COOH CH3COCl CH3CONH2

2 Acet
Acetaldehyde Acetic acid Acetyl chloride Acetamide
CH3CH2CHO CH3CH2COOH CH3CH2COCI CH3CH2CONH2

3 Propion
Propion aldehyde Propionic acid Propionyl chloride Propionamide
CH3CH2CH2CHO CH3CH2CH2COOH CH3CH2CH2COCI CH3CH2CH2CONH2

4 Butyr
n–Butyraldehyde n–Butyric acid n–Butyryl chloride n–Butyramide
CH3CH2CH2CH2C CH3CH2CH2CH2C CH3CH2CH2CH2CO

CH3CH2CH2CH2COCI
5 Valer HO OOH NH2
n–Valeryl chloride
n–Valeraldehyde n–Valeric acid n–Valeramide
3C+1 Double CH2=CH–CHO CH2 = CH–COOH CH2 = CH–COCI CH2=CH–CONH2

Acryl
bond Acrylaldehyde Acrylic acid Acryl chloride Acrylamide
4C + 1
Double bond CH3CH2 = CH3CH2 =
CH3CH2 = CH–COCl
(at 2nd Croton CH3–CH=CH–CHO CH–COOH CH–CONH2
Crotonyl chloride
Carbon. Crotonaldehyde Crotonic acid Crotonamide
atom)

–N — C(Oisonitrile)
—
If Suffix isocyanide is used
than. Carbon atom of – NC
not counted.
No. of carbon If suffix carbyl amine is —COOR
Prefix –CN(–O nitrile)
atoms used. Carbon atom of – NC Ester
• not counted. i
If O-isonitrile is used 
Carbon atom of – NC
counted
H–C N H–N — C HCOOCH3

1 Form —
Formonitrile Formoisonitrile Methyl formate
 CH3COOCH3
CH3C  N CH3–N —— C
2 Acet Methyl acetate
Acetonitrile Acetoisonitrile

CH3CH3 C  N CH3CH2N — — C CH3CH2COOCH3
3 Propion
Propionitrile Propionisonitrile Methyl propionate
CH3CH2CH2 C  N CH3CH2CH2N —  C CH3CH2CH2COOCH3

4 Butyr —
n–Butyronitrile n–Butyroisonitrile Methyl n–butyrate
CH3 — CH — CH 2— COOCH3 
 C  | 
CH3CH2CH2CH2 C  N CH3CH2CH2CH2N —  
5 Valer — CH3
n–Valeronitrile n–Valeroisonitrile Methyl isovalerate
3 C +1 Double CH2 = CH – C  N CH2 = CH–NC CH2=CHCOOCH3

Acryl
bond Acrylonitrile Acrylisonitrile Methyl acrylate
4C + 1 Double
CH3CH = CH – C  N CH3–CH=CH–NC CH3CH=CHCOOCH3
bond (at 2nd Croton
Crotononitrile Crotonoisonitrile Methyl crotonate
Carbon. atom)
Other Examples
O O
|| ||
1. H—C—O—C—H Formic anhydride
O O
|| ||
2. CH3 — C — O — C — CH3 Acetic anhydride
O O
|| ||
3. H — C — O — C — CH3 Acetic formic anhydride

O
||
4. H  C  O  C 2H5 Ethyl formate
5. CH3  C  CH3 Dimethyl ketone or acetone

||
O
• i
6. CH3  C  CH2  CH3 Ethylmethyl ketone
||
O
7. CH3 – CH2 – NH – CH3 Ethyl methyl amine or N-Methylaminoethane
8. (CH3)3N Trimethylamine or N, N–Dimethyl aminomethane
Some common names of hydrocarbon alkyl groups

(A) Iso alkyl group
CH3
|
A compound having  CH  CH3 group is called iso alkyl group
CH3  CH  CH3  CH  CH2  CH3  CH  CH2  CH3

e.g. | | |
CH3 CH3 CH3
Iso propyl Iso butyl Iso pentane
Note: Iso alkyl group name can be used in IUPAC Nomenclature and its first letter 'I' is consider for alphabetical
seniority
1 2 3 4 5 6
e.g. C H3  C H  C H  C H2  C H 2  C H 3 3–Isopropyl–2–methylhexane
| |
CH3 CH  CH3
|
CH3
(B) Neo alkyl group

 CH3 
 
 | 
Compound having  CH3  C  CH2   group is called neo alkyl group.
 | 
 CH3 
 
CH3 CH 3 CH3
| | |
e.g. CH3  C  CH2 – CH 3  C  CH 3 CH3  C  CH2  CH3
| | |
CH3 CH 3 CH3
Neopentyl Neopentane Neohexane
(C) Types of carbon and hydrogen atoms in alkanes

The carbon atoms in an alkane molecule may be classified into four types as primary (1°), secondary (2°),
tertiary (3°) and quaternary (4°) as follows
(a) A carbon atom attached to one another (or no other) carbon atom is called a primary carbon atom and is
designated as 1° carbon
1 1 1 1
e.g. (i) C H3  C H3 (ii) C H3  CH2  C H3

(b) A carbon atom attached to two other carbon atoms is called a secondary carbon atom and is designated as 2°
carbon
2 2 2
e.g. (i) C H3  C H2  C H3 (ii) CH3 – C H2 – C H2 – CH3
(c) A carbon atom attached to three other carbon atoms is called a tertiary carbon atom and is designated as 3°
carbon.
• i
CH3 CH3
| |
e.g. (i) CH3  C H  CH3 (ii) CH3  C H  CH2  CH3
3 3
(d) A carbon atom attached to four other carbon atoms is called a quaternary carbon atom and is designated as 4°
carbon
CH3 CH3
| |
4 4
e.g. (i) CH3  C  CH3 (ii) CH3  C  CH2  CH3
| |
CH3 CH2  CH3
The hydrogen atoms attached to 1°, 2° and 3° carbon atoms are called primary (1°) secondary (2°) and tertiary
(3°) hydrogen atoms. It may be noted here that there is nothing like quaternary hydrogen atom. Since a quarternary
carbon does not carry any hydrogen.
Ex.1 How many 1°, 2°, 3° and 4° carbon atoms are present in following molecule.
CH3
|
CH3 – CH – C – CH2 – CH – CH3
| | |
CH3 CH3 CH2 – CH3
Sol. 1° Carbon atoms = 6 , 2° Carbon atoms = 2 , 3° Carbon atoms = 2 , 4° Carbon atom = 1

Note : Primary, secondary, tertiary & quaternary carbon atoms in a molecule are denoted by the letters p, s, t and q
respectively.
Ex.2 How many 1°, 2°, 3° and 4° carbon atoms are present in following molecule
CH3
|
CH3  C  CH2  CH  CH3
| |
CH3 CH3
1o
C H3
|
1o 4o 2o 3o 1o
Sol. C H3  C  C H2  C H  C H3
| |
1o
C H3 1o CH3
1° Carbon atoms = 5 , 2° Carbon atom = 1 , 3° Carbon atom = 1, 4° Carbon atom = 1

5. IUPAC system of nomenclature
The basic criteria for naming a structure by IUPAC system is choice of a parent name or the basic carbon
skeleton.
Nomenclature of alkanes is fundamental, to naming whole class of organic compounds because it helps us to
identify the basic carbon skeleton.
General rules for IUPAC nomenclature
• The IUPAC system is the most rational and widely used system of nomenclature in organic chemistry. The mosti
important feature of this system is that any given molecular structure has only one IUPAC name and any given
IUPAC name denotes only one molecular structure.
The IUPAC name of any organic compound consists of five parts, i.e.,
1. Word root 2. Primary suffix 3. Secondary suffix 4. Primary prefix 5. Secondary prefix
Thus, a complete IUPAC name of an organic compound consists of the following parts in the given
sequence:
Secondary prefix + Primary prefix + Word root + Primary suffix + Secondary suffix
5.1 Word root :

It is the basic unit of the name. It denotes the number of carbon atoms present in the principal chain (the longest
possible continuous chain of carbon atoms including the functional group and based upon the common names
of alkanes) of the organic molecules.
Cha in le ngth W ord root Cha in le ngth W ord root Cha in le ngth W ord root
C1 Meth C9 Non C20 Icos
C2 Eth C10 Dec C30 Triacont
C3 Prop C11 Undec C 40 Tetracont
C4 But C12 Dodec C 50 Pentacont
C5 Pent C13 Tridec C 60 Hexacont
C6 Hex C14 Tetradec C70 Heptacont
C7 Hept C15 Pentadec C 80 Octacont
C8 Oct C 16 Hexadeca C 100 Cent & Hect
5.2 Primary Suffix.

A primary suffix is always added to the word root to indicate whether the carbon chain is saturated or unsaturated.
The three basic primary suffixes are given below :
Type of carbon chain Primary suffix General name
(a) Saturated – ane Alkane
(b) Unsaturated with one double bond – ene Alkene
(c) Unsaturated with one triple bond – yne Alkyne
If the parent carbon chain contains two, three or more double or triple bonds, numerical prefix such as di (for
two), tri (for three), tetra (for four) etc. are added to the primary suffix. For example,

Type of carbon chain Primary suffix General name
(a) Unsaturated with two double bonds (a) + diene Alkadiene
(b) Unsaturated with two triple bonds (a) + diyne Alkadiyne
• (c) Both double and triple bonds enyne Alkenyne i
5.3 Secondary suffix :

A secondary suffix is then added to the primary suffix to indicate the nature of the functional group present in the
organic compounds. Secondary suffix of important functional groups are given below in their decreasing order of
seniority.
Class Name Suffix Prefix
1. R – COOH Alkanoic Acid – oic acid (carboxylic acid) carboxy
2. R – SO3H Alkane sulhonic Acid – sulphonic acid sulpho
3. R – C – O – C – R Alkanonic Anhydride – oic anhydride (carboxylic ------------

|| || anhydride)
O O
4. R – COOR Alkyl alkanoate – oate (carboxylate) alkoxy carbonyl

or alkanoyl oxy
5. R – C – X Alkanoyl halide –oyl halide (carbonyl halide) halo carbonyl

||
O
6. R – C – NH2 Alkanamide – amide (carboxamide) carbamoyl

||
O
7. R – C  N Alkanenitrile – nitrile (carbonitrile) cyano
8. R – C – H Alkanal – al (carbaldehyde) formyl / oxo

||
O
9. R – C – R Alkanone – one oxo

||
O
10. R – OH Alkanol – ol hydroxy
11. R – SH Alkanethiol – thiol mercapto
12. R – NH2 Alkanamine – amine amino

The following examples illustrate the use of word root, primary suffix and secondary suffix in naming of organic
compounds.
Organic compounds Word root Primary suffix Secondary suffix IUPAC name
CH3CH2 OH Eth an(e) ol Ethanol
CH3CH2 CH 2NH 2 Prop an(e) amine Propanamine

• i
CH3CH2 CH 2COOH But an(e) oic acid Butanoic acid
CH3CH2 CN Prop an(e) nitrile Propanenitrile
CH2 = CHCHO Prop en(e) al Propenal
HC  CCOOH Prop yn(e) oic acid Propynoic acid
5.4 Primary prefix :

A primary prefix is used simply to distinguish cyclic from acyclic compounds.
For example, in case of carbocyclic compounds, (cyclic compounds containing only carbon atoms in the ring),
a primary prefix, cyclo is used immediately before the word root. Thus.
CH2
CH2 CH2
e.g. Cyclo + pent + ane = Cyclopentane
CH2 CH2 Primary prefix Word root Primary suffix IUPAC name
If the prefix cyclo is not used, it simply indicates that the compound is acyclic or open chain.
5.5 Secondary prefix :

In IUPAC system of nomenclature, certain groups are not considred as functional groups but are treated as
substituents. These are called secondary prefixes and are added immediately before the word root (or the
primary prefix in case of carbocyclic compounds) in alphabetical order to denote the side chains or substituent
groups. The secondary prefixes for some groups which are always treated as substituent groups (regardless of
the fact whether the organic compound is monofunctional or polyfunctional) are given below :
Substitue nt group Se conda ry pre fix Substitue nt group Se conda ry pre fix
–F Fluoro – OCH3 (– OMe) Methoxy
– Cl Chloro – OC2 H5(–OEt) Ethoxy
– Br Bromo –R Alkyl
–I Iodo – CH3 (– Me) Methyl
– NO 2 Nitro – C 2H5 (– Et) E thyl
– NO Nitroso – CH 2CH2 CH3(n-Pr) n-Propyl

N  N Diazo – CH(CH3)2 (– iPr) Isopropyl
– OR Alkoxy – C(CH3 )3 (t-Bu) t-Butyl
Secondary Primary
Organic compounds Word root IUPAC name
prefix suffix
CH3CH2 – Br Bromo eth ane Bromoethane
CH3 – NO2 Nitro meth ane Nitromethane
C2H5 – OC2H5 Ethoxy eth ane Ethoxyethane

Br
|
4
CH
5 3
e.g. H2C CH2 4-Bromo + cyclo + hex + an (e) + 1-ol
Primary Word Primary
H2C6 2
CH2 Secondary suffix Secondary
prefix prefix root suffix
• 1CH
i
|
OH
Ex. Write IUPAC name of following compound

SO3H CH3
I
(a) (b)
OH
CH3 CH
CH3 CH3
SO3H
5 1
2
I
Sol. (a) 2 – Iodo – 3 – methylcyclopentanesulfonic acid.
4 3 CH3
Here Secondary prefix = 2 – Iodo – 3 – methyl
Primary prefix = cyclo
Word root = pent
Primary suffix = ane
Secondary suffix = sulfonic acid
(b) 2 – Isopropyl – 5 – methylcyclohexanol
Here Secondary prefix = 2 – Isopropyl – 5 – methyl
Word root = hex
Primary suffix = an(e)
Secondary suffix = ol
6. IUPAC nomenclature of branched / complex alkanes

6.1 (a) Select the longest chain of carbon atoms in the molecule.
(b) Count the number of carbon atoms in that chain and name according to the following rules.
e.g.
Longest chain has 7 carbons.

(c) When chains of equal lengths are competing for selection, that chain is selected which has more number of
substituents.
Here the chain shown is selected.

6.2 Numbering of the parent carbon chain :
Carbon atoms in the longest chain selected as above is numbered consecutively from one end to the other such
that the substituents attached get the lowest number.
In the above example, according to this rule, the numbering will be done as :
• i
By this numbering, locant (substituents) get the number 2, 3 and 4 compared to 4, 5 and 6 if numbering is done
from other end.
6.3 Each alkyl substituent is named according to number of carbon atoms present in it and it is prefixed by the
number to which it is located in the main chain.
In the above example, substituents are as follow :
–CH3 (methyl) group at carbon No. 2  2–methyl
–C2H5 (ethyl) group at carbon no. 3  3–ethyl
–CH2CH2CH3 (propyl) group at carbon no. 4 
4–propyl
Hence, the above compound is named as :
3–Ethyl–2–methyl–4–propylheptane
6.4 If the same substituent occurs more than once in the molecule, the prefix di (for two), tri (for three), etc. are used
to indicate how many times it appears.
The above example can be written with a little modification as :
e.g.
Methyl at No. 2,3, Ethyl at no. 3, Propyl at no. 4

This will be named as : 3–Ethyl–2,3–dimethyl–4–propylheptane
6.5 The name of the compound is composed in such a manner that each substituent with its number and name is
written alphabetically just before the word root. Prefixes di, tri, tetra etc. are not considered in deciding alphabetical
order.
 Ethyl will be written before methyl which will be written before propyl.
Note that in the above examples, this pattern has been compiled with.
 Also, as per convention,
(1) numbers are separated each other by commas(,).
(2) numbers are separated from words by hyphens and
(3) write the name of the compound as a single word (with no space between)
e.g. Write the IUPAC name of
1. Primary suffix is ane as all are single bonds

2. Chain is numbered as shown
3. Root word is hex
4. Prefixes methyl appears twice
 it is 2, 4–dimethyl and 3 – ethyl
5. While arranging in alphabetical order Replicators di, tri, tetra are not considered.
 3 – Ethyl–2, 4–dimethylhexane
7. IUPAC nomenclature of alkenes/alkynes
7.1 Alkenes :
Functional group :
(1) Select the longest chain containing carbon–carbon double bond. This need not be the longest chain in the
compound as a whole. Parent name will be alkene corresponding to number of carbon atoms in the longest
• chain. i
e.g.
Longest chain is as shown above. It has 6 atoms  hexene = parent name

(2) Carbon atoms in the longest chain is numbered so that doubly bonded carbon atom gets the lowest number.
The position of double bond is indicated by the smaller of the numbers assigned to two carbon atoms of double
bond.
 The above example can be rewritten as,
Position of double bond will be indicated as no. 1.

Hence, name will be, 3–Ethyl–3–methylhex–1–ene
e.g.
2, 2, 5, 5-Tetramethylhex-3-ene
7.2 Alkynes
Parent chain selection and numbering of longest chain is exactly same as that for alkenes.
e.g.
4,4–Dimethylpent–1–yne
8. IUPAC nomenclature of hydrocarbons containing both double and

triple bonds
(i) Such hydrocarbon is named as alkenyne (not alkynene).
(ii) Numbering is done in a manner that double and triple bonds get the lowest possible number. If double bond
and triple bond both have same number then double bond is given preference our triple bond.
HC  C – CH2 – CH = CH2
(wrong) 1 2 3 4 5 (numbering is done from alkyne)
(write) 5 4 3 2 1 (numbering is done from alkene)
Ex. Write IUPAC name of the following compounds.
(a) (b)
Ans. (a) Oct-1-en-4-yne (b) Hepta-3,6-dien-1-yne

9. IUPAC nomenclature of alicyclic compounds
(1) The names of alicyclic compounds are obtained by adding the prefix "cyclo"
e.g.
• Cyclobutane Cyclopentene i
(2) The numbering of the carbon atoms in the ring is done in such a way that the substituent which comes first
in the alphabetical order is given the lowest possible number and it does not violate the lowest set of locants
rule.
CH3
CH3 1
3 C2H5
6 2
4 2
e.g. 1 5 3
5
CH2CH3 4
6 CH3
1 – Ethyl – 3 – methyl cyclohexane 2 – Ethyl – 1, 4 – dimethyl cyclohexane
C2H5 I
3
2 Br
4
CH3
5 1
CH3 6
Cl
3 – Ethyl – 1, 1 – dimethyl cyclohexane 2 – Bromo – 1 – chloro – 3 – iodocyclohexane

(3) When the ring contains more or equal number of carbon atoms than the alkyl group attached to it, then it is
named as a derivative of cycloalkane and the alkyl group is treated as substituent
CH2 – CH2 – CH3
e.g.
Propylcyclopropane
(4) The alkane chain contains greater number of carbon atoms than present in the ring, then the compound is
considered as the derivative of alkane and the ring is designated as substituent.
1 2 3 CH3 – CH2 – CH – CH2 – CH2 – CH3

4
e.g.
2 – Cyclopropylbutane 3 – Cyclopentylhexane
(5) If ring has unsaturation and side chain is saturated then ring is selected as parent chain.
If side chain has unsaturation and ring is saturated then side chain is selected as parent chain.
If both have unsaturation the chain with maximum unsaturation has selected as parent chain.
If equal unsaturation then longest chain is selected as parent chain.
If unsaturation and number of carbon atoms both are equal then ring is selected as parent chain.
6
5 1 3 2
4
e.g. 4 5 1
2
3 6
1-Ethylcyclohex-1-ene 6-Ethyl-3, 3 -dimethylcyclohex-1-ene Cyclohexyl ethene

(6) If more than one alicyclic ring is attached to a single chain then the compound is named as a derivative of
alkane and the ring are treated as a substituent group.
e.g. CH2
Dicyclopropylmethane
• (7) If a multiple bond and some other substitutents are present in the ring, the numbering is done in such a wayi
that the multiple bond gets the lowest number
NO2
3
4 2
e.g.
5 1
6
3 – Nitrocyclohex – 1 – ene
(8) If a compound contains an alicyclic ring directly linked to the benzene ring. It is named as a derivative of
benzene.
e.g.
Cyclohexylbenzene
(9) If functional group is present in cyclic compounds than the main chain is taken in which principal functional
lie's, if the principal functional group is present in ring also then main chain will be taken for the maximum no. of
carbon atoms.
OH
1 1 3
2
6
2
e.g.
5 3 OH
4
2-Propylcyclohexan-1-ol 1-Cyclohexylpropan-2-ol 2-Propyl cyclopropan-1-ol
(10) When chain terminating functional group is directly attached with ring then ring is taken as parent chain &
special suffix is used for this functional group.
Functional Group Suffix

CHO Carbaldehyde
COOH Carboxylic Acid
COX Carbonyl halide
COOR Alkyl Carboxylate
CONH2 Carboxamide
CN Carbonitrile
CN CHO
e.g.
Cyclohexanecarbonitrile Cyclohexanecarbaldehyde
O
2
COOC2H5
1
2-Cyclohexyl ethanoic acid Ethyl 2–oxocyclohexane–1–carboxylate

10. IUPAC nomenclature of compounds containing functional groups
10.1 Rules for non chain terminating functional groups
(1) Parent chian : Select the longest possible chain with maximum functional group and maximum unsaturation
without caring whether it also denotes the longest possible chain or not.
• 4 3 2 i
e.g. CH3 – CH2 – CH – CH2 – CH3 2-Ethyl butan-1-ol
|
1
CH2OH
(Parent chain contains four rather than five carbon atoms)
(2) Lowest number for the functional group

Numbering is done from that side of the chain which gives lowest locant to the principle functional group followed
by double and triple bonds.
O O
6 5 4 3|| 2 1 1 2 3 4|| 5 6
e.g. CH3 – CH – CH2 – C – CH2 – CH3 CH3 – CH – CH2 – C – CH2 – CH3
| |
CH3 (I) correct CH3 (II) wrong
5-Methyl hexan-3-one
( C = O group gets lowest number 3) ( C = O group gets number 4 which is not lowest)
(3) If a compound contains two or more like groups, the numerical prefixes di, tri, tetra etc. are used
CH2  CH  CH2 CH3 – C – CH2 – C – CH3

e.g. | | | || ||
OH OH OH O O
Propane  1,2,3  triol Pentane-2, 4-dione
10.2 Rules for chain terminating functional groups

(1) When a chain terminating functional group such as – CHO, – COOH, – COOR, – CONH2, – COCl, – C  N etc.
is present, it is always given number 1 (one.)
O
4 3 2 ||
e.g. CH3 – CH2 – CH – CH3 CH3 – C  C – CH2 – C – H
| 5 4 3 2 1
1
COOH Pent-3-yn-1-al
2-Methylbutan-1-oic acid
e.g. Write the IUPAC name of
3 4 5
CH3  CH2  CH  CH2  CH  CH3
1
| | 7
2 6
CN  CH2 CH2  CH3
1. The longest chain containing functional group is of 7 carbon atoms. Therefore, the word root is hept
& the chain is numbered as shown.
2. There is no multiple bond in it. Hence, the primary suffix is ane.
3. The functional groups is – CN. Hence, secondary suffix is nitrile
4. Moreover, there is a methyl group on carbon 5 and ethyl group on carbon 3.
5. The IUPAC name is, therefore, 3-Ethyl-5-methylheptanenitrile

(2) The name for benzene as substituent is phenyl. In case the phenyl ring is further substitued, the carbon
atoms of the ring directly attached to the parent chain in such a ways that the substituent on the ring gets the
least possible number. For example
• i
(3) If the organic molecule contains more than one similar complex substitutents, then the numeral prefixes
such as di, tri, tetra etc. are replaced by bis, tris, tetrakis etc. respectively.
e.g.
10.3 Rules for IUPAC nomenclature of polyfunctional compounds :

(1) When an organic compound contains two or more different functional groups then senior functional group is
selected as the principal functional group while other functional groups are treated as substituents.
(2) Some functional group such as all halo groups (fluoro, bromo, chloro, iodo), nitroso (NO) nitro (– NO2) and
alkoxy (–OR) are always treated as substituent groups.
e.g.
Numbering the principal chain order is

[Principal functional group > double bond > triple bond > substituents]
O
5 || 3
4 2 1
e.g. CH3 – C – CH2 – CH2 – CHO
4-Oxopentan-1-al
[– CHO > C=O]
O
6 5 || 2 4 1 3
O = CH – CH2 – CH2 – C – CH2 – COOH
3, 6-Dioxohexanoic acid or 5-Formyl-3-oxopentanoic acid
[COOH > C & CHO]
||
O
(3) If more than one same chain terminating group are present then the principal chain is selected including the
functional groups and numbring is done from that side which gives lowest locant to unsaturation and
substituents.
1 2 3 4 5
e.g (a) HOOC – CH 2 – CH2 – COOH (b) N C C H  C H2  C H2  C N
1 2 3 4 |
Butane-1, 4-dioic acid CH3
2  Methylpentanedinitrile
O
CH2CH2–CH2–CH–CH2–C–O–C2H5
(c) 3 2 1 Ethyl-3-(3-hydoxy propyl) pent-4-enoate
OH CH=CH2
4 5
Parent chain contains five rather than six carbon atoms

11. Nomenclature of aromatic compounds
The aromatic compounds are cyclic compounds which contain one or more benzene type rings. Benzene is the
simplest hydrocarbon of aromatic series which has planar cyclic ring of six carbon atoms having three double
bonds in alternate positions as shown below.
CH
1
• HC CH 6 2 i
HC CH or 5 3
4
CH
(i) Nuclear substituted –
The functional group is directly attached to the benzene ring, in the IUPAC system they are named as derivatives
of benzene. The position of the substituents in disubstituted benzenes are indicated either by prefixes such as
o-(ortho) for 1, 2, m-(meta) for 1, 3 and p-(para) for 1, 4 position. However, many of their common names have
also been adopted by the IUPAC system.
(ii) Side chain substituted –
The functional group is present in the side chain of the benzene ring in the IUPAC system, these are usually
named as phenyl derivatives of the corresponding aliphatic compounds.
The IUPAC and common names of a few important members of each family are given below.
(1) Aromatic hydrocarbons (arenes)
Hydrocarbons which contain both aliphatic and aromatic units are called arenes . These are of two types
(a) Hydrocarbon containing one ring only.
CH3 CH3
1
1 CH3 2
2
e.g. 3
CH3
1, 2 – Dimethyl benzene 1, 3 – Dimethyl benzene
(o – Xylene) (m – Xylene)
CH3
1
2
3
4
CH3
1, 4 – Dimethyl benzene Isopropylbenzene
(p – Xylene) (Cumene)
3 2 1
CH = CH2 CH2CH = CH2
Phenylethene 3 – Phenylprop-1-ene
(Styrene) (Allyl benzene)
3 2 1
C CH CH2 C CH
Phenylethyne 3-Phenylprop-1-yne
(Phenyl acetylene) (Propargyl benzene)

(b) Hydrocarbon containing condensed or fused ring
3
4 2
8 1 8 9 1
7 2 7 2 5 1
6
6 3 6 3
5 4 5 10 4 7 10
• 8 9 i
Naphthalene Anthracene (Phenanthrene)
2. Aryl groups :
CH2 CH C
Phenyl (Benzyl) (Benzal) (Benzo)

CH3
CH3 CH3 1
1 1
2
2 2
3
3 4
2 – Tolyl 3 – Tolyl 4 – Tolyl

or (o – Tolyl) or (m – Tolyl) or (p – Tolyl)
3. Other aromatic examples

(i) Phenols – monohydric
OH
OH 1
2
3
4
CH3
Hydroxybenzene 4 – methyl phenol
(phenol) (p –cresol)
(ii) Dihydric and polyhydric phenols
OH
OH OH
1 1
OH
2
2
3
OH OH
Benzene – 1, 2 – diol Benzene – 1, 3 – diol Benzene – 1, 4 – diol
(Catechol) (Resorcinol) (Quinol)
(iii) Aromatic Alcohols

2 1
CH2OH CH3 – CH – OH

Phenyl methanol 1 – phenylethanol

(Benzyl alcohol) (–phenyl ethyl alcohol)

(iv) Aromatic ethers
OCH3 O – C6H5
• Methoxy benzene Phenoxybenzene i

(Anisol) (Diphenyl ether)
(v) Aldehydes
CHO CHO
1 OH
2
Benzenecarbaldehyde 2 – Hydroxybenzenecarbaldehyde
(Benzaldehyde) (Salicylaldehyde)

CH2 – CH2 – CHO
3 – Phenylpropanal
(  – phenylpropionaldehyde)
(vi) Ketones
1 2
CO CH3 COC6H5
Methyl phenyl ketone Diphenyl ketone

(Acetophenone) (Benzophenone)
(vii) Nitro Compounds

NO2 NO2
1
2
3 NO2
Nitrobenzene 1, 3 – Dinitrobenzene
(m – Dinitrobenzene)
OH
CH3 1
NO2 6 NO2
1 2
NO2
5 3
4
NO2
2 – Nitro toluene 2, 4, 6 – Trinitrophenol

(o – Nitro toluene) (T.N.P) (Picric acid)

• i
2, 4, 6-Trinitrotoluene (TNT)
an explosive
(viii) Amines
(a) Aryl amines
NH2 NH2
NH2
Benzenamine Benzene –1, 2 – diamine

(Aniline) (o – phenylenediamine)
N(CH3)2 NHC6H5
N, N – Dimethylbenzenamine N – Phenyl benzenamine

(N, N – Dimethylaniline) (Diphenyl amine)
(b) Aryl alkyl amine

CH2NH2 CH2 – CH2 – NH2
Phenylmethanamine 2 – Phenyl ethanamine

(Benzylamine) (  – phenyl ethyl amine)
(ix) Arenediazonium Salts
N N.Cl N NHSO4
Benzene diazonium chloride Benzene diazonium hydrogen sulphate
(x) Cyanides and Isocyanides
C N N C
Benzenecarbonitrile Benzeneisonitrile
(Benzonitrile) (Phenyl isocyanide)

(xi) Carboxylic Acids
COOH COOH COOH
1 1
CH3 COOH
2 2
Benzenecarboxylic acid 2 – Methylbenzene Benzene – 1, 2 -dicarboxylic acid

• i
(Benzoic acid) carboxylic acid (Phthalic acid)
(o – toluic acid)
O O
(xii) Anhydrides : || ||
C6H5  C  O  C  C6H5
Benzenecarboxylic anhydride
3
CH3 4 2
O
(xiii) Esters : 1
O – C – CH3
4–Methylphenyl ethanoate
O
C – NH2
(xiv) Amides :
Benzenecarboxamide
(xv) Halogen derivatives
Cl
Cl Cl 1
1 1
Cl
2
Cl
Chlorobenzene 1,2 – Dichlorobenzene 1, 4 – Dichlorobenzene
or o – Dichlorobezene or p – Dichlorobenzene
3 2 1
CHCl2 CH2 – CH2 – CH2 – Br
Phenyldicholoromethane Benzo chloride 1 – Bromo – 3 – phenylpropane

(Benzal chloride)
CH = CH – Cl
1 – chloro – 2 – phenylethene
Ex. Write IUPAC name of following aromatic compounds
CH3
|
CH2 – CH – CHO
3 2 1
(a) (b)
2-Methyl-3-phenylpropanal

12. Some important 1993 recommendations for IUPAC nomenclature of organic compounds
1. Locants (numerals and / or letters) are placed immediately before the part of the name to which they relate.
For example.
CH3CH2CH = CH2 should be named as but-1-ene
CH3CH2CH2OH should be named as propan-1-ol
• similarly, a few more examples are given as following : i
2. The locant 1 is often omitted when there is no ambiguity. For example.
In all the above examples locant 1 for the functional group is omitted because the position of the functional group
is unambiguous. However, in the following cases the position of the functional group must be mentioned.
Here, we cannot write simply propanol (or propanamine) because there are two propanols ; propan-1-ol and
propan-2-ol.
3. Arrangement of Prefixes
(i) Simple prefixes such as methyl, ethyl, chloro, nitro, hydroxy, etc. are arranged alphabetically.
The prefixes di, tri, etc. are however not considered for comparison.
2 1
e.g. CH2CH2
| |
Cl Br
1-Bromo-2-chloroethane
(ii) The name of a prefix for a substituted substituent is considered to begin with the first letter of its complete
name.
e.g.
for the substituted 1-chloropropyl, 'C' is taken as the first letter.

(iii) When two or more prefixes consist of identical roman letters priority for citation is given to the group which
contains the lowest locant at the first point of difference.
For example,
Here, 1-chloroethyl gets priority over 2-chloroethyl.

Common and IUPAC Names of Some Organic Compounds
S.No. Compound Common names IUPAC name

1. CH4 Methane or Marsh gas Methane
or Fire damp or
• Carbane i
2. H3 C  CH  CH3 Isobutane 2-Methylpropane
|
CH3
3. H3C  CH  CH2  CH3 Isopentane 2-Methylbutane

|
CH3
CH3
|
4. H3 C  C  CH3 Neopentane 2, 2-Dimethylpropane
|
CH3
CH3
|
5. CH3  CHCH2CH2CH3 Isohexane 2-Methylpentane
CH3
|
6. CH3  C  CH2CH3 Neohexane 2-2-Dimethylbutane
|
CH3
7. CH2 = CH2 Ethylene Ethene
8. CH3CH = CH2 Propylene Propene
9. CH3CH2 – CH = CH2 -Butylene But-1-ene
10. CH3CH = CHCH3 -Butylene But-2-ene
11. CH3(CH2)2CH = CHCH3 -Hexylene Hex-2-ene
12. Isobutylene 2-Methylpropene
13. CH2 = C = CH2 Allene Propadiene

14. HC  CH Acetylene Ethyne
15. H3C – C  CH Methyl acetylene Propyne
16. CH3 – Cl Methyl chloride Chloromethane
17. CH3  CH  CH3 Isopropyl iodide 2-Iodopropane

|
I
18. CH3 CH2  CH  CH3 sec-Butyl chloride 2-Chlorobutane

|
Cl
CH3
|
19. CH3  CH  CH2  Cl Isobutyl chloride 1-Chloro-2-methylpropane

S.No. Compound Common name IUPAC name
CH3
|
20. CH3  C  Cl tert-Butyl chloride 2-Chloro-2-methyl propane
|
CH3
• i
21. CH2  Br Ethylene dibromide 1, 2-Dibromoethane
|
CH2  Br
22. CH3  CH  Br Ethylidene bromide 1, 1-Dibromoethane
|
Br
23. CH2 = CH – Cl Vinyl chloride Chloroethene
24. CH2 = CH – CH2 – Br Allyl bromide 3-Bromo-1-propene
Ethyl alcohol or
25. CH3 – CH2 – OH (Methylcarbinol) Ethanol
n  Propyl alcohol or
26. CH3CH2CH2 – OH (Ethyl carbinol) Propan-1-ol
27. CH3  CH  CH3 Isopropyl alcohol Propan-2-ol

|
OH
28. CH2 = CH – CH2 – OH Allyl alcohol Prop-2-en-1-ol

29. CH  C – CH2 – OH Propargyl alcohol Prop-2-yn-1-ol
CH3  CH  CH2
30. | | Propylene glycol Propane-1, 2-diol
OH OH
31. HO – CH2 – CH2 – CH2 – OH Trimethylene glycol Propane-1, 3-diol
32. CH2  CH  CH2 Glycerol or Glycerine Propane-1, 2, 3-triol

| | |
OH OH OH
33. H – CHO Formaldehyde Methanal
34. CH3 – CHO Acetaldehyde Ethanal

35. CH3CH2CH2 – CHO n-Butyraldehyde Butanal
36. Isobutyraldehyde 2-Methylpropanal
37. CH2 = CH – CHO Acrolein Propenal

38. CH3CH = CH – CHO Crotonaldehyde But-2-enal
39. CH3 – CO – CH3 Dimethyl ketone or Acetone Propanone
40. CH3 – CO – CH2CH3 Ethyl methyl ketone Butanone
41. CH3 – CO – CH2CH2CH3 Methyl n-propyl ketone Pentan-2-one
42. CH3CH2 – CO – CH2CH3 Diethyl ketone Pentan-3-one
43. CH3CO – CH = CH2 Methylvinyl ketone But-3-en-2-one
44. H – COOH Formic acid Methanoic acid

45. CH3 – COOH Acetic acid Ethanoic acid
46. CH3CH2CH2 – COOH n-Butyric acid Butanoic acid
47. CH3CH2CH2CH2COOH n-Valeric acid Pentanoic acid
• i
48. Iso-butyric acid 2-Methylpropanoic acid
49. CH2 = CH – COOH Acrylic acid Propenoic acid
50. COOH Oxalic acid Ethanedioic acid

|
COOH
51. Malonic acid Propanedioic acid
52. H2C  COOH succinic acid Butanedioic acid

|
H2C  COOH
53. Glutaric acid Pentanedioic acid
H
|
H3 C  C  COOH
54. | Lactic acid 2-Hydroxypropanoic acid
OH
O
55. || Pyruvic acid 2-Oxopropanoic acid
H3 C  C  COOH
56. Tartaric acid 2,3  Dihydroxyb u tane

HOCHCOOH
dioic acid
|
HOCHCOOH
2  Hydroxypro pane  1,2,

57. Citric acid 3  tricarboxy lic acid
58. HO  CH  COOH Malic acid 2  Hydroxy  bu tan e

| dioic acid
CH2COOH
59. Maleic acid cis-But-2-enedioic acid
60. Fumaric acid trans-But-2-enedioic acid
61. CH2 = CH – COOH Acrylic acid Propenoic acid

62. H3C – CH = CH – COOH Crotonic acid But-2-enoic acid
63. H – COOCH3 Methyl formate Methyl methanoate
64. H – COOC2H5 Ethyl formate Ethyl methanoate
• 65. CH3 – COOC2H5 Ethyl acetate Ethyl ethanoate i

66. H – COCl (unstable) Formyl chloride Methanoyl chloride
67. CH3 – COCl Acetyl chloride Ethanoyl chloride
68. (CH3CO)2O Acetic anhydride Ethanoic anhydride
69. (CH3CH2CO)2O Propionic anhydride Propanoic anhydride
70. H – CONH2 Formamide Methanamide
71. CH3 – CONH2 Acetamide Ethanamide
72. CH3 – CH2 – CONH2 Propionamide Propanamide
73. CH3 – O – N = O Methyl nitrite Methyl nitrite
74. CH3CH2 – O – N = O Ethyl nitrite Ethyl nitrite
75. CH3 – NH2 Methylamine Methanamine
76. (CH3CH2)2NH Diethylamine N-Ethylethanamine
77. (CH3)3N Trimethylamine or N,N-Dimethyl methan-
N,N-Dimethylamino- amine
methane
78. H2N – SO3H Sulphamic acid Aminosulphonic acid
79. CH3 – CN Methyl cyanide or Ethanenitrile
Acetonitrile
80. CH3 – N+  C¯ Methyl isocyanide or Methane isocyanide
Methyl carbylamine
81. CH3CH2 – N+  C¯ Ethyl isocyanide or Ethaneisocyanide
Ethyl carbylamine
82. Dioxane 1, 4-Dioxacyclohexane
83. Trioxane 1,3,5-Trioxacyclohexane
84. Toluene Methylbenzene or Toluene
85. Xylene (o,m,p) (o,m,p) Dimethylbenzene
1, 3, 5  Trimethyl
86. Mesitylene
benzene

Structure Isomerism
1. Definition
When two or more compounds have same molecular formula but they differ in their physical properties or
chemical properties or both then they are called isomers & the phenomena is called isomerism. Isomers are
also sometimes called as isomerides.
• i
Classification of isomerism
2. Structural isomerism :
When two or more organic compounds have same molecular formula but different structural formula,
(i.e., they differ in connectivity of atoms) then they are called structural isomers and the phenomena is called
structural isomerism
Structural isomers have always different IUPAC name
Ex.1 CH3  CH  CH  CH3 , CH3 CH2CH  CH2 

But  2  ene But  1  ene  structural Isomers
CH3
|
CH3  CH  CH2 CH3 
Ex.2 CH  CH2  CH3 , |  Identical compounds
| CH3  (not isomers )
CH3 2  Methylbutane


2  Methyl bu tan e
Isomers Characteristics Conditions

They have different size of They have same nature of
(1) Chain Isomers
main chain or side chain locants
They should have same size of
They have different position of
(2) Positional Isomers main chain and side chain and
locants
same nature of locant
Chain and positional isomerism is
(3) Functional Isomers Different nature of locant
not considered
Different nature of alkyl group They should have same nature of
(4) Metamerism along a polyvalent functional functional groups chain &
group positional isomer is ignored
The two functional isomers

Different position of hydrogen
(5) Tautomerism remains in dynamic equilibrium
atoms
to each other

2.1 Chain Isomerism or nuclear isomerism or skeletal isomerism
Chain isomers have the same molecular formula but differ in the order in which carbon atoms are bonded to each
other.This type of isomerism is due to difference in the arrangement of carbon atoms i.e. straight or branched
chain of carbon atoms. It is also known as nuclear or skeletal isomerism
Condition : – 1. Size of main chain or side chain or both should be different.

• 2. Nature of functional group, multiple bond or substituent should not change. i
Ex.3 (A) CH3 – CH2CH2 – CH3
Butane 2–Methylpropane
Size of main chain = 4 Size of main chain = 3
Size of side chain = 0 Size of side chain = 1
Isomeric pair :
When more than one structure can be written with a given molecular formula, each of the structure with respect
to any other structure is called an isomeric pair.
Isomerism between two structures 'a1' & 'a2' can also be seen as a relation a1Ra2 between them.
CH3
|
Ex.4 CH3  CH2  CH2  CH2  CH3 , CH3  CH2  CH  CH3 , CH3  C  CH3
| |
(a1 ) CH3
CH3
(a 3 )
(a 2 )
a1 R a2  CI (chain isomers)
a1 R a3  CI
a2 R a3  CI
Ex.5 C6H14 = 5 isomers
CH3  CH2  CH2  CH2  CH2  CH3 CH 3  CH 2  CH 2  CH  CH 3 CH3  CH2  CH  CH2  CH3
| |
(a1 ) , C H3 , CH3
(a 2 ) (a 3 )
CH3
| CH3  CH  CH  CH3
CH3  CH2  CH  CH3 | |
| CH3 CH3
CH3 (a 5 )
(a 4 )
a1 R a2  CI
a1 R a3  CI
a1 R a4  CI
a1 R a5  CI
a2 R a3  not CI
a2 R a4  CI
a2 R a5  CI
a3 R a4  CI
a3 R a5  CI
a4 R a5  not CI

No. of alkane isomers as a function of no. of carbon atoms :
no. of
mole cula r form ula no. of isom ers
ca rbon atom s
1 CH4 1
• 2 C2 H6 1 i
3 C3 H8 1
4 C4 H10 2
5 C5 H12 3
6 C6 H14 5
7 C7 H16 9
8 C8 H18 15
9 C9 H20 35
10 C10 H22 75
15 C15 H32 4347
20 C20 H42 36,719
Chain isomerism in alicyclic compounds :

Ex.6 C8H16

Size of side chain = 2 Size of side chain 1 = 1
Size of side chain 2 = 1
Ex.7

Ex.8
a1 R (a2 – a5)  C.I.

a2 R (a3 – a5)  not C.I.
a3 R (a2, a4, a5)  not C.I.
a4 R (a2 , a3 , a5)  not C.I.

Chain isomerism in aromatic compounds
(1) (2) (3) (4)
(1) R (2) C.I.

• (1) R (3) C.I. i
(1) R (4) C.I.
(2) R (3) C.I.
(2) R (4) C.I.
(3) R (4) not C.I.
Ex.9 Molecular formula is C5H12
(i) CH3 – CH2 – CH2 – CH2 – CH3 (ii) CH3  CH2  CH  CH3
|
CH3
Pentane 2 – Methyl butane
CH3
|
CH3  C  CH3
(iii) |
CH3
2, 2 – Dimethyl propane
Size of main chain = 3
Size of side chain = 2
Compound (i) and (ii), (i) and (iii), (ii) and (iii) are chain isomers
2.2 Position isomerism :

When two or more organic compounds have same molecular formula but they differ in the position of the
functional group or the substituent, then they are called position isomers & the phenomena is called position
isomerism.
Condition : Same size of main chain or side chain but different position of group or substituents or functional
group.
Ex.10 (a) H3 C  CH2  CH  CH2 (but  1  ene ) 

position isomers
H3 C  CH  CH  CH2 (but  2  ene)
HC  C  CH2  CH2  CH3 (pent  1  yne) 

(b) position isomers
H3 C  C  C  CH2  CH3 (pent  2  yne)
(c) H3 C  H2C  H2C  Cl (1  chloropropane ) 

H3 C  CH  CH3 (2  chloropropane ) position isomers
Isopropyl chloride 
|
Cl
(d) Cl – CH = CH – Cl ] position isomers
(dichloro ethene) (dichloroethene)

or (ethylidene chloride) or (ethylene chloride)

(e) C8H10 (3-aromatic position isomers)
(I) (II) (III) position isomers
o-xylene m-xylene
p-xylene
• i
(f) C7H7NO2 (3-aromatic position isomers)
(I) (II) (III)
(I) R (II)  P. I.

(I) R (III)  P. I.
(II) R (III)  P. I.
(g) C6H3 (OH)3  (3 aromatic position isomers)
(I) (II) (III)
2.3 Functional isomerism

Compound having same molecular formula but different functional groups in their molecules show functional
isomerism and are called functional isomers.
Condition : Functional group should be different, chain and position isomerism are not considered.
Formula Functional Isomers

(i) CnH2n Alkene, Cycloalkane
(ii) CnH2n-2 Alkadiene, Alkyne, Cycloalkene

(iii) CnH2n+2O Alcohol, Ether
(iv) CnH2nO Aldehyde, Ketone, Oxirane (epoxy)
Acid, ester, hydroxy, carbonyl
(v) CnH2nO2 (aldehyde, ketone compounds)
Ex.11 CH3 – CH2OH CH3 – O – CH3

Ethanol Methoxymethane
Functional groups – OH Function groups – O –
Functional groups – COOH Functional groups

Ex.12 What type of isomerism exist between four structural isomers of C4H9NH2
CH3  CH  CH2  CH3 CH3  CH  CH2  NH2
| |
NH2 CH3
(I) ( II)
• CH3
i
|
CH3  C  NH2
| CH3  CH2  CH2  CH2  NH2
CH3 ( IV )
( III )
Ans. (I) and (II) are chain isomers (I) and (III) are chain isomers
(I) and (IV) are position isomers (II) and (III) are position isomers
(II) and (IV) are chain isomers (III) and (IV) are chain isomers
Ex.13 Functional isomers of CH3 – C  CH is
(A) CH2 = C = CH2 (B) (C) (D) Both A and B

Ans. D (Hint : sp carbon not possible in C3–C7 rings.)
2.4 Ring chain isomers :

When two or more organic compounds have same molecular formula but they differ in their structures due to one
being a cyclic compound & the other one an open chain compound, then they are called ring chain isomers &
the phenomena is called ring-chain isomerism or functional isomerisum.
Ex.14 Write all isomers of C4H8 and indicate relationship between them :
C4H8
(1) R(2)  R.C.I. (2) R(3)  R.C.I (3) R(5)  CI

(1) R(3)  P.I. (2) R(4)  C.I. (4) R(5)  RCI
(1) R(4)  R.C.I. (2) R(5)  RCI
(1) R(5)  C.I. (3) R(4)  R.C.I
Ex.15 Compound CH3 – CH2 – CH2 – C  CH and show..

(A) Position isomers (B) Chain isomers
(C) Ring chain isomers (D) All of these
Ans. C
Ex.16 1, 2–Epoxy propane and prop–2–en–1–ol (Allyl alcohol) are
(A) Position isomers (B) Functional isomers
(C) Ring chain isomers (D) Both B and C
Ans. (D)
2.5 Metamerism
This type of isomerism is due to the difference in the nature of alkyl groups attached to the polyvalent atom
or functional group. Metamers belong to the same homologous series. Compounds like ethers, thioethers,
secondary amines etc. show metamerism.
Condition : 1. Functional group should be polyvalent, hetroatomic.
2. Nature of functional group should not change
3. Chain and position isomerism is not considered.

Ex. 17 C2 H5 – O – C 2 H5 C3H7 – O – CH3
Diethyl ether Methyl propyl ether
Hydrocarbon groups – C2H5 , – C2H5 Hydrocarbon groups – C3H7, – CH3
Ex. 18
• i
Hydrocarbon groups – CH3 , –C3H7 Hydrocarbon groups
– CH3, – C2H5 , – C2H5
Ex. 19
Hydrocarbon groups – C2H5 , – CH3 Hydrocarbon groups – CH3, – C2H5
O O
CH3 – C – NH – CH3 H – C – NH – CH2CH3

Ex. 20
N–Methylethanamide N–Ethylmethanamide
Hydrocarbon groups – CH3, – CH3 Hydrogen groups – H, – CH2CH3
Ex. 21
Groups – CH3, – CH3 Groups – H, – CH2 – CH3
O O
|| ||
Ex.22 Compound CH3  CH2  C  NH  CH3 and CH3  C  NH  CH2  CH3 are
( I) ( II)
(A) Functional isomers (B) Position isomers

(C) Metamers (D) All of these
Ans. C
Ex.23 Metamer of the compound P is

O
P= C–O
O
(A) (B) O–C
O
(C) O–C (D) All of these
Ans. C

2.6 Tautomerism
Two compounds have different functional groups due to shiffting of H-atom. The two isomers remain in dynamic
equilibrium. These two can be isolated.
Tautomerism is the phenomenon in which two structural isomers differ in the relative positions of their atoms and
are spontaneously interconvertable and can exist in dynamic equilibrium. The two forms in tautomeric equilibrium
are called tautomers of each other. The interconvertibility of tautomers is a chemical reaction which involves
making and breaking of bonds.
• i
O OH
|| |
e.g. CH3  C  CH3 CH2  C  CH3
( I) ( II)
Tautomers (I) and (II) are structural isomers that are formaly related only by the shift of a hydrogen atom and one
or more pi bonds. Tautomerism, thus in a single way, can also be defined as follows type of isomerism occuring
by the migration of atom (generally acidic hydrogen from carbon to electronegative atom and
vice-versa) and the movement of a double bond is called tautomerism. Tautomers are true isomers and either of
the individual tautomeric forms may be isolated.

1. Write the IUPAC name of following compounds.
(i) H3 C — CH2 — CH — COOH (ii) 3-Bromocyclohexane-1-sulphonic acid
|
OC 2H5
(iii) (iv) 3-Cyano-3-ethoxy-4-nitropentanoyl bromide
Sol. (i) 2-Ethoxybutanoic acid (ii)
(iii) 1,1, 2-Trimethylcyclopentane (iv)
2. Draw the structure of following IUPAC name.
(i) (ii) 3-Methoxycarbonylpropanoic acid
Sol. (i) 3-Ethylpenta-1,4-diyne (ii)

3. Find total number of structure isomers of dimethyl cyclopropane and dimethyl cyclobutane are respectively.
(A) 4, 6 (B) 3, 4 (C) 4, 5 (D) 2, 3
Ans. (D)
Sol.
• i
4. How many structures of cycloalkanone are possible with molecular formula C5H8O.
Ans. 6
Sol.
5. Find out the total number of cyclic isomers of the compound (X) C4H7Cl.
Ans. 4.
8
Sol. X = C4H7Cl DU = 5 – =1
2
Total = 4

`
IUPAC NOMENCLATURE
Ex.1 How many 1°, 2°, 3° and 4° carbon atoms are present in following molecule.
CH3
|
CH3 – CH – C – CH2 – CH – CH3
| | |
CH3 CH3 CH2 – CH3
Sol. 1° Carbon atoms = 6 , 2° Carbon atoms = 2 , 3° Carbon atoms = 2 , 4° Carbon atom = 1
Note : Primary, secondary, tertiary & quaternary carbon atoms in a molecule are denoted by the letters p,
s, t and q respectively.
Ex.2 How many 1°, 2°, 3° and 4° carbon atoms are present in following molecule
CH3
|
CH3  C  CH2  CH  CH3
| |
CH3 CH3
Sol.
1o
C H3
|
1o 4o 2o 3o 1o
C H3  C  C H 2  C H  C H3
| |
1o
C H3 1o CH3
1° Carbon atoms = 5 , 2° Carbon atom = 1 , 3° Carbon atom = 1, 4° Carbon atom = 1
Ex.3 Write IUPAC name of following compound
CH3
SO3H
OH
I
CH
(a) CH3 (b) CH3 CH3
Sol. (a) 2 – Iodo – 3 – methylcyclopentanesulfonic acid.

Here Secondary prefix = 2 – Iodo – 3 – methyl
Word root = pent
Primary suffix = ane
Secondary suffix = sulfonic acid
(b) 2 – Isopropyl – 5 – methylcyclohexanol

Here Secondary prefix = 2 – Isopropyl – 5 – methyl
`
Word root = hex

Primary suffix = an(e)
Secondary suffix = ol
Ex.4 Write IUPAC name of the following compounds.
(a) (b)
Ans. (a) Oct-1-en-4-yne (b) Hepta-3,6-dien-1-yne
Ex.5 Write IUPAC name of following aromatic compounds
CH3
|
CH2 – CH – CHO
3 2 1
Ans. (a) 2-Methyl-3-phenylpropanal (b)
STRUCTURAL ISOMERISM
CH3  CH  CH  CH3 CH3 CH2CH  CH2  structural Isomers

But  2  ene But  1  ene 
Ex.1 ,
CH3
|
CH  CH2  CH3 CH3  CH  CH2CH3 
| |  Identical compounds
CH3 CH3  (not isomers)

Ex.2
2  Methyl bu tan e , 2  Methylbutane 
Ex.3 (A) CH3 – CH2CH2 – CH3

Butane 2–Methylpropane
Isomeric pair :
When more than one structure can be written with a given molecular formula, each of the structure
with respect to any other structure is called an isomeric pair.
Isomerism between two structures 'a1' & 'a2' can also be seen as a relation a1Ra2 between them.
CH3
|
CH3  CH2  CH  CH3
CH3  C  CH3
|
CH3  CH2  CH2  CH2  CH3 |
CH3 CH3
( a1 ) (a 2 ) (a 3 )
Ex.4 , ,
Ans. a1 R a2  CI (chain isomers)
a1 R a3  CI
a2 R a3  CI

`
Ex.5 C6H14 , possible isomers?
Ans.
CH3  CH2  CH2  CH  CH3
CH3  CH2  CH  CH2  CH3
|
CH3  CH2  CH2  CH2  CH2  CH3 |
C H3 CH3
(a1 ) ,
(a 2 ) , ( a 3)
CH3
|
CH3  CH2  CH  CH3 CH3  CH  CH  CH3
| | |
CH3 CH3 CH3
(a 4 ) (a 5 )
,
a1 R a2  CI
a1 R a3  CI
a1 R a4  CI
a1 R a5  CI
a2 R a3  not CI
a2 R a4  CI
a2 R a5  CI
a3 R a4  CI
a3 R a5  CI
a4 R a5  not CI
Ex.6 C8H16
Ans.
Ex.7
Ans.

`
Ex.8
Ans. a1 R (a2 – a5)  C.I.

a2 R (a3 – a5)  not C.I.
a3 R (a2, a4, a5)  not C.I.
a4 R (a2 , a3 , a5)  not C.I.
Ex.9 Molecular formula is C5H12
Ans.
CH3  CH 2  CH  CH3
|
CH3
(i) CH3 – CH2 – CH2 – CH2 – CH3 (ii)
Pentane 2 – Methyl butane
CH3
|
CH3  C  CH3
|
(iii) CH3
2, 2 – Dimethyl propane
Size of main chain = 3
Size of side chain = 2
Compound (i) and (ii), (i) and (iii), (ii) and (iii) are chain isomers
H3 C  CH2  CH  CH2 (but  1  ene ) 

position isomers
H3 C  CH  CH  CH2 (but  2  ene )
Ex.10 (a)
HC  C  CH2  CH2  CH3 (pent  1  yne ) 
position isomers
H3 C  C  C  CH2  CH3 (pent  2  yne )
(b)
H3 C  H2C  H2C  Cl (1  chloropropane ) 
H3 C  CH  CH3 (2  chloropropane ) position isomers
Isopropyl chloride 
|
Cl
(c)
(d) Cl – CH = CH – Cl ] position isomers

(dichloro ethene) (dichloroethene)
or (ethylidene chloride) or (ethylene chloride)
(e) C8H10 (3-aromatic position isomers)
position isomers
(I) o-xylene (II) m-xylene (III) p-xylene

(f) C7H7NO2 (3-aromatic position isomers)
`
(I) (II) (III)
(I) R (II)  P. I.

(I) R (III)  P. I.
(II) R (III)  P. I.
(g) C6H3 (OH)3  (3 aromatic position isomers)
(I) (II) (III)

Ex.11 CH3 – CH2OH CH3 – O – CH3
Ethanol Methoxymethane
Functional groups – OH Function groups – O –
Functional groups – COOH Functional groups
Ex.12 What type of isomerism exist between four structural isomers of C4H9NH2
CH3  CH  CH2  CH3 CH3  CH  CH2  NH 2
| |
NH 2 CH3
( I) ( II)
CH3
|
CH3  C  NH 2
|
CH3 CH3  CH2  CH2  CH2  NH 2
( III) ( IV )
Ans. (I) and (II) are chain isomers (I) and (III) are chain isomers
(I) and (IV) are position isomers (II) and (III) are position isomers
(II) and (IV) are chain isomers (III) and (IV) are chain isomers
Ex.13 Functional isomers of CH3 – C  CH is
(A) CH2 = C = CH2 (B) (C) (D) Both A and B

Ans. D (Hint : sp carbon not possible in C3–C7 rings.)

`
Ex.14 Write all isomers of C4H8 and indicate relationship between them :
C 4 H8
(1) R(2)  R.C.I. (2) R(3)  R.C.I (3) R(5)  CI

(1) R(3)  P.I. (2) R(4)  C.I. (4) R(5)  RCI
(1) R(4)  R.C.I. (2) R(5)  RCI
(1) R(5)  C.I. (3) R(4)  R.C.I
Ex.15 Compound CH3 – CH2 – CH2 – C  CH and show.

(A) Position isomers (B) Chain isomers
(C) Ring chain isomers (D) All of these
Ans. C
Ex.16 1, 2–Epoxy propane and prop–2–en–1–ol (Allyl alcohol) are
(A) Position isomers (B) Functional isomers
(C) Ring chain isomers (D) Both B and C
Ans. (D)
Ex. 17 C 2 H5 – O – C2 H5 C3H7 – O – CH3

Ans. Diethyl ether Methyl propyl ether
Hydrocarbon groups – C2H5 , – C2H5 Hydrocarbon groups – C3H7, – CH3
Ex. 18
Ans. Hydrocarbon groups – CH3 , –C3H7 Hydrocarbon groups
– CH3, – C2H5 , – C2H5
Ex. 19
Ans. Hydrocarbon groups – C2H5 , – CH3 Hydrocarbon groups – CH3, – C2H5
O O
CH3 – C – NH – CH3 H – C – NH – CH2CH3
N–Methylethanamide N–Ethylmethanamide
Ex. 20 Hydrocarbon groups – CH3, – CH3 Hydrogen groups – H, – CH2CH3

`
O
H – C – NH – CH2CH3
N–Ethylmethanamide
Ex. 21 Hydrogen groups – H, – CH2CH3
Ans. Groups – CH3, – CH3 Groups – H, – CH2 – CH3
O O
|| ||
CH3  CH2  C  NH  CH3 CH3  C  NH  CH2  CH3
Ex.22 Compound
( I) and
( II) are
Ans. C
Ex.23 Metamer of the compound P is
O
C–O
P=
O
O–C
(A) (B)
O
O–C
(C) (D) All of these
Ans. C

1. Write the IUPAC name of following compounds.

H3 C — CH2 — CH — COOH
|
OC 2H5
(i) (ii) 3-Bromocyclohexane-1-sulphonic
acid
(iii) (iv) 3-Cyano-3-ethoxy-4-nitropentanoyl

-bromide
Sol. (i) 2-Ethoxybutanoic acid (ii)
(iii) 1,1, 2-Trimethylcyclopentane (iv)
2. Draw the structure of following IUPAC name.
(i) (ii) 3-Methoxycarbonylpropanoic acid
Sol. (i) 3-Ethylpenta-1,4-diyne (ii)
3. Find total number of structure isomers of dimethyl cyclopropane and dimethyl cyclobutane are
respectively.
(A) 4, 6 (B) 3, 4 (C) 4, 5 (D) 2, 3
Ans. (D)
Sol.
4. How many structures of cycloalkanone are possible with molecular formula C5H8O.
Ans. 6
Sol.

5. Find out the total number of cyclic isomers of the compound (X) C4H7Cl.
Ans. 4.
Sol. X = C4H7Cl DU = 5 – 4 = 1
Total = 4

Type (I) : Very Short Answer Type Questions : [01 Mark Each]
1. Write the structure of following IUPAC name :
(i) 1, 1-Dibromo-3-ethyl- 4-flourohexane (ii) 5-Bromomethyl-6-methylhept-3-ene

(i) 2-Methylpentane-2,4-diol (ii) 4-Methylhexan-2-ol
3. Write the correct IUPAC name of the following :
(i) H3 C — N — CH — CH3 (ii) CH3 – CH2  CH  NH  CH3

| | |
CH3 CH3 CH3

(i) 3-Ethynylhexa-1,4-diene (ii) 1-Cyclobutylprop-1-ene
5. Write the correct IUPAC name of the followings :
(i) (ii) HOOC — CH2 — CH2 — CH — SO 3H

|
CH3
(i) (ii)

(i) 2-Methoxybutan-1-ol (ii) 4-Chloro-2-methylphenol
(i) (ii)
9. What is isomerism? Give an example.
10. What is positional isomerism? Give an example.
11. What is Metamerism? Give one example.
12. Write all cyclic isomers of C3H6O.
13. Identify the molecular weight of the compound ‘X’ containing carbon and hydrogen atoms only with 3 and 2
bonds in one molecule.
14. Write the ring chain functional isomer of compound But-2-ene are \
Type (II) : Short Answer Type Questions : [02 Marks Each]
(i) (ii)
(iii) (iv)
16. Identify the relationship between the given compounds.
(1) and (2) and
(3) and (4) CH3 COOCH3 and CH3COCH2OH
17. Write down the IUPAC name of the following compound:

(i) Methyl benzoate (ii) Phthallic acid (iii) Neopentane (iv) Isooctane
18. What is the type of hybridisation of each carbon in the following :
(1) CH3Cl (2) (CH3)2CO (3) CH3CN (4) HCONH2
19. Which of the following represents the correct IUPAC name for the compounds concerned ?
(1) 2,2-Dimethylpentane or 1, 2-Dimethylpentane
(2) 2,4,7- Trimethyloctane or 2,5,7-Trimethyloctane
(3) 2-Chloro-4-methylpentane or 4-Chloro-2-methylpentane
(4) But-3-yn-1-ol or But-4-ol-1-yne.
20. Expand each the following condensed formulae into their complete structural and bond line formulae :
(1) HOCH2CH2NH2 (2) CH3(CH2)3OH
(3) CH3CH2COCH2CH3 (4) CH3CH=CH(CH2)3CH3
21. Write common & IUPAC name of following structure:
CH3 OH CHO
CH = CH2
CH3 OH
(i) (ii) (iii) (iv)
CH3
22._ Identify the relationship between the given compounds.

Cl
Cl
(1) and (2) and
Br
Br
(3) and (4) and


Section (A) : Fundamental of Organic Chemistry
A-1. Write the number of  and  bonds in the following molecules.
CH3
(a) (b) OH (c) N –CH 3
A-2. What is the nature of marked carbon atom in the following compounds.
(a) (b) (c)
A-3. Find the number of 1°, 2° & 3° hydrogen atoms in the following compounds
(a) (b) CH3–CH2–CH3 (c) CH3–CH2–CH2–CH3
A-4. Draw formulae for the first four members of each homologous series begining with the following.
(a) H–COOH (b) H–CH=CH2 (c)
A-5. Find the hybridization state of each carbon atoms in following compound.
CH2 = C = CH – CH2 – C  C – CH2 – NH2
A-6. Calculate the molecular weight of the lowest hydrocarbon which contains sp & sp2 hybridised carbon atoms
only.
A-7 Write the total number of bonds in the following compounds.
(a) (b) (c)
Section (B) : Classification and General Rules of IUPAC Nomenclature

B-1. Classify the following compounds as homocyclic, heterocyclic, alicyclic, aromatic, saturated and
unsaturated.
(a) (b) (c) (d)

B-2. Indicate the following as 1°, 2° and 3° amines.
CH3
(a) (b) NH (c)
N (d) N –CH 3
B-3. Indicate the following as 1°, 2° and 3° alcohol.
(a) (b) (c)
B-4. Write the common name of the following alkyl groups.
(a) (b) (c)
(d) –CH2–CH3 (e) CH3–CH2–CH2–

B-5. Write the priority order of given functional groups.
–COOH, –CN, –CHO, –OH, –COCH3, –NH2
Section (C) : IUPAC-Nomenclature of Alkane

C-1. Write IUPAC name of the following compounds :
(a) (b) (c) (d)
C-2. Write IUPAC name of the following

Me Me
(i) Me (ii)
Me
(iii) (iv)
C-3. Write the IUPAC name of following compounds
(i)
(ii)
C-4. Write IUPAC name of the following compounds:-

(a)
(b)
(c)
C-5. Write the correct IUPAC name of the following compounds.
CH3
|
(i) (ii) CH3 — CH2 — CH2 — CH2 — CH2 — CH — C — CH2CH3
| |
CH3 CH2 — CH2 — CH3
(iii)
Section (D) : IUPAC-Nomenclature of Alkene & Alkyne

D-1. Write the general formula of alkenes. Give common and IUPAC names of first three members.
D-2. Write the general formula of alkynes. Give common and IUPAC names of first three members.
D-3. Write IUPAC name of the following :-
(i) (CH3)3 C – CH = CH2 (ii) CH2 = CH – CH = CH2
CH3 CH3
(iii) CH3–CH2–CH2–C–CH2–C=CH2 (iv)

CH3
D-4. Write the IUPAC name of the following compounds:-

CH3 CH2 – CH3 CH3
–
–
–
(a) CH3 – CH2 – – CH = CH – CH2 – CH3 (b) CH3 – CH2 – CH – CH – CH – CH = C – CH3

– – – –
CH2
CH2
CH – CH3
CH3
D-5. Draw the bond line structures of the following compounds.

(a) 2-Methylhept-3-ene (b) 2,6-Dimethylhepta-1, 5-diene
D-6. Write IUPAC name of the following
(i) (ii) (iii)
D-7. Write the IUPAC name of the following compounds:-

(a) CH3 – – C  C – CH3 (b) (c)
D-8. Write IUPAC name of the following

(i) (ii) CH3–CH=CH–C  CH
(iii) CH  C–CH2–CH = CH2 (iv) CH2=CH–CC–CH3
Section (E) : IUPAC-Nomenclature of Cyclic Compounds

E-1. Write correct IUPAC name of the following
(i) (ii) (iii) (iv)
E-2. Write the correct IUPAC name of the following compounds.
(a) (b)
(c) (d)
E-3. Write the correct IUPAC name of the following compounds.

CH3
(a) CH3 (b) (c)
E-4. Write structures of the following IUPAC name.

(i) 3-Methylcyclohexene (ii) 1, 3-Dicyclopentyl propane
(iii) 1-Methyl-4-propylcyclohexane (iv) 2-Ethyl-1,1-dimethylcyclopentane
E-5. Write the IUPAC name of the following
(i) (ii) (iii) (iv)
E-6. Write IUPAC names of the following hydrocarbon (use common naming for hydrocarbon groups.)
(a) (b) (c) (d)

E-7. Identify the parent chain in the following compounds as ring or side chain.
(a) (b) (c)
(d) (e) (f)
Section (F) : IUPAC of Functional groups

F-1. Write the correct IUPAC name of the following compounds.
CH = CH – COCH3 OH OH
(a) (b) CH2 – CH – CH2 – CH3
(c) (CH3)3COH (d)
F-2. Write the correct IUPAC name of the following compounds.

Cl CH3 F
| | |
(a) (b) CH3  CH  CH2  CH  CH  CH2  CH3
|
Br
(c) (d)
F-3. Write IUPAC names of following ethers :
(a) (b) (c) (d)
Section (G) : IUPAC of Functional groups ( )

G-1. Write the correct IUPAC name of the following compounds.
(a) (b) CH3  CH2  CH  CH  CH  CH2  CHO
|
CH3
(c) (d)
G-2. Write the structure of the following molecules :

(a) 4-Formyl-2-oxocyclohexane-1-carboxylic acid. (b) 2-Cyano-3-oxopentanedioic acid
(c) 3-Methyl-2-methylenebut-3-enoic acid (d) 5-Oxocyclohex-2-ene-1-carbonitrile
Section (H) : IUPAC of Functional groups ( )

H-1. Write IUPAC Name
O
(a) CH3CH2 – CH – C – OCH3 (b) (c)
– –
CH2
CH3
H-2. Write IUPAC names of following compounds.
(a) (b)
(c) (d)
Section (I) : IUPAC-Nomenclature of Aromatic compounds

I-1. Write IUPAC name of the following
(a) (b)
(c) (d)
I-2. Write the correct IUPAC name of the following :
(a) (b)
(c) (d)
Section (J) : Structural Isomerism
J-1. Identify the relationship between the given compounds.
(a) and (b) and
(c) and
J-2. Identify the relationship among the following :
(a)
(b)
(c)
(d)
J-3. Identify the relationship between the given compounds.
(a) & (b) &
(c) & (d) &
Section (K) : Number of Structural Isomers

K-1. Write the total sum of degree of unsaturation (D.U.) of following compound.
K-2. How many number of all structurally isomeric dienes with molecular formula C5H8 are possible ?
K-3. How many esters are possible of formula C4H8O2? What is relation between them?
Section (A) : Fundamental of Organic Chemistry
A-1. Number of bonds in given compound is :
CH2=C=CH-CCH
(A) 10 (B) 12 (C) 14 (D) 16
A-2. Number of 3º and 2º carbon atoms in the following compound are.
(A) 5, 6 (B) 5, 7 (C) 4, 6 (D) 6, 6
A-3. Molecular formula of naphthaquinone is
(A) C12H8O2 (B) C11H6O2 (C) C10H6O2 (D) C10H8O2
A-4.
In above compound total number of 2º hydrogen atoms are :

(A) 3 (B) 18 (C) 6 (D) 9
A-5. An organic compound has molecular formula C9H18. It is a saturated hydrocarbon and its all hydrogen atoms are
identical. Its structural formula can be :
(A) (B)
(C) (D)
A-6.
Incorrect statement for the above structure :

(A) I, II & III have CnH2n-2 general formula (B) I , II & III have same empirical formula
(C) I , II are identical and homologue of compound III. (D) I, II & III have same molecular formula
Section (B) : Classification and General Rules of IUPAC Nomenclature
B-1. compound is :
(A) Alicyclic heterocyclic (B) Aromatic heterocyclic

(C) Saturated heterocyclic (D) Unsaturated homocyclic
B-2. Which of the following is not an alicyclic compound ?
(A) (B) (C) (D)

N
|
H
B-3. The saturated heterocyclic compound is :
(A) (B) (C) N (D)

N
.. |
H
B-4. Which of the following has not bridgehead carbon :
(A) (B) (C) (D)
B-5. Which of the following compound is unsaturated hydrocarbon.
(A) (B) CH3–C  N (C) (D)
B-6. Which of the following is a correct priority order of functional groups?
(A)
(B)
(C)
(D)
Section (C) : IUPAC-Nomenclature of Alkane
C-1. The correct IUPAC name of the alkane is :
(A) 2-Ethyl-4-methylhexane (B) 5-Ethyl-3-methylhexane

(C) 3,5-Dimethylheptane (D) 3,5-Dimethylhexane
C-2. The correct structure of 6-Ethyl-2,3,5-trimethylnonane is :
(A) (B)
(C) (D)
C-3. The correct IUPAC name of the following compound is :
(A) 1-Bromo-1-ethyl-2-fluoro-2-iodo-1-nitroethane. (B) 3-Bromo-4-fluoro-4-iodo-3-nitrobutane.

(C) 2-Bromo-1-fluoro-1-iodo-2-nitrobutane. (D) 1-Fluoro-1-iodo-2-bromo-2-ethyl-2-nitroethane.
C-4. A student named a certain compound as 2, 3-diethylbutane. its correct IUPAC names is
(A) 2, 3-Dimethylhexane (B) 3, 4-Dimethylhexane
(C) 2-Ethyl-3-methylpentane (D) 2-Ethylbutane
C-5. Which alkane would have only the primary and tertiary carbon ?
(A) Pentane (B) 2-Methylbutane
(C) 2, 2-Dimethylpropane (D) 2, 3-Dimethylbutane
C-6. The common and IUPAC names for the group, (CH3)2CHCH2–respectively are
(A) Isobutyl, 2-methylpropyl (B) Isobutyl, 1-methylpropyl
(C) tert-Butyl, 1, 1-dimethylethyl (D) sec-Butyl, 2-methylpropyl
Section (D) : IUPAC-Nomenclature of Alkene & Alkyne

D-1. Select the structure with correct numbering in the chain :
(A) (B)
(C) (D)
D-2. The correct IUPAC name of the compound

(A) 4-Ethylpent-1-ene (B) 2-Ethylpent-4-ene (C) 4-Methylhex-1-ene (D) 3-Methylhex-1-ene
D-3. The correct structure of 2-Ethyl-3-methylhexa-1,4-diene.
(A) (B) (C) (D)
D-4. The correct IUPAC name of the compound is –

F I
C
Cl C CH2
CH2 CH2 Br
(A) 4-Bromo-1-chloro-2-fluoroiodomethylbutene
(B) 4-Bromo-2-chloromethyl-1-fluoro-1-iodobut-1-ene
(C) 2-(2-Bromoethyl)-3-chloro-1-fluoro-1-iodoprop-1-ene
(D) 1-Bromo-3-chloromethyl-4-fluoro-4-iodobut-1-ene
D-5. Ethoxyethene is written as follows, H2C = CH – O – CH2 – CH3.
The structure of 2-Chloro-1-ethoxyethene (incorrect name) with correct numbering will be
1 2 1 2
(A) H2C  CH – O – CH2 – CH2 – Cl (B) CH2  CH – O – CH – CH3
|
Cl
2 1 1 2
(C) H2C  C – O – CH2 – CH2 – Cl (D) Cl – CH  CH – O – CH2 – CH3
|
Cl
D-6. The correct IUPAC name of the given compound is
(A) 3–Chloro–1–fluoro–1–iodo–4–methoxybut–1–en–3–yne
(B) 4–Methoxy–2–chloro–1–fluoro–1–iodobutenyne
(C) 3–Chloro–4–fluoro–4–iodo–1–methoxybutenyne
(D) 2–Chloro–1–fluoro–1–iodo–4–methoxybutenyne
Section (E) : IUPAC-Nomenclature of Cyclic Compounds

E-1. In which of the following side chain (acyclic chain) is the main chain.
(A) (B)
(C) (D)
E-2. In which of the following compound IUPAC numbering is correct :
(A) (B)
(C) (D)
E-3. IUPAC name for is
(A) (1-Methylpropyl)cyclobutane (B) 2-(n-butyl)cyclobutane

(C) 2-Cyclobutylbutane (D) 1-Cyclobutylbutane
E-4. The correct IUPAC name of is :
(A) 1-Cyclopentyl-1, 1-dimethylbutane (B) 2-Cyclopentyl-2-methylpentane

(C) 2-Methyl-2-cyclopropylpentane (D) 1, 1-Dimethyl-1-cyclopentylbutane
E-5. In which of the following cyclic chain is the main chain ?
(A) (B) (C) (D)
E-6. IUPAC name of the compound is
(A) 1-Cyclohexyl-3-methylpent-1-ene (B) 3-Methyl-5-cyclohexylpent-1-ene

(C) 1-Cyclohexyl-3-ethylbut-1-ene (D) 1-Cyclohexyl-3,4-dimethylbut-1-ene
E-7. The correct IUPAC name of the compound
(A) 1-Ethenylcyclohexa-2, 4-diene (B) 5-Ethenylcyclohexa-1, 3-diene

(C) 6-Ethenylcyclohexa-1, 3-diene (D) Cyclohexa-2, 4-dienylethene
Section (F) : IUPAC-Nomenclature of Functional groups

F-1. The IUPAC name of
Br
|
CH3  CH  CH2  CH2  CH2  C  CH3 is
| |
OH Br
(A) 6, 6-Dibromoheptan-2-ol (B) 2, 2-Dibromoheptan-6-ol

(C) 6, 6-Dibromoheptan-2-al (D) None of these
F-2. The correct IUPAC name of the compound is :
(A) 6-Ethyl-1-methyl-4-oxohept-6-ene-1-sulphonic acid

(B) 7-Ethyl-5-oxooct-7-ene-2-sulphonic acid
(C) 2-Ethyl-7-sulphooct-1-ene-4-one
(D) 7-Methylene-5-oxononane-2-sulphonic acid
(A) 4-Ethyl-3-methylnonane-2, 8- diol (B) 6-Ethyl-7-methylnonane-2, 8-diol

(C) 5-Ethyl-1, 6, 7-trimethylheptane-1, 7-diol (D) 4-Ethyl-2-methylnonane-2, 7-diol
F-4. The correct structure of 6-Amino-4-hydroxycylohex-2-ene-1-sulphonic acid.
(A) (B)
(C) (D)
(A) 3-(1-Methylethenyl)-4-hydroxypentan-2-one
(B) 3-(1-Hydroxyethyl)-4-methylpent-4-en-2-one
(C) 3-(1-Hydroxymethyl)-4-methylenepentan-2-one
(D) 3-(1-Oxoethyl)-4-methylpent-4-en-2-ol.
F-6. IUPAC name of the compound CH3  NH  CH  CH2  CH  CH3 is

| |
CH3 CH3
(A) 2-(N-methylamino)-4-methylpentane (B) N-Methyl-4-methylpentan-2-amine
(C) 2-(N-methylamino)-3-isopropylpropane (D) 2-(N-methylamino)-1, 4, 4-trimethylbutane
Section (G) : IUPAC-Nomenclature of Functional groups ( )

G-1. The IUPAC name of the following compound is :
(A) 3-Methylbut-2-enoic acid (B) 3-Methylbut-3-enoic acid

(C) 2-Methylbut-1-en-4-oic acid (D) 3-Methylenebutanoic acid
G-2. The IUPAC name of the following is :

CH3 CH  CH  CH2  CH  CH2COOH
|
NH2
(A) 3-Aminohept-5-enoic acid (B) 5-Aminohex-2-enecarboxylic acid
(C) 3-Aminohept-4-enoic acid (D) 5-Aminohept-2-enoic acid
G-3. is named as :
(A) 2, 3-Dimethylenebutanal (B) 3-Methyl-2-methylenebut-3-enone

(C) 3-Methyl-2-methylenebut-3-enal (D) 2, 3-Dimethylenebutanone
G-4. The correct IUPAC name of compound is :
(A) 1-Chloropentane-1, 4-dione (B) 4-Chlorocarbonylbutan-2-one

(C) 4-Oxopentanoyl chloride (D) 3-Oxobutanecarbonyl chloride
CH2  CHO
|
G-5. IUPAC name of the compound OHC  CH2  CH2  CH  CH2  CHO is
(A) 4, 4-Di(formylmethyl) butanal (B) 2-(formylmethyl) butane-1, 4-dicarbaldehyde
(C) Hexane-3-acetaldial (D) 3-(2-oxoethyl) hexanedial
G-6. The correct IUPAC name of following compound is
COOH
OH
CH2NH2
(A) 4-Aminomethyl-3-hydroxycyclohex-5-ene-1-carboxylic acid
(B) 2-Aminomethyl-5-carboxycyclohex-3-en-1-ol
(C) 4-Aminomethyl-5-hydroxycyclohex-2-ene-1-carboxylic acid
(D) 3-Hydroxy-4-aminomethylcyclohex-5-en-1-oic acid
Section (H) : IUPAC-Nomenclature of Functional groups ( )
H-1.
The IUPAC name of the compound is :

(A) Propanoic anhydride (B) Dipropanoic anhydride
(C) Ethoxy propanoic acid (D) 1-Oxopropyl propanoate
H-2. The IUPAC name of the compound is :
(A) Cyclobutanedioic anhydride (B) Butanedicarboxylic anhydride

(C) Cyclobutanedicarboxylic anhydride (D) Butanedioic anhydride
H-3. The correct IUPAC name of following compound is
(A) Methyl -2-ethylpropanoate (B) Methyl butane-2-carboxylate

(C) Methyl- 2-methylbutanoate (D) Methoxypentanone
H-4. The IUPAC name of is
(A) Ethoxymethanone (B) Ethyl 2-methylpropanoate

(C) Ethoxypropanone (D) 2-Methylethoxypropanone
H-5. Ethyl ethanoyloxyethanoate is :
(A) CH2 (B) CH2 (C) CH2 (D) CH2
H-6. The IUPAC name of the compound is :
(A) N-Ethyl-2-ethylpropanamide (B) N-Ethyl-2-methylbutanamide

(C) N-Ethyl-2-methylpropanecarboxamide (D) N-Ethyl-2-ethylethanecarboxamide
H-7. IUPAC name of the compound BrCH2  CH  CO  CH2  CH2CH3 is

|
CONH2
(A) 2-Bromomethyl-3-oxohexanamide (B) 1-Bromo-2-amido-3-oxohexane
(C) 1-Bromo-2-amido-n-propylketone (D) 3-Bromo-2-proponyl-propanamide
Section (I) : IUPAC-Nomenclature of Aromatic compounds

I-1. The IUPAC name of the following compound is :
(A) 5-Bromo-3-hydroxybenzenecarbaldehyde (B) 3-Bromo-5-formylphenol

(C) 3-Bromo-5-hydroxybenzenecarbaldehyde (D) 1-Bromo-3-formyl-5-hydroxybenzene
I-2. The IUPAC name of the compound is :
(A) 2-Cyano-1-formylbenzene-4-carboxylic acid (B) 3-Cyano-4-formylbenzene-1-carboxylic acid

(C) 4-Carboxy-2-cyanobenzene-1-carbaldehyde (D) 2-Formyl-5-carboxybenzene-1-carbonitrile
I-3. IUPAC name of
(A) 4-Chlorophenyl benzoate. (B) Phenyl-4-chlorobenzenecarboxylate.

(C) Benzyl-4-chlorobenzenecarboxylate. (D) 4-Chloro diphenylcarboxylate.
I-4. The correct IUPAC name of the compound.
(A) N–Formyl-4-chlorobenzenamine (B) N–Formyl-4-chloroaniline

(C) N–(4-chlorophenyl)methanamide (D) N–(Parachlorophenyl)–N–formylaniline
I-5. IUPAC name of the compound is
(A) 2-Chlorocarbonyl ethylbenzenecarboxylate (B) 2-Carboxyethylbenzoyl chloride

(C) Ethyl 2-(chlorocarbonyl)benzenecarboxylate (D) Ethyl 1-(chlorocarbonyl)benzenecarboxylate
I-6. The correct IUPAC name of the compound
(A) 2-Phenoxycarbonylbenzenecarboxylic acid (B) Phenyl-2-carboxybenzenecarboxylate

(C) 2-Benzoyloxybenzenecarboxylic acid (D) 2-Benzyloxycarbonylbenzenecarboxylic acid
Section (J) : Structural Isomerism

J-1. Isomers have essentially identical.
(A) Structural formula (B) Chemical properties
(C) Molecular formula (D) Physical properties
J-2. Compound with same molecular formula but different structural formula are called.
(A) Isomers (B) Isotopes (C) Isobars (D) Isoelectric
J-3. Which compound is not the isomer of 3-Ethyl-2-methylpentane ?
(A) (B)
(C) (D)
J-4. What is the correct relationship between the following compounds ?

CH3  CH2  CH  CH2  CH3 , CH3  CH2  CH2  CH2  CH2
| |
CH3 CH3
(A) Chain isomers (B) Position isomers
(C) Functional isomers (D) Identical
J-5. What is the relation between 3-Ethylpentane and 3-Methylhexane ?

(C) Functional isomers (D) Relation
J-6. CH3 – CH2 – NH – CHO ; CH3  CH  CHO

|
NH2
I II
Which type of isomerism is observed between I and II.
(C) Functional isomers (D) Metamers
J-7. Which of the following is a pair of metamers ?
(A) (B)
(C) (D)
J-8. The correct relationship among the following pairs of given compounds is
(I, II) (II, III)

(A) Functional Isomers Metamers
(B) Metamers Functional isomers
(C) Metamers Metamers
(D) Functional Isomers Functional isomers
J-9. Which of the given set of molecules have similar molecular formula :
(A) Nonane,2-methylheptane
(B) 3-Isopropylcyclopent-1-ene, 3-methylhexane
(C) 3-Methylcyclopent-1-ene,penta-1,3-diene
(D) Ethylcyclohexane, oct-2-ene
J-10. Which amongs the following are not correctly matched.
(A) & CH2=CH–CH=C=CH–CH=CH2 are ring chain isomers.
(B) & are positional isomers.
(C) & are chain isomers.
(D) & are functional group isomers.
J-11. Molecular formula C4H10O represent

(A) Two primary alcohol (B) One secondary alcohol
(C) One tertiary alcohol (D) All of these
Section (K) : Number of Structural Isomers
K-1. Degree of unsaturation in is
(A) 3 (B) 2 (C) 4 (D) 6.

K-2. How many positional isomers are possible for dimethylcyclohexane.
(A) 3 (B) 4 (C) 5 (D) 6
K-3. How many aromatic isomers are possible for trichlorobenzene (C6H3Cl3) ?
(A) 2 (B) 3 (C) 4 (D) 5
K-4. The number of ether isomers represented by formula C4H10O is (only structural)
(A) 4 (B) 3 (C) 2 (D) 1
K-5. Total number of 2° amine isomers of C4H11N would be (only structural)
(A) 4 (B) 3 (C) 5 (D) 2
K-6. Find the number of total structurally isomeric 3° amides with molecular formula C5H11NO.
(A) 4 (B) 3 (C) 2 (D) 5
K-7. How many structural isomers of all the tertiary alcohols with molecular formula C6H14O.
(A) 2 (B) 3 (C) 4 (D) 5
K-8. The number of structural isomers for C5H10 is :
(A) 8 (B) 6 (C) 9 (D) 10

(A) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is correct explanation for
STATEMENT-1.
(B) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is not correct explanation for
STATEMENT-1.
(C) STATEMENT-1 is true, STATEMENT-2 is false.
(D) STATEMENT-1 is false, STATEMENT-2 is true.
(E) Both STATEMENTS are false.
1. Statement-1 : The locant (2, 6, 7) is preferred over the locant (3, 4, 8).
Statement-2 : The first term, i.e. 2 in the first set is lower than the first term, i.e. 3 in the second set.
2. Statement-1 : The IUPAC name of CH3 CH = C H–C  CH is pent-2-en-4-yne and not pent-3-en-1-yne
Statement-2 : While deciding the locants for double bond and triple bonds, lowest locant rule for multiple bonds
is followed.
CH3
3. Statement-1 : The correct IUPAC name for the compound, CH is (1-methylethyl) cyclopentane.
CH3
Statement-2 : It is named as a derivative of cyclopentane because the number of carbon atoms in the ring is
more than in the side chain.
H
4. Statement-1 : is called cyclohexane nitrile.
CN
Statement-2 : It contains six carbon atoms in the ring and –CN as the functional group.
5. Statement-1 : The IUPAC name for the compound C2H5–C–CH2OH is 2-ethyl prop-2-en-1-ol
CH2
Statement-2 : Ethyl (C2H5–) rather than methylene (=CH2) is considered as the substituent group because 'e' of
ethyl comes first in alphabetical order than 'm' of methylene.
6. Statement-1 : The IUPAC name of citric acid is 2-hydroxy propane 1,2,3,- tricarboxylic acid
COOH
HOOC COOH
OH
Statement-2 : When an unbranched carbon chain is directly linked to more than two like functional groups, then
it is named as derivative of parent alkane which does not include the C-atoms of the functional groups.
7. Statement-1 : The IUPAC name for the compound, OHC–CH2–CH2–COOH is butane -3-formyl-1-oic acid
Statement-2 : COOH is considered as substituent group while CHO is considered as the principal functional
group.
8. Statement-1 : The IUPAC name for the compound C6H5 COOCH2CH2COOH is 3-benzoyloxypropanoic acid.
Statement-2 : C6H5CH2O is called benzoyloxy group
9. Statement-1 : Pentane and 2-methyl pentane are homologues

Statement-2 : Pentane is straight chain alkane, while 2-methyl pentane is a branched chain alkane.
10. Statement-1 : Butane and 2-methyl butane are chain isomers

Statement-2 : Butane is a straight chain alkane while 2-methyl butane is a branched chain alkane.
11. Statement-1 : Neopentane is chain isomer of n-pentane.

Statement-2 : Molecular formula of neopentane and n-pentane is C5H12.
12. Statement-1 : Alkanes containing more than three carbon atoms exhibit chain isomerism
Statement-2 : All the C-atoms in alkanes are sp2–hybridized
13. Statement-1 : All the carbon atoms in CH2=C=CH2 are sp2 hybridised.
Statement-2 : All the C atoms have 3 sigma and 1  bond in the above compound.
14. Statement-1 : All the carbon atoms of but-2-ene lie in one plane.
Statement-2 : Double bond carbon atoms are sp2-hybridized.

1. Find the number of 1º, 2º & 3º hydrogen atoms in the following compounds :
(a) (b) (c) (d)
2. Identify the following as bicyclo (bridgehead), spiro or isolated compounds.
(a) (b) (c) (d)
3. Identify the degree of functional groups in the given compound :
(a) (b)
(c) CH3–CH2–NH–CH2–CH3 (d)
4. There are two acyclic hydrocarbon with molecular formula C4H4. Draw them.
5. Write the common name of the following compounds :
CH3 CH3 CH3 CH3

| | | |
(a) CH3 – CH – CH3 (b) CH3 – C – CH3 (c) CH3 – CH – CH2 – CH3 (d) CH3 – C – CH2 – CH3
| |
CH3 CH3
6. Write the correct IUPAC name of the following hydrocarbon (alkyl) groups.
(a) (b) (c) (d)
7. Write IUPAC name of the following compounds.
Cl I CH2  CH2  Cl
| | |
(a) Br  CH  CH  CH  CH  CH (b) CH3  CH  CH  CH2  CH3
2 2 3
|
CH3
Cl Br NO 2 Cl CH3 F
| | | | | |
(c) CH3  CH2  CH  CH  CH2  CH  CH2  CH3 (d) CH3  C  CH2  CH  CH  CH2  CH3
|
Br

(a) (b) (c) (d)
9. Write the IUPAC name of the following hydrocarbon groups.

CH3
|
(a) –CH=CH2 (b) –CCH (c) — C  CH (d) –CH2–CH=CH2
2
10. Write the IUPAC name of the following hydrocarbon groups.

CH3
(a) =CH–CH3 (b) | (c) –CH2–CCH (d) –CH=CH–CCH
 C  CH3

(a) 6-Chloro-4-ethyl-5-methylhept-5-en-1-yne (b) 3, 7-Dimethylocta-1, 3, 6-triene.
(c) 2, 3, 3-Trimethylhepta-1,5-diene (d) 4, 8-Dimethylnona-3, 7-diene-1, 5-diyne
12. Write IUPAC names of following compounds.
(a) (b) (c) (d)
13. Write IUPAC names of the following.
(a) (b) (c) (d)
14 . Write structure of the given molecules

(a) 1-Cyclobutylprop-1-ene (b) 3-Bromo-6-ethylcyclohexa-1, 4-diene
(c) 3, 5-Dimethylcyclohex-1-ene (d) 2-Cyclobutyl-4-ethylhex-1-ene
(a) (CH3)2 CHCH = CHCH2OH (b)
(c) H3 C — N — CH — CH3 (d) Cl CH2COCH2

| |
CH3 CH3
16. Write structure of the given molecules-7

(a) 3-Methoxy-5, 5-dimethylcyclohex-2-en-1-ol (b) 5–Methyl-2-(methylethyl) cyclohexan-1-amine
(c) 2–Chloro–3–methylcyclohex–3–ene–1–thiol (d) 3 –Bromo– 4–methyl cyclopentan-1-one
17. Write correct IUPAC name of the following compounds
(a) (b)

(a) (b)
OCH3 O
| ||
(c) (d) CH  CH  CH  CH  C  Cl
3 2 2
19. Write structure of the given molecules :

(a) 4-Sulphopentanoic acid (b) 2-Amino-3-hydroxypropanoic acid
(c) 3-Ethyl - 7 - methylocta - 2, 6 - dienal (d) 2, 2–Dimethyl– 4–oxopentanenitrile
20. Write IUPAC names of following compounds
(a) (b)
(c) (d)
21. Write IUPAC names of following compounds.
(a) (b)
(c) (d)
(a) (b) (c) (d)
23. Write structure of the given molecules :

(a) 2, 4, 6-Trimethylbenzenecarbonyl chloride (b) 3-Mercaptobenzaldehyde
(c) 3-Sulphobenzenecarboxylic acid (d) 4-Methylbenzenesulphonic acid
24. Identify the relationship between compound I, II and III.

25. Identify the relationship between the given compounds.
(a) and (b) and
(c) and (d) and
26. What is the degree of unsaturation in a compound with molecular formula C9H6N4?
27. What is the number of all aldehydes (structurally isomeric) with molecular formula C5H10O ?

Single choice type
1. Which of the following is homologue of CH3 NH CH2 CH2 CH3
(A) CH3CH2NHCH2CH3 (B) CH3CH2CH2NH2 (C) CH3–CH–NH2 (D) CH3CH2NH–CH3
CH3
2. Number of 10, 20, 30 and 40C present in compound (A) are respectively
(A) 7, 4, 5 and 1 (B) 7, 3, 4 and 1 (C) 7, 3, 5 and 1 (D) 7, 4, 4, 1

3. An example of an alicyclic compound is
(A) Benzene (B) Hexane (C) Cyclohexane (D) Furan.
4. Which of the following is not a cyclic compound ?
(A) Anthracene (B) Pyrrole (C) Isobutylene (D) Phenol
5. IUPAC name of the compound is
(A) 2, 2, 5-Trimethyl-4-(1-methylpropyl) nonane

(B) 4, 8, 8-Trimethyl-6-(1-methylpropyl) nonane
(C) 3, 6-Dimethyl-4-(1-methylene tertiary butyl) nonane
(D) 6, 6-Dimethyl-2-propyl-4-(1-methylpropyl) heptane
6. IUPAC nomenclature of the given organic compound will be : (CH3)2C(CH2CH3)CH2CH(Cl)CH3 :

(A) 5-Chloro 3, 3-dimethyl hexane (B) 4-Chloro-2-ethyl-2-methyl pentane
(C) 2-Chloro-4-ethyl-4-methyl pentane (D) 2-Chloro-4, 4-dimethyl hexane
7. In the structure of 4-Isopropyl-2,4,5-trimethylheptane, number of 10, 20 & 30 H’s are respectively.

(A) 18, 5, 4 (B) 21, 4, 3 (C) 18, 4, 3 (D) 21, 5, 4
8. What is the correct IUPAC name of the incorrect name Hepta-1,4-dien-6-yne :
(A) Hepta-3,6-dien-1-yne (B) Hepta-3,4-dien-1-yne
(C) Hepta-3,5-dien-1-yne (D) Hept-3-yne-1,4-diene

9. IUPAC name of the compound CH2  CH  CH  C  CH2 is
| |
CH2CH3 Cl
(A) 3-Ethyl-4-chloropenta-1, 4-diene (B) 2-Chloro-3-ethylpenta-1, 4-diene
(C) 4-Chloroethenylpent-1-ene (D) 3-Ethenyl-4-chloropent-4-ene
10. The correct IUPAC name of is :
(A) 1, 4-Diethyl-2-methyl-5-propylcyclohexane (B) 1, 4-Diethyl-5-methyl-2-propylcyclohexane

(C) 2, 5-Diethyl-1-methyl-4-propylcyclohexane (D) 2, 5-Diethyl-4-methyl-1-propylcyclohexane
11. The correct IUPAC numbering in the compound is :
(A) (B) (C) (D)
12. The correct IUPAC name of the compound :
(A) 1-Ethylidenecyclohex-2-ene (B) 3-Ethylidenecyclohex-1-ene

(C) 2-Ethylidenecyclohex-1-ene (D) 3-Ethenylcyclohex-1-ene
13. The correct IUPAC numbering in the compound is :
(A) (B)
(C) (D)

O
||
14. IUPAC name of the following compound CH3 – CH – C – CH – O – CH2 – CH3 is :
| |
OCH3 CH3
(A) 2-Ethoxy-4-methoxypentan-2-one. (B) 2-Ethoxy-4-methoxypentan-3-one.

(C) 2-Ethoxy-3-methoxypentan-3-one. (D) None of the above
15. The correct structure of 3-Formyl-5-oxocyclohex-3-enecarbonyl chloride is :
(A) (B)
(C) (D)
16. The IUPAC name of the compound is :
(A) Cyclobutenedioic anhydride (B) Butenedicarboxylic anhydride

(C) Cyclobutenedicarboxylic anhydride (D) Butenedioic anhydride
17. The correct IUPAC name of the compound is :
(A) 1, 2, 3-Triaminobutane-1, 3-dione (B) 2, 4-Diamino-3-oxobutanamide

(C) 1, 3-Dioxobutane-1, 2, 4-triamine (D) 1, 3, 4-Triaminobutane-2, 4-dione
18. IUPAC name of the following molecule is
COOH
Br
COOH
(A) 2-Bromobenzene-1,4-dioic acid
(B) 3-Bromobenzene-1,4-dicarboxylic acid
(C) 2-Bromobenzene-1,4-dicarboxylic acid
(D) 3-Bromobenzene-1,6-dicarboxylic acid

19. IUPAC name of the following compound
COOH
Br
HO NO2
(A) 2-Bromo-5-hydroxy-3-nitro benzoic acid (B) 6-Bromo-5-nitro-3-hydroxy benzoic acid
(C) 3-Nitro-2-bromo-5-hydroxy benzoic acid (D) 2-bromo-3-Nitro-5-hydroxy benzoic acid
20. ,
Relation between above compounds is:

(A) Position isomers (B) Chain isomers (C) Identical (D) Functional isomers
21. Which type of isomerism is observed between I and II ?
CH3 – CH2 – C – OCH3 ,

||
O
(I) (II)
(A) Functional isomerism (B) Metamerism

(C) Position isomerism (D) Stereoisomerism
22. Which one of the compound is not isomer of others ?
(A) (B) (C) (D)
23. Which type of isomerism is observed between I and II ?
(A) Functional isomerism (B) Metamerism

(C) Chain isomerism (D) Position isomerism
24. Ethyl 3–(propanoyloxy)cyclopentanecarboxylate & Diethyl cyclopentane–1,2–dicarboxylate are
(A) Chain isomers (B) Positional isomers
(C) Metamers (D) Functional isomers
25. How many positional isomers are possible for 3–ethylpentane (including itself)
(A) 1 (B) 2 (C) 3 (D) 4
26. The total number of unsaturated cyclic structure possible for a compound with the molecular formula C4H6 is:
(A) 3 (B) 4 (C) 5 (D) 6

27. All the members of a homologus series have same
(A) Functional group (B) Empirical formula
(C) General formula (D) All of these

28. The pair of compounds having the same general formula.
(A) and (B) and
(C) and (D) and H—CC—CC—H
29. Which functional groups are not present in given compound :
(A) Amide (B) Alcohol (C) Amine (D) Aldehyde
30. The compound with only primary hydrogen atoms is/are

(A) Hexamethylcyclopropane (B) Neohexane
(C) Tetramethylbutane (D) Hexamethylbenzene
31. Correct IUPAC names as per rules are

(A) 1,1,1-Trichloro-2,2-diphenylethane (B) 3-Cyclopentylbut-1-ene
(C) Cyclopenta-2,4-diene (D) 1-Bromo-2,3-dichlorocyclopropane
32. In which of the given molecules cyclic part is/are parent chain :
(A) (B)
(C) (D)
33. Which of the following is/ are incorrect IUPAC name : -
(A) 2-Methylbutan -3-one
(B) 3-Ethenylpent-1-en-4-yne
OH
CH3
(C) 3-(2-Aminoethyl)-2-methylcyclohexan-1-ol
CH2CH2NH2
(D) 4-Methyl-3-oxopentan-2-ol

34. Which is/are the correct IUPAC name of the corresponding structures
OH
CH3
(A) 3-(N-Ethylamino)-2-methylcyclohexan-1-ol
NHCH2CH3
(B) 3-Bromo-2–chlorobutanal
CN
|
(C) CH2  CH  CH2  CH3 Methyl-3-cyanopentanoate
|
COOCH3
(D) Cyclohexanal
35. Which of the following IUPAC name are correct.
(A) 2-Methylcyclopentanecarboxamide.
(B) Cyclohexanoyl chloride.
(C) 2-Methylcyclobutanecarbonitrile
(D) Methyl 2-bromocyclohexanecarboxylate
36. Which of the following pairs of structures represent the constitutional isomers ?
(A) CH2=CHCH2CH3 and
(B) CH3OCH2CH3 and
(C) (CH3)3CCH2CH2CH2OH and (CH3)2 CHCH2OCH2CH2CH3

(D) CH2ClCHClCH2CHO and CHCl2CH=CH–CH2–OH
37. Which of the following is the correct relationship ?
NH2
NHCH3 CH2 – CH2 – NH2 CH2 – NHC2H5
CH3 CH3
CH3 CH3 CH3

CH3
I II III IV
(A) I & II are functional isomers. (B) II & IV are metamers.
(C) I & IV are position isomers. (D) I & III are chain isomers.

38. Which relationship is/are correct ?
(A) & Identical
Br Br
Br Br
(B) H & H Position isomer
H H
H
CH3O
(C) & Functional isomer
COOH
H
CH3 OC2H5
(D) C=C & Metamers

H H

Column I Column II
(A) and (p) Homologs
(B) and (q) Functional isomers.
(C) and (r) Chain isomers.
(D) and (s) Have same general formula
(t) Have same empirical formula.

2. Column – I Column – II
(A) and (p) Isomers
(B) and (q) Positional Isomers
(C) and (r) Functional Isomers
(D) and (s) Homologues
Comprehension # 1 (Questions 1 to 3)
A saturated hydrocarbon (P) has six membered ring. Three alkyl groups attached to the ring alternate to each
other.
(i) First group has only two carbon atoms.
(ii) Second group has four carbon atoms and its all hydrogen atoms are chemically same.
(iii) Third group has total five carbon atoms. Its main chain contains three carbon atoms with ethyl as a
substituent.
1. How many 3° hydrogen atoms are present in the hydrocarbon (P) ?
(A) 2 (B) 3 (C) 4 (D) 5
2. How many 2º carbon present in the compound (P).
(A) 10 (B) 12 (C) 6 (D) 8
3. IUPAC name of hydrocarbon (P) is
(A) 1–(1–Ethylpropyl)–3–ethyl–5–(1,1–dimethylethyl)cyclohexane
(B) 1–Ethyl–3–(1–ethylpropyl)–5–(1,1–dimethylethyl)cyclohexane.
(C) 1–(1,1–Dimethylethyl)–3–ethyl–5–(1–ethylpropyl)cyclohexane
(D) 1–(1,1–Dimethylethyl)–3–ethyl–5–(2–ethylpropyl)cyclohexane
Comprehension # 2 (Questions 4 to 6)
There are three isomeric compounds P, Q, R with molecular formula C4H6O3. Compound P is a saturated
hydroxy carboxylic acid compound Q is a symmetrical anhydride while R is an aldehydic ester.
4. Which of the following is P ?
(A) (B)
(C) (D)

5. Which of the following is the metamer of Q ?
(A) (B)
(C) (D)
6. Which of the following is R ?
(A) (B) (C) (D)

* Marked Questions are more than one correct options.
1. Write IUPAC name of the following [IIT-JEE 2002]
4_ The IUPAC name of C6H5COCI is : [IIT-JEE-2006]

(A) Benzoyl chloride (B) Benzene chloro ketone
(C) Benzene carbonyl chloride (D) Chloro phenyl ketone
5. The number of structural isomers for C6H14 is : [IIT- JEE 2007]
(A) 3 (B) 4 (C) 5 (D) 6
6. The IUPAC name of the following compound is : [IIT-JEE-2009]
(A) 4-Bromo-3-cyanophenol (B) 2-Bromo-5-hydroxybenzonitrile

(C) 2-Cyano-4-hydroxybromobenzene (D) 6-Bromo-3-hydroxybenzonitrile

7. The total number of cyclic isomers possible for a hydrocarbon with the molecular formula C4H6 is / are :
[IIT-JEE 2010]
8. In allene (C3H4), the type(s) of hybridisation of the carbon atoms is (are) : [IIT-JEE 2012]
(A) sp and sp3 (B) sp and sp2 (C) only sp3 (D) sp2 and sp3
9. The carboxyl functional group (– COOH) is present in : [IIT-JEE 2012]

(A) picric acid (B) barbituric acid (C) ascorbic acid (D) aspirin
PART - II : AIEEE PROBLEMS (LAST 10 YEARS)

* Marked Questions are more than one correct options.
1. Which of the following compounds has wrong IUPAC name: [AIEEE- 2002]
(A) CH3–CH2–CH2–COO–CH2CH3  Ethyl butanoate
(B)  3-Methylbutanal
(C)  2-Methyl-3-butanol
(D)  2-Methyl-3-pentanone
2. The general formula CnH2nO2 could be for open chain [AIEEE- 2003]
(A) diketones (B) carboxylic acids (C) diols (D) dialdehydes.
3. The IUPAC name of the compound is [AIEEE- 2004]

HO
(A) 3, 3 - dimethyl - 1 - hydroxy cyclohexane (B) 1, 1 - dimethyl - 3 -hydroxy cyclohexane
(C) 3, 3 - dimethyl - 1 - cyclohexanol (D) 1, 1 - dimethyl - 3 - cyclohexanol
4. The IUPAC name of the compound shown below is [AIEEE 2006]

Cl
|
Br
(A) 2 - Bromo-6-chlorocyclohex-1-ene (B) 6-Bromo-2-chlorocyclohexene

(C) 3-Bromo-1-chlorocyclohex-1-ene (D) 1-Bromo-3-chlorocyclohexene
5. The IUPAC name of is : [AIEEE-2007, 3/120]
(A) 5, 5-Diethyl -4, 4-dimethylpentane (B) 3-Ethyl-4,4-dimethylheptane

(C) 1, 1-Diethyl-2, 2-dimethylpentane (D) 4, 4-Dimethyl-5, 5-diethylpentane
6. The correct decreasing order of priority for the functional groups of organic compounds in the IUPAC system of
nomenclature is [AIEEE-2008, 3/105]
(A) –SO3H, –COOH, –CONH2, –CHO (B) –CHO, –COOH, –SO3H, –CONH2
(C) –CONH2, –CHO, –SO3H, –COOH (D) –COOH, –SO3H, –CONH2, –CHO

7. The IUPAC name of neopentane is : [AIEEE-2009, 4/144]
(A) 2, 2-dimethylpropane (B) 2-methylpropane
(C) 2, 2-dimethylbutane (D) 2-methylbutane
8. Aspirin is known as : [AIEEE 2012]

(A) Acetyl salicylic acid (B) Phenyl salicylate
(C) Acetyl salicylate (D) Methyl salicylic acid
PART - III : CBSE PROBLEMS (LAST 10 YEARS)

(a) CH3–CH2–CO–NH–C6H5 [CBSE – 2005] (b) CH3–CH(NO2)CH2CH3 [CBSE – 2006]
CH3–CH–CH2–CH3
Br
(c) CH3–CO–CH2–CO–CH3 [CBSE – 2007, 2006] (d) [CBSE – 2008]
CH3
(e) [CBSE – 2008] (f) Cl–CH2–C  C–CH2–Br [CBSE – 2008]

OH
CH3
O = C – O –C2H5
O
(g) [CBSE – 2009, 2005] (h) (CH3)2 CH–CH2–C–CH(CH3 )2 [CBSE – 2009]
Cl
CH3
CH3
O CH3
(i) H [CBSE – 2010] (j) [CBSE – 2011]
H CH3–C–CH = C – CH3
CH3 Br
COOH
(k) [CBSE – 2011] (l) CH3CONH2 [BICE – 2010]

Br Cl
(m) (CH3)2CH–CH2–CO–Cl [BICE – 2010] (n) CH3–O–C2H5 [BICE – 2010]
COOH
(o) CH3–CH2–CN [BICE – 2010] (p) [BICE – 2010]
2. Write the structure of the following compounds :

(a) Hex-2-en-4-ynoic acid [CBSE – 2006]
(b) 2-chloro-3-methyl pentane [CBSE – 2009]
(c) 1-Phenyl propan-2-ol [CBSE – 2010]
(d) 2-(2-Chlorophenyl) - 1 -iodooctane [CBSE – 2011]

(e) 1-Bromo-4-sec. butyl-2-methylbenzene [CBSE – 2011]

Br
1. (i) (ii)
Br
OH OH
| |
2. (i) CH3  C  CH2  CH  CH3 (ii) CH3  CH  CH2  CH(OH) – CH3
| |
CH3 CH2CH3
3. (i) N,N-Dimethylpropan-2-amine (ii) N-Methylbutan-2-amine
4. (i) (ii)
5. (i) 4-Bromo-5-chloro-3-methylhexane-3-sulphonic acid

(ii) 4-Sulphopentanoic acid
6. (i) 3-Bromo-2-methylbutanal (ii) 4-Bromo-4-chlorobutan-2-one
7. (i) CH3 — CH2 — CH — CH2OH (ii)

|
OCH3
8. (i) Cyclohexylbenzene (ii) Ethyl 3-phenylbenzene-1-carboxylate
9. The phenomenon of existence of two or more compounds possessing the same molecular formulae but different
properties is known as isomerism. e.g. C2H5OH & CH3–O–CH3.
10. When two or more compounds differ in the position of substituent atom or functional group on the carbon
skeleton, they are called position isomers and the phenomenon is termed as position isomerism.
e.g. Cl–CH2–CH2–CH3 (1-chloropropane) & CH3–CH(Cl)–CH3 (2-chloropropane).
11. Metamerism arises due to different alkyl chains on either side of the polyvalent functional group in the molecule.
Ex. CH3 –CH2–O–CH2–CH3 and CH3 –O–CH2–CH2–CH3
12. , ,
13. H – C  C – H, Mol wt. = 26
14.

15. (i) 2, 4-Dimethylhex-2-enoylchloride (ii) N-phenylcyclohexanecarboxamide
(iii) Ethanoic propanoic anhydride (iv) Isopropyl 3-hydroxycyclohexane-1-carboxylate
16. (1) Chain Isomers (2) Chain Isomers (3) metamers (4) Functional isomers
17. (i) Methyl benzene carboxylate (ii) Benzene-1,2-dicarboxylic acid

(iii) 2, 2-Dimethyl propane (iv) 2, 2, 4 -Trimethyl pentane
18. (1) (2) (3) (4)
19. (1) 2,2-Dimethylpentane (2) 2,4,7- Trimethyloctane

(3) 2-Chloro-4-methylpentane (4) But-3-yn-1-ol
20. (1) H2N–CH2–CH2–OH and
(2) CH3 – CH2 – CH2 – CH2 – OH and
(3) and
(4) CH3 – CH = CH – CH2 – CH2 – CH2 – CH3 and
21. (i) 1, 2 – Dimethyl benzene (o – Xylene) (ii) Phenylethene (Styrene)

(iii) 4 – methyl phenol (p –cresol) (iv) 2 – Hydroxybenzenecarbaldehyde (Salicylaldehyde)
22._ (1) Homologues (2) Position isomers (3) Functional isomers (4) Metamers
EXERCISE - 1
PART - I
A-1. (a) 19  bonds, 6 bonds (b) 22  bonds (c) 20  bonds
A-2. (a) 3° carbon (b) 2° carbon (c) 4° carbon

A-3. (a) 1° H  9, 3° H  1 (b) 1°H  6, 2°H  2 (c) 1°H  6, 2°H  4
A-4. (a) H–COOH, CH3–COOH, CH3–CH2–COOH , CH3–CH2–CH2–COOH

(b) CH2=CH2, CH3–CH=CH2, CH3–CH2–CH=CH2, CH3–CH2–CH2–CH = CH2
(c) CH3–CO–CH3, CH3–CO–C2H5, C2H5–CO–C2H5,C3H7–CO–C2H5
A-5.
A-6. H2C = C = CH2

M.W. = 40.
A-7 (a) 24 (b) 20 (c) 19
B-1. (a) Homocyclic, alicyclic, saturated (b) Homocyclic, aromatic, unsaturated
(c) Heterocyclic, alicyclic, saturated (d) unsaturated.
B-2. (a) 2° (b) 2° (c) 3° (d) 3°
B-3. (a) 2° (b) 3° (c) 1°

B-4. (a) isopropyl group (b) sec-butyl group (c) Tert-butyl group
(d) Ethyl group (e) n-propyl group
B-5. Seniority order of functional groups :
–COOH > –CN > –CHO > > –OH > –NH2
C-1. (a) 2-Methyl propane (b) 2, 2-Dimethyl propane

(c) 2-Methyl butane (d) 2, 2-Dimethyl butane
C-2. (i) (ii)
(iii) (iv)
C-3. (i) 2,2,3-Trimethylpentane (ii) 5-(1,2-Dimethylpropyl)nonane
C-4. (a) 5-Ethyl-3-methyloctane (b) 4-Ethyl-2,2,6-trimethylheptane (c) 3-Methylhexane
C-5. (i) 4-Ethyl-3, 7-dimethylnonane

(ii) 4-Ethyl-4,5-dimethyldecane
(iii) 4-(1,1-Dimethylethyl)-5-(1-methylethyl) octane
D-1. General formula  CnH2n

H2C = CH2 Ethylene Ethene
CH3–CH=CH2 Propylene Propene
CH3–CH2–CH=CH2 -Butylene 1-Butene
D-2. General formula  CnH2n–2
(1) CH  CH Acetylene Ethyne
(2) CH3–CCH Methyl acetylene (Allylene) Propyne
(3) CH3–CC–CH3 Dimethyl acetylene (Crotonylene) But-2-yne
D-3. (i) (ii)
(iii) (iv)
D-4. (a) 5-Methylhept-3-ene (b) 5-Ethyl-2,6-dimethyl-4-(3-methylbutyl)oct-2-ene

D-5. (a) (b)
1 2 3 4 5
D-6. (i) (ii) (iii) CH3–C C–CH–CH3
CH3
4-Methylpent-2-yne
D-7. (a) 4-Methylpent-2-yne (b) 4-Propylhept-2-yne (c) 3,4,4-Trimethylhex-1-yne
D-8. (i) (ii)
(iii) (iv)
E-1. (i) (ii)
(iii) (iv)
E-2. (a) 1, 3, 5 Trihexylcyclohexane (b) Cyclohexylcyclohexane

(c) 3 – Cyclopropylprop – 1 – ene (d) 1–(Hex–3–enyl)cyclohex–1–ene
E-3. (a) 1,5-Dimethylcyclopent-1-ene
(b) 1-Cyclohexyl-4-cyclopropylbutane
(c) 1-(1,1-Dimethylethyl)-2-(1-methylethyl) cyclopentane
E-4. (i) (ii)
(iii) (iv)

1
2
E-5. (i) (ii)
1-cyclobutylethene
(iii) (iv)
E-6. (a) s-Butylcyclohexane (b) t-Butylcyclohexane

(c) Isopropylcyclohexane (d) Neopentylcyclopentane
E-7. (a) ring (b) side chain (c) ring (d) ring
(e) side chain (f) side chain
F-1. (a) 4 – Cyclohexylbut – 3 – en– 2-one (b) 2 – (2 – hydroxybutyl) cyclohexan – 1 – ol
(c) 2-Methylpropan-2-ol (d) 3-Chlorobutan-1-ol
F-2. (a) 1-Chloro-5-methylhexan-2-one (b) 2-Bromo-2-chloro-5-fluoro-4-methylheptane

(c) 2-Methoxy-N-methylethan-1-amine (d) 3-Bromo-2-chloro-5-methyloctane
F-3. (a) Methoxyethane (b) Ethoxyethane
(c) Epoxyethane (d) 1-chloro-2, 3-epoxypropane
G-1. (a) 3-Methylbutanoic acid (b) 5-Methylhept-3-en-1-al.

(c) 4-Oxopentanoyl chloride (d) 4-(But-2-enyl)non-6-enoic acid
G-2. (a) (b)
(c) (d)
H-1. (a) Methyl-2-ethylbutanoate

(b) Ethyl-3-methylpent-4-en-1-oate
(c) 3,3 Dimethyl –2 – (1–methylethyl)butanamide
H-2. (a) Ethanoic 2-methylpropanoic anhydride (b) Benzenecarboxylic anhydride
(c) Pent-2-enedioic anhydride (d) Cyclohexane-1, 2-dicarboxylic anhydride
I-1. (a) Methylbenzene (b) Isopropylbenzene

(c) Diphenylmethane (d) 1-Chloro-1-phenylethane.
I-2. (a) Cyclohexylbenzene (b) 4-Bromo-3, 6-diphenyloctane
(c) 1, 2-Dichloro-4-ethyl-5-nitrobenzene (d) 4-Chloro-1-nitro-2-propylbenzene
J-1. (a) Chain Isomers (b) Functional isomers (c) Homologs.
J-2. (a) I, II & III are functional isomers
(b) I, & II are position isomers, (I or II) & III are functional isomers.
(c) I, II & III are functional isomers
(d) I & II are chain isomers, I & III are chain isomers and II & III are position isomers
J-3. (a) Chain Isomers (b) Functional isomers (c) Metamers. (d) Position isomers
K-1. 9 K-2. 6 K-3. 4, Metamers

PART - II
A-1. (B) A-2. (A) A-3. (C) A-4. (C) A-5. (B)
A-6. (C) B-1. (A) B-2. (D) B-3. (C) B-4. (D)
B-5. (D) B-6. (B) C-1. (C) C-2. (A) C-3. (C)
C-4. (B) C-5. (D) C-6. (A) D-1. (D) D-2. (C)
D-3. (C) D-4. (B) D-5. (D) D-6. (D) E-1. (C)
E-2. (C) E-3. (A) E-4. (B) E-5. (B) E-6. (A)
E-7. (B) F-1. (A) F-2. (B) F-3. (A) F-4. (B)
F-5. (B) F-6. (B) G-1. (B) G-2. (A) G-3. (C)
G-4. (C) G-5. (D) G-6. (C) H-1. (A) H-2. (D)
H-3. (C) H-4. (B) H-5. (D) H-6. (B) H-7. (A)
I-1. (C) I-2. (B) I-3. (B) I-4. (C) I-5. (C)
I-6. (A) J-1. (C) J-2. (A) J-3. (B) J-4. (A)
J-5. (A) J-6. (C) J-7. (B) J-8. (C) J-9. (D)
J-10. (B) J-11. (D) K-1. (C) K-2. (B) K-3. (B)
K-4. (B) K-5. (B) K-6. (D) K-7. (B) K-8. (D)
PART - III
1. (A) 2. (D) 3. (A) 4. (D) 5. (C)
6. (A) 7. (E) 8. (C) 9. (B) 10. (D)
11. (B) 12. (C) 13. (E) 14. (A)
EXERCISE - 2
PART - I
1. (a) (1°, 2°, 3°) H atoms = (9, 4, 1) (b) (1°, 2°, 3°) H atoms = (3, 10, 1)
(c) (1°, 2°, 3°) H atoms = (6, 16, 0) (d) (1°, 2°, 3°) H atoms = (0, 18, 4)
2. (a) Bicyclo bridgehead (b) Bicyclo bridgehead (c) Isolated (d) Spiro
3. (a) 2° (b) 1° (c) 2° (d) 1°
4. H 2C = C = C = CH2 & HC  C – C = CH2

5. (a) Isobutane (b) Neopentane (c) Isopentane (d) Neohexane
6. (a) 1-methylethyl (b) 1-methylpropyl (c) 1, 2-dimethylpropyl (d) 2, 3-dimethylbutyl
7. (a) 1-Bromo-3-chloro-4-methylpentane (b) 1-Chloro-3-ethyl-4-iodopentane
(c) 4-Bromo-3-chloro-6-nitrooctane (d) 2-Bromo-2-chloro-5-fluoro-4-methylheptane

8. (a) Pent-2-ene (b) But-1-yne
(c) 3-Methylbut-1-ene (d) 4–Ethyl–2–methylhex-1-ene
9. (a) ethenyl (b) ethynyl (c) 1-methylethenyl (d) prop-2-enyl
10. (a) ethylidene (b) 1-methylethylidene (c) prop-2-ynyl (d) but-1-en-3-ynyl
11. (a) (b)
CH3 CH3 CH3 CH3

| | | |
(c) CH3  CH  CH  CH2  C  C  CH2 (d) H3C  C  CH  C  C  C  CH  C  CH
|
CH3
12. (a) 3-Ethyl-1, 1-dimethylcyclohexane (b) 1-Ethyl-3-methyl-5-propylcyclohexane

(c) 2-Bromo-1-chloro-4-fluorocyclohexane (d) 4-Bromo-1-chloro-2-fluorocyclohexane
13. (a) cyclohexylethene (b) 1-Ethylcyclohex-1-ene
(c) 1-Ethenylcyclohex-1-ene (d) 1-cyclohex-1-enylbuta-1,3-diene
14 . (a) (b) (c) (d)
15. (a) 4-Methylpent-2-en-1-ol (b) 4, 5–Dimethylhex–5–ene–2–thiol

(c) N,N-Dimethylpropan-2-amine (d) 1-Chloro - 4 - methylpentan - 2 - one
16. (a) (b) (c) (d)
17. (a) 3-propylpent-4-en-2-one (b) 3-Ethenylpentane-2,4-dione

18. (a) Pent–2–enoic acid (b) 3-Bromo-2-methylbutanal
(c) 2, 4-Dimethylhex-2-enenitrile (d) 3-Methoxypentanoyl chloride
19. (a) (b)
(c) (d)
20. (a) Methyl methanoate (b) 2-Ethoxycarbonylethanoic acid

(c) Phenyl benzenecarboxylate (d) 2-Ethanoyloxy benzenecarboxylic acid
21. (a) 2-Methylpropanamide (b) N-Methylpropanamide
(c) N, N-Dimethyl-2-methylpropanamide (d) N-Phenylbenzenecarboxamide
22. (a) 5-Formyl-2-nitrobenzoic acid (b) 4-Ethoxycarbonylbenzoic acid

(c) 4-Nitroaniline (d) 3-Methylphenol
23. (a) (b) (c) (d)
24. 1 & 2 are Position, 1 & 3 are Position, 2 & 3 are Position
25. (a) Metamers (b) Functional isomers (c) Chain isomers (d) position Isomers
26. 9 27. 4
PART - II
1. (D) 2. (C) 3. (C) 4. (C) 5. (A)
6. (D) 7. (B) 8. (A) 9. (B) 10. (A)
11. (D) 12. (B) 13. (B) 14. (B) 15. (A)
16. (D) 17. (B) 18. (C) 19. (A) 20. (C)
21. (A) 22. (D) 23. (B) 24. (C) 25. (A)
26. (B) 27. (A,C) 28. (A,B,D) 29. (C,D) 30. (A,C,D)
31. (A,B,D) 32. (A,D) 33. (A,B,D) 34. (A,B,C) 35. (A,C,D)
36. (A,C,D) 37. (A,B,D) 38. (A,B,C,D)
PART - III
1. (A – p,s), (B – q,s,t), (C – r,s,t), (D – q,s,t) 2. (A – p), (B – p,q), (C – p,r), (D – s).
PART - IV
1. (C) 2. (C) 3. (C) 4. (D) 5. (B)
6. (B)
EXERCISE - 3
PART - I
1. (4-Hydroxyphenyl) ethanal 2. 3-Aminobenzoic acid 3. 4-Methylbenzenesulphonic acid
4_ (C) 5. (C) 6. (B) 7. 5 8. (B)
9. (D)
PART - II
1. (C) 2. (B) 3. (C) 4. (C) 5. (B)
6. (D) 7. (A) 8. (A)

PART - III
1. (a) N-Phenyl propanamide (b) 2-Nitrobutane
(c) Pentane-2,4-dione (d) 1-Bromo-2-secbutyl benzene
(e) 2,5-Dimethyl phenol (f) 1-Bromo-4-chlorobut-2-yne
(g) Ethyl-4-chloro benzene carboxylate (h) 2,5-Dimethyl hexan-3-one
(i) 4-Bromo-3-methylpent-2-ene (j) 4-Methylpent-3-en-2-one
(k) 3-Bromo-5-chloro benzoic acid (l) Ethanamide
(m) 3-Methyl butanoyl chloride (n) Methoxy ethane
(o) Propane nitrile (p) 4-Methyl hexanoic acid
CH3 Cl
2. (a) CH3–C C–CH = CH–COOH (b) CH3–CH2–CH–CH–CH3
OH
(c) CH2–CH–CH3 (d) I–CH2–CH–CH2–CH2–CH2–CH2–CH2CH3

Cl
Br
Me
(e)
CH–CH2–CH3
CH3


Single choice type
1. Which alkane would have only the primary and tertiary carbon ?
(A) Pentane (B) 2-Methylbutane
(C) 2, 2-Dimethylpropane (D) 2, 3-Dimethylbutane
2. The common and IUPAC names for the group, (CH3)2CHCH2–respectively are
(A) Isobutyl, 2-methylpropyl (B) Isobutyl, 1-methylpropyl
(C) tert-Butyl, 1, 1-dimethylethyl (D) sec-Butyl, 2-methylpropyl
3. C3H6O can be
(A) Carboxylic acid (B) Ester
(C) Cyclic ketone (D) Aldehyde
4. Arrange the following molecules in increasing order of  to  bond ratio
N
N O
H
(I) (II) (III) (IV)
(A) I < II < III < IV (B) I < II < IV < III (C) II < I < IV < III (D) IV < II < I < III
5. Which of the following is heterocyclic compound ?

O OH
O O O
(A) (B) (C) (D)
O HO
O
6. IUPAC name of the following molecule is
CH2OH
COOH
(A) 4-Hydroxy methyl-1-carboxy cyclohex-3-ene
(B) 4-Hydroxy methyl cyclohex-3-ene carboxylic acid
(C) 1-Hydroxy methyl cyclohexene-4-carboxylic acid
(D) 4-(Hydroxy methyl cyclohex-3-enyl) methanioic acid
7. The IUPAC name of compound

CONH2
NH 2CO–CH 2–CH 2–CH–CH 2–CH 2–CH2–CH 3
(A) 1, 3–Dicarbamoylheptane (B) 4-Carbamoyloctane
(C) 2-Butyl pentanediamide (D) 2-Butyl pentane diamino ketone
8. Correct IUPAC name of the following compound is
O NH2
HC–CH–CH–COOH
COOH
(A) 2-Amino-3-Formyl butane-1,4-dioic acid (B) 2-formyl-3-amino butane-1,4-dioic acid
(C) 3-Amino-2-formyl butane-1,4-dioic acid (D) 2-Amino-3-carboxy-4-oxo butanoic acid

9. ,
Relation between the above compounds :

(A) Position isomers (B) Chain isomers (C) Homologs (D) No relation
10. Which one is not metamer of ?
(A) (B)
(C) (D)
11. Which one of the following is not the pair of the functional isomers.
(A) and (B) and
(C) and (D) and

12. Which of the following is / are heterocyclic compound (s)
(A) (B)
H2N OH
(C) (D)
N
H
13. Find out correct statement (s) about given molecule

O
(A) Compound is homocyclic (B) Number of 20 carbon in given compound is 4

(C) Number of  bonded carbon atoms are 7. (D) Number of bonded carbon atoms are 6.
14. Select the correct statement is.
(A) Homologues cannot be represented by same general formula
(B) C5H11–has eight alkyl group (C) C4H9 – has four alkyl group
(D) (CH3)3 CNH2 & NH2 are homologues

15. Find out the correct statement(s) about given molecule.
CH3  C  C  CH  CH  CH  CH2
(A) All the carbon atoms in given molecule are identical.
(B) IUPAC name is hepta-1, 3-dien-5-yne
(C) It has 4 sp2 hybrid carbons, 2 sp hybrid carbons and 1 sp3 hybrid carbon.
(D) All the carbon atoms in given molecule are different.
16. Which of the following is/are incorrect IUPAC name
(A) 4-Chloro-3-methyl cyclopentan-1-ol
(B) 1-Amino-3-bromo hexan-1-one
(C) 4-Chloro-3-methyl-cyclohexane carboxylic acid
(D) 3-Bromo-1-methyl hexan-1-ol
17. The incorrect IUPAC name is/are :-
(A) CH3–CO–CH(CH3)2 (B) CH3–CH–CH–CH3
2-Methyl-3-butanone
CH3 CH2–CH3
2, 3-Dimethyl pentane
CH3
(C) CH3–C C–CH (D) CH3–CH–CH–CH3
CH3
4-Methyl-2-pentyne Cl Br
3-Chloro-2-butane
18. Which of the following compound has wrong IUPAC name ?
(A) (B) CH3–CH–CH2–CHO
CH3
3-Methyl-butanol
(C) CH3–CH–CH–CH3 (D) CH3–CH–C–CH2–CH3

OH CH3 CH3 O
2-Methyl-3-butanol 2-Methyl-3-pentanone
19. The metamer and functional isomer of N, N-Diethylethanamine is/are

(A) N, N-Dimethylbutan-2-amine and N-Propylbutan-1-amine respectively
(B) N-Ethyl-N-methylpropan-2-amine and N-methylpentan-2-amine respectively
(C) N-Ethyl-N-methylpropan-1-amine and N-Isopropylpropan-1-amine respectively
(D) N,N-Dimethylpropan-2-amine and N-Ethylbutan-2-amine respectively
20. Which of the following are functional isomers of methyl ethanoate ?
O O O
|| || ||
(A) CH3 – CH2 – COOH (B) CH3 C (C) CH 3 – O – CH 2 – C – H (D) CH2 – C – CH3
CH H |
| OH
OH
21. Which of the following of compounds are position isomers
(A) and (B) and
(C) and (D) and

1. Identify the bridgehead atoms in the following molecule.
(a) (b) (c) (d)
2. Find the number of 1º, 2º & 3º hydrogen atoms in the following compounds.
(a) (b) (c) (d)
3. Write the most branched alkane hydrocarbon with the given molecular formula.
(a) C4H10 (b) C5H12 (c) C6H14 (d) C7H16
4. Classify the following compounds as homocyclic, heterocyclic, alicyclic, aliphatic, aromatic, saturated
and unsaturated.
(a) (b) (c) (d)
5. Write bond line structural formula for each of the following :
(a) (b) (c)
(d) (e)
6. Find the longest chain in each of the following.
(a) (b)
(c) (d)

(a) (b)
CH3
|
(c) (d) CH3 — CH2 — CH2 — CH2 — CH2 — CH — C — CH2CH3
| |
CH3 CH2 — CH2 — CH3
8. Write the structure of the following compounds :

(a) 2,3-Dimethylpentane (b) 3-Ethyl-4-methylhexane
(c) 3-Ethyl-2,2-dimethylhexane (d) 4-Methyl-5-(1-methylethyl)octane
(a)
CH3
|
(b) CH3  C  CH2  CH2  CH  CH2  CH2  CH2  CH3
| |
CH3 CH3  C  CH3
|
CH3  CH  CH3
CH3 CH3
| |
(c) CH3  CH2  CH2  CH2  CH  CH  CH  CH3
|
CH2 CH3
| |
CH2  CH  CH3
(d)
10. Do the correct numbering in the following compounds.

(a) (b) (c) (d)

(a) (b) (c) (d)
12. Write structure from the given IUPAC names.

(a) 1-Bromo-2-(1-methylethyl)buta-1, 3-diene
(b) 3-Bromo-2-chloro-5-methyloct-3-ene
(c) 3-Ethynylhexa-1,4-diene
(d) 5-Bromomethyl-6-methylhept-3-ene
13. Write structure of the given molecules
(a) 4-Bromo-1-chloro-2-fluorocyclohexane (b) 2-Bromo-5-(methylethyl)-1, 3-dinitrocyclohexane
(c) 4-Ethyl-2-methyl-1-propylcyclohexane (d) 1-Cyclopropylbutane
14. A hydrocarbon (R) has six membered ring in which there is no unsaturation. Two alkyl groups are attached to the
ring adjacent to each other. One group has 3 carbon atoms with branching at 1st carbon atom of chain and
another has 4 carbon atoms. The larger alkyl group has main chain of three carbon atoms of which second
carbon is substituted. Correct IUPAC name of compound (R) is
(a) (b) (c) (d)
(a) (b) (c) (d)
(a) (b) CH3  CH  CH2  SO3H

|
OH
(c) (d) CH3 — CH2 — CH — CH2OH

|
OCH3
18. Write IUPAC name of the following
(a) (b) (c) (d)

19. Write IUPAC names of following ethers
(a) (b) (c) (d)
OH OH
| |
(a) CH3  C  CH2  CH  CH3 (b)
|
CH3
(c) CH3 – CH – C – CH – CH3 (d)

| || |
CH3 O O OCH2 – CH3

O
(a) (b)
O O
(c) (d)
22. Write correct IUPAC name of the following compounds
(a) (b) (c) (d)

O O
|| ||
(a) (b) CH  C  CH  CH  C  OH
3 2 2
CH 2 — CH — CH 2
(c) | | | (d)
CN CN CN
(a) (b)
(c) (d)

(a) (b)
O
||
(c) H2C  CH  CH2  CH2  C  NH2 (d)
(a) (b) (c) (d)
(a) (b) (c)
28. Write IUPAC name of the following :
(a) (b) (c) (d)
(a) `(b)
(c) (d)

30. What is the relation between following compounds ?
(a) ,
(b) ,
(c) CH3  CH2  C  H , CH3  C  CH3

|| ||
O O
(d) ,
31. What is the relation between following compounds ?
(a) , (b) , (c) , (d) ,
32. The ring chain functional isomer of compound But-2-ene are.
33. Write all structurally isomeric ethers with molecular formula C5H12O.
34. Write all structurally isomeric esters with molecular formula C5H10O2.
35. Write all structurally isomeric ketones with molecular formula C6H12O.
36. Write all acyclic structural isomers of C5H10.

37. The degree of unsaturation of the following compound is :
38. How many number of all aldehydes (structurally isomeric) with molecular formula C5H10O are possible?
39. What is the number of all (structurally isomeric) alkynes with molecular formula C6H10.
40. How many aromatic have benzen ring structural isomers are possible for C7H8O.

PART - I
1. (D) 2. (A) 3. (D) 4. (C) 5. (C)
6. (B) 7. (C) 8. (A) 9. (B) 10. (B)
11. (D) 12. (C,D) 13. (A,C) 14. (B,C) 15. (B,C)
16. (A,B,D) 17. (A,D) 18. (B,C) 19. (B,C) 20. (A,B,C,D)
21. (A,B)
PART - II
1. (a) 4 & 6 (b) 3 & 5 (c) 1 & 4 (d) 1 & 4
2. (a) (1ºH, 2ºH, 3ºH) = (12, 4, 0) (b) (1ºH, 2ºH, 3ºH) = (6, 10, 2)
(c) (1ºH, 2ºH, 3ºH) = (6, 16, 0) (d) (1ºH, 2ºH, 3ºH) = (6, 4, 2)
3. (a) (b) (c) (d)
4. (a) Homocyclic, alicyclic, unsaturated (b) Heterocyclic, aromatic, unsaturated

(c) Heterocyclic, alicyclic, saturated (d) Aliphatic, saturated.
5. (a) (b) (c) (d) (e)
6. (a) (b) (c) (d)
7. (a) 4-Ethyl-3, 7-dimethylnonane (b) 5-Ethyl-5-methyl decane

(c) 3-Ethyl-2, 6-dimethyl-5-(1-methylethyl)octane (d) 4-Ethyl-4,5-dimethyldecane
8. (a) (b) (c) (d)
9. (a) 4-(1,1-Dimethylethyl)-5-(1-methylethyl) octane

(b) 2,2–Dimethyl–5–(1,1,2–trimethylpropyl)nonane
(c) 5-(1,2-dimethylpropyl)-2-Methylnonane
(d) 3,3–Diethyl–4–methyl–5–(1-methylethyl)octane
10. (a) (b) (c) (d)
11. (a) 4-Ethylhex-1-ene (b) 5-Methylhex-2-ene

(c) 2(1-Methylethyl)penta-1, 4-diene (d) 7-Ethyl-2,4,5,6-tetramethyldeca-1,8-diene

Cl CH2  CH2  CH3

| |
12. (a) (b) CH3  CH  C  CH  CH  CH3
|
Br
(c) (d)
13. (a) (b) (c) (d)
14.
1-(1-Methylethyl)-2-(2-methylpropyl)cyclohexane
15. (a) 1(Cyclohexa-2, 5-dienyl) cyclohexa-1,3-diene (b) 1(Buta-1,3-dienyl)cyclohexa-1,4-diene.
(c) Methylenecyclohexane (d) Ethylidenecyclohexane
16. (a) Cyclohexylidenecyclohexane (b) 3,6-Dimethylenecyclohexa-1, 4-diene
(c) 2-Cyclopropylidenebutane (d) 3(Cycloprop-2-enylidene)but-1-ene
17. (a) 2, 2, 3–Trimethylpentan–3–amine (b) 2-Hydroxypropane-1-sulphonic acid

(c) N,N–Diethylethanamine (d) 2-Methoxybutan-1-ol
18. (a) 2-(2-Hydroxypropyl)cyclohexan-1-one (b) 1-(2-Hydroxycyclohexyl)propan-2-one

(c) 2-(2-Oxopropyl)cyclohexan-1-one (d) 5-Hydroxycyclohex-2-en-1-one
19. (a) 1-Isopropoxypropane (b) 2-Methoxy-2-methylpropane

(c) 1-chloro-1,3-epoxypropane (d) 4-chloro-1,2-epoxybutane
20. (a) 2-Methylpentane-2,4-diol (b) 4-Bromo-5-chloro-3-methylhexane-3-sulphonic acid

(c) 2–Ethoxy–4–methoxypentan-3-one (d) 3–Methylbut–3–en–2–ol
21. (a) 3,3-Dimethylcyclohexan-1-ol
(b) 2, 4, 6-Trimethylenecyclohexane-1, 3, 5-trione
(c) 3–Ethylamino–2–methylcyclohexan-1-ol
(d) 2-(3-Oxobutyl) cyclohexan-1-one
22. (a) 3-(1-Oxoethyl) hexane-2, 5-dione (b) 3-Ethenylpentane-2, 4-diol

(c) 3-Ethylpent-4-en-2-ol (d) 2-Hydroxymethyl-3-oxobutane-1-sulphonic acid.
23. (a) Chlorocarbonylethanoic acid (b) 4-Oxopentanoic acid
(c) Propane-1,2,3-tricarbonitrile (d) Propane - 1, 2, 3-tricarboxylic acid
24. (a) 2-Oxopropanedioic acid (b) 2-Ethenylpropanedioic acid
(c) Methanetricarboxylic acid. (d) 3-Oxopropanoyl chloride
25. (a) Ethyl-2-methylpropanoate (b) Ethanoicpropanoic anhydride

(c) Pent-4-enamide (d) 1-Ethanoyloxypropane-2-sulphonic acid

26. (a) Propanamide (b) N, N-Dimethylethanamide
(c) 2-Carbamoylethanoyl chloride (d) Methylcyclohexanecarboxylate
27. (a) 1–(2–Chlorophenyl)–2–(4–Chlorophenyl) ethane

(b) 2-Chloro-1, 4-dinitrobenzene
(c)1, 2-Dibromo-1, 2-diphenylethane
28. (a) 3-Chlorocarbonylbenzenecarboxylic acid (b) 4-Hydroxybenzenecarbonyl chloride

(c) Methyl-4-ethanoyloxybenzenecarboxylate (d) 3-Hydroxybenzene-1-sulphonic acid
29. (a) Methyl-3-nitrobenzenecarboxylate (b) Ethyl-3-phenylbenzene-1-carboxylate

(c) Ethyl-2–methyl-2-(3–nitrophenyl)propanoate (d) 1, 1, 1-Trichloro-2, 2-bis(4-chlorophenyl) ethan
30. (a) Position isomers (b) Metamer (c) Functional isomers (d) chain isomers
31. (a) Chain isomers (b) Position isomers (c) Identical (d) Chain isomers
32. or
33. (i) CH3–O–CH2–CH2–CH2–CH3 (ii) (iii)
(iv) (v) CH3–CH2–O–CH2–CH2–CH3 (vi)
34. (i) (ii) (iii)
(iv) (v) (vi)
(vii) (viii) (ix)
35. (i) (ii) (iii) (iv)
(v) (vi)
36. (i) (ii) (iii)
(iv) (v)
37. 9 38. 4 39. 7 40. 5

IUPAC NOMENCLATURE & STRUCTURAL ISOMERISM

EXERCISE # 1
PART - I
K-1. M.F. of compound (I) is C8H8
D.U. = 5
5+2+2=9
K-2. (i) CH2=C=CH–CH2–CH3 (ii) CH2=C= (iii) CH2=CH–CH=CH–CH3
(iv) CH2=CH–CH2–CH=CH2 (v) CH2= (vi) CH3–CH=C=CH–CH3
K-3.
All are metamers.
PART - II
A-2.
* = 3ºcarbon,  = 2ºcarbon
A-5.
This structures has 1º H-atoms and all are identical.
B-1. (Alicyclic heterocyclic)

B-3. N saturated heterocyclic compound.

|
H
B-5. According to IUPAC only alkene and alkyne are unsaturated hydrocarbon.
C-3. (2-Bromo-1-fluoro-1-iodo-2-nitrobutane)
C-5.
D-5. 2-Chloro-1-ethoxyethene
1 2
Cl – C  C – O – C – C
correct name 1-Chloro-2-ethoxyethene.
D-6.
E-3. If the no. of C-atoms in the ring and in the side chain are the same, then the name of ring appears in word root
and side chain appears as secondary prefix.
G-6.
4-Aminomethyl-5-hydroxycyclohex-2-ene-1-carboxylic acid
H-3. Methyl2–methylbutanoate esfFky2–esfFkyC;wVsuks,V
H-5. CH3— C —O—CH2— C —OC2H5

|| ||
O O
(ethanoyloxy) (ethanoate) (ethyl)
J-3.
It has only six carbon atoms.
J-5. and
Carbon skeleton is different in both compounds.

J-6. ;
Amide functional group Aldehyde and 1º amine
J-8. I, II & III are metamers because functional group is diester & there is only change in alkyl group attachment.
J-9. molecular formula = C8H16 molecular formula = C8H16
J-10. & are functional group isomers.
J-11. , , , ,
K-2.
K-6. (i) (ii) (iii)
(iv) (v)
K-7. (i) (ii) (iii)
EXERCISE # 2
PART - I
27. (i) CH3–CH2–CH2–CH2–CHO (ii) (iii) (iv)

PART - II
7. 1º, 2º & 3º H’s are that which is attach at 1º , 2º & 3º carbon respectively.
20. ,
3, 5-Dimethylcyclohex-1-ene.
21. Ester group in I and ketone group in II compound.
22.
It has different molecular formula and different DU.
23. There is change in C skeleton across the functional group.
C–C–C–C–C
|
24. & 25. C
|
C
26.
30. (A) 1º Hydrogen = 18
CH3
(B) H3C–C–CH2–CH3 1º Hydrogen = 12

CH3
2º Hydrogen = 2
CH3 CH3
(C) H3C–C–––C–CH3 1º Hydrogen = 18

CH3 CH3
(D) 1º Hydrogen = 18

33. The correct IUPAC name is :
(A) 3-Methylbutan -2-one
(B) 3-Ethynylpenta-1,4-diene
(D) 2-Hydroxy-4-methylpent-3-one
34. The correct IUPAC name of is Cyclohexanecarbaldehyde.
37. I & IV have different functional group. i.e. 1º & 2º amine therefore these are functional isomers.
38. (A) Compounds have same connectivity and same orientations.

(B) Compounds have different positions for substituents.
(C) Compounds have different functional groups.
(D) Compounds have different groups on two sides of polyvalent functional group.
PART - IV
Sol. (1 to 3)
(1) No. of 3° H atoms = 4

(2) Type of ‘C’ = 13
(3) 1–(1,1–Dimethylethyl)–3–ethyl–5–(1–ethylpropyl)cyclohexane
EXERCISE # 3
PART - I
4_ IUPAC name of is benzene carbonyl chloride.
5. Molecular formula C6H14
6.
2-Bromo-5-hydroxybenzonitrile (–CN group gets higher priority over –OH and –Br)

7. The DU of C4H6 = 2.
It can have (a) two rings (b) one double bond and one ring.
, , , ,
8. C3H4
9. picric acid ; barbituric acid
ascorbic acid ; aspirin
PART - II
1. 3-Methyl-2-butanol
2. Diketones : CnH2n –2O2, Carboxylic acid : CnH2nO2, Diols : CnH2n+2O2, Dialdehydes : CnH2n–2O2
3.
4. 3- Bromo -1-chlorocyclohex-1-ene
5. (3-Ethyl-4,4-dimethylheptane)
CH3
|
CH3 — C — CH3
7. |
CH3
2, 2-dimethylpropane

8. Aspirin (Acetyl salicylic acid)
PART - I
1.
2. Isobutyl, 2-methyl propyl
3. CH3–CH2–CH=O (Aldehyde)
5. Hetero atom is present in cyclic chain.
9. Carbon skelton is different in both compounds.
10.
This compound is functional isomer of the given compound.
20. All have different functional groups than ester.
PART - II
38. (i) CH3–CH2–CH2–CH2–CHO (ii) (iii) (iv)
39. (i) H–C C–CH2–CH2–CH2–CH3 (ii) H–C C– –CH2–CH3 (iii) H–C C–CH2– –CH3
(iv) H–C C– (v) CH3–CC–CH2–CH2–CH3 (vi) CH3–C C–
(vii) CH3–CH2–C  C–CH2–CH3
40.

STEREOISOMERISM
297 STEREOISOMERISM Chemistry
Introduction :
The particular kind of isomers that are different from each other only in the way the atoms are oriented in
space are called stereoisomers. These isomers have same connectivity of atoms and groups.
Stereoisomers have remarkably different physical, chemical and biological properties.
e.g. The two stereoisomers of butenedioic acid are maleic acid and fumaric acid. Fumaric acid is an essential
metabolic intermediate in both plants and animals, but maleic acid is toxic and irritating to tissues.
O O
|| ||
HO – C C – OH
C=C
H H
Maleic acid
m.p. 138°C
toxic, irritant
Classification of Stereoisomers :
1. Configurational Isomers :
(I) These isomers differ in the configuration (The spatial arrangement of atoms that characterises a particular
stereoisomer is called its configuration).
(II) Configurational isomerism arises due to noninterconvertibility at room temperature. Since they are non
interconvertible they can be separated by physical or chemical methods.
1.1 Geometrical isomerism :

Isomers which possess the same molecular and structural formula but differ in the arrangement of atoms
or groups in space due to restricted rotation are known as geometrical isomers and the phenomenon is
known as geometrical isomerism.
Conditions of geometrical isomerism :

( I ) Geometrical isomerism arises due to the presence of a double bond or a ring structure
(i.e. , – N = N – or ring structure)
Due to the rigidity of double bond or the ring structure the molecules exist in two or more orientations. This
rigidity to rotation is described as restricted rotation / hindered rotation / no rotation.
Ex. and (Restricted Rotation)

(II) Different groups should be attached at each doubly bonded atom.
a a a a a d
Ex. C=C , C=C and C=C
b b b d b e
On the other hand, following types of compounds can not show geometrical isomerism :
and are identical but not geometrical isomers.
Examples of Geometrical isomers :

(I) Along C=C bond
CH3 CH3
CH3 Br CH3 H CH3 H
(a) C=C & C=C (b) C & C
H H H Br
H CH3
(II) Along C = N – bond
CH3 .. CH 3 OH CH3 .. CH3 OH

(a) C=N & C=N. (b) C=N & C=N.
. .
H OH H C2H5 OH C2H5
CH3 CH3 CH3 ..

.. CH3 NH2
OH
N C N C N.
(c) & N. (d) & .
. C2H5 NH2 C2H5
OH
(III) Along – N = N – bond

.. .. .. CH3 .. .. .. Ph
(a) N N & N N. (b) N=N & N = N ..
.
CH3 CH3 CH3 Ph Ph Ph
(IV) Along  bond of cycloalkane

CH3 CH3 CH3 H H3C CH3 H CH3
(a) & (b) &

H H H CH3 H H CH3 H
(V) Along C=C in ring structures :

Usually in cycloalkenes double bond has cis configuration. Their trans isomers do not exist due to large
angle strain. But if the ring is large enough then the trans stereoisomer is also possible. The smallest trans
cycloalkene that is stable enough to be isolated & stored is trans-cyclooctene.
(a)  (b) 

Configurational nomenclature in geometrical isomerism :
Configuration Criteria Remarks
If the two similar groups are on same side of restricted
cis / trans Similarity of groups
bond the configuration is cis otherwise trans.
If the two senior groups are on same side of restricted
E/Z Seniority of groups bond the configuration is Z (Z = zusammen = together)
otherwise E (E = entgegen = opposite).
Sequence rules (Cahn - Ingold - Prelog sequence rules) :

For deciding the seniority of groups following (CIP) rules are applied :
Rule I : The group with the first atom having higher atomic number is senior. According to this rule the
seniority of atoms is :
I > Br > Cl > S > F > O > N > C > H
Rule II : The higher mass isotope is senior.

Thus (a) – T > – D > – H. (b) – C14H3 > – C12 H3
Rule III : If the first atom of group is identical then second atom is observed for seniority.
F F
| |
(a) – CH2Cl > – CH2OH > – CH2NH2 > – CH2CH3 > – CH3 (b)  C  Cl >  C  Cl
| |
OH NH2
Rule IV : Groups containing double or triple bonds are assigned seniority as if both atoms were duplicated
or triplicated that
(Y) (C)
C–Y | |
>C=Y is written hypothetical as | | & –CY is written hypothetical as C–Y
(Y) (C) | |
(Y) (C)
Ex. for deciding seniority among – C  CH, – CH = CH2, their hypothetical equivalents are compared.
C C C C
| | | |
CCH > CCH
| |
C C | |
( for  C  C  H) H H
( for  CH  CH2 )
Rule V : Bond pair is senior to lone pair.
Ex. In which compound, Cis-trans nomenclature cannot be used

Cl CH3
(A) CH3–CH=CH–CH3 (B) CH3–CH=CH–COOH (C) C=C (D) C6H5–CH=CH–CHO

Br C 2H 5
Ans. C
Ex. Which of the following structures will display geometrical isomerism ?
(A) CH3 CH = CCl2 (B) CH3 CCl = CBr CH3 (C) CH3CH = CHBr (D) Ph–CH=N–OH
Ans. (B, C, D)
CH3 H H CH3 CH3 Cl CH3 Cl

C C C C
Sol. (A) C & C (B) C & C
Cl Cl Cl Cl H3C Br Br H3C
Both are identical Non – identical

H CH3 H CH3
C C
(C) & C Non–identical (D) & Non–identical
C
H Br Br H
Ex. Identify E and Z form of stilbene
(A) (B)
Ans. (A) E (B) Z

Number of Geometrical isomers :
Number of geometrical isomers can be found by calculating the number of stereocentres in the compound.
(stereocentre is defined as an atom or bond bearing groups of such nature that an interchange of any two
group will produce a stereoisomer).
Nature of No. of G.I.

compound (n=no. of Example No. of Isomers
stereocentres) isomers
I : (cis, cis)
(I) Compound 2
n
4 II : (trans, trans)
with dissimilar CH3 – CH = CH – CH = CH – C2H5
III : (cis, trans)
ends IV : (trans, cis)
(II) Compound I : (cis, cis)
with similar n
1 II : (trans, trans)
2
n–1
+ 22 CH3 – CH = CH – CH = CH – CH3 3 III : (cis, trans)
ends and even
stereocentres ~
= (trans, cis)
(III) Compound I : (cis, cis, cis)
n 1
with similar n–1
II : (cis, cis, trans)
2 + 22 ~
ends and odd CH3 – CH = CH – CH = CH – CH = CH – CH3 6 = (trans, cis, cis)
stereocentre III : (cis, trans, trans)
~
= (trans, trans, cis)
IV : (trans, trans, trans)
V : (cis, trans, cis)
VI : (trans, cis, trans)
Physical Properties of Geometrical Isomers :

Br Br H Br
Physical properties Remarks
C=C C=C
H I H Br II H
cis-isomer has resultant of dipoles while in

Dipole moment I > II trans isomer dipole moments cancel out
Molecules having higher dipole moment have
Boiling point I > II higher boiling point due to larger intermoleculer
force of attraction
Solubility (in H2O) I > II More polar molecules are more soluble in H2O.
More symmetric isomers have higher melting

Melting point II > I points due to better packing in crystalline lattice
& trans isomers are more symmetric than cis.
The molecule having more vander waal strain

Stability II > I are less stable. In cis isomer the bulky groups
are closer they have larger vander waals strain.

1.2 Optical Isomers :
Introduction and Definitions :
(1) Optical activity & plane-polarised light : Ordinary light is an electromagnetic wave, which has
oscillation in all the directions perpendicular to the path of propagation. When ordinary light is passed
through Nicol prism it has all its oscillations in the same plane and is called plane-polarised light.
Certain compounds rotate the plane of polarised light in a characteristic way when it is passed through their
solutions. These compounds are referred to as optically active compounds. The angle of rotation can be
measured by an instrument called polarimeter.
(II) dextrorotatory compounds : If the substance rotates plane-polarised light to the right i.e. in clockwise
direction it is called dextrorotatory & indicated by 'd' or (+).
(III) laevorotatory compounds : If light is rotated towards left i.e. in anticlockwise direction the substance
is said to be laevorotatory and indicated by 'l ' or (–).
(IV) Specific rotation []. Specific rotation is the number of degrees of rotation observed if a
1-dm (10-cm) tube is used and the compound has concentration 1 gm/mL. Thus specific rotation [] is

[]t =
 C
[] = Specific rotation ;  = observed angle of rotation (degree)
l = Pathlength (dm) ; C = concentration (gm/ml)
 = wavelength (nm) ; t = temperature (25°C)
Cause of optical activity :

The foundation of modern theory of stereochemistry was laid by Louis Pasteur when he observed two different
kind of crystals, which were mirror images of each other. Aqueous solution of both types of crystals showed
optical rotation that was equal in magnitude but opposite in direction. Pasteur believed that this difference in
optical activity was associated with the three dimensional arrangement of atoms in the two types of crystals.
Later van't Hoff and LeBel proposed that all the four valencies of carbon are directed towards the four corners
of regular tetrahedron, and if all the four substituent attached to such a carbon are different the resulting
molecule lack symmetry and such a molecule is referred to as asymmetric molecule and asymmetry of the
molecule is responsible for optical activity in such organic compounds.

Element of symmetry and concept of molecular dissymmetry/asymmetry and chirality.
(I) Plane of symmetry :
It is an imaginary plane which bisects the molecule in two equal halves in such a way that each half of the
molecule is the mirror image of the other half.
(II) Centre of symmetry :

The centre of symmetry is defined as the point in a molecule through which if a straight line is drawn from any
part of the molecule this line encounters identical groups at equal distances in opposite direction.
(III) Asymmetric and dissymmetric compounds :

A molecule which does not possess any element of symmetry (there are all 23 elements of symmetry) is
called asymmetric. A molecule which does not possess plane of symmetry and centre of symmetry is called
dissymmetric.
(IV) Condition for optical activity :
The minimum condition for a compound to show optical activity is molecular dissymmetry i.e. absence of
plane of symmetry, centre of symmetry and alternating axis of symmetry.
(V) Chirality :
A compound which is non-superimposable to its mirror image is called chiral while a compound which is
superimposable to its mirror image is called achiral. All dissymmetric (or asymmetric) compounds are
chiral & vice-versa.
(VI) Chiral centre :
A compound in which a carbon is atttached with four different groups lacks symmetry and is called chiral
carbon or asymmetric carbon. It is represented by C*. e.g.
(a) CH3  CH  CH3 (2-chloropropane) :

|
Cl
I has no chiral centre since two groups (a & b) are identical. Its is superimposable on its mirror image II ( III).
*
CH3  C H  C 2H5 (2-chlorobutane) :
(b)
|
Cl
I has one chiral centre it is asymmetric & it is not superimposable to its mirror image II ( III).
The necessary condition for chirality is not just the presence of asymmetric carbon atoms but the asymmetry
of the molecule as a whole.

Projection formula in optical isomerism :
(I) Wedge-dash projection formula :
It is a convenient way of depicting three dimensional structure in two dimension. In this projection four bonds
of a tetrahedral molecule is shown by two lines (in the plane), one wedge (up the plane) and one dash line
(down the plane)
(II) Fischer projection formula :

It is also a convenient way of depicting three dimensional structure in two dimension.
Rules for writing Fischer projection formula :
(i) The molecule is drawn in the form of cross (+) with the chiral carbon at the intersection of horizontal &
vertical lines.
(ii) On vertical line, main chain is taken with first carbon at the top.
(iii) The horizontal lines represent the bonds directed towards the viewer and vertical lines represent away
from the viewer
*
CH2  C H  CHO
Ex. (a) glyceraldehyde | | can be represented in two different Fischer projection as
OH OH
*
(b) Alanine CH3  C H  COOH can be represented in two different Fisher projections as
|
NH2
Configurational nomenclature in optical isomers :

(I) D - L System (Relative configuration) :
This method is used to relate the configuration of sugars and amino acids by the help of enantiomers of
glyceraldehyde. The configuration of (+)-glyceraldenyde has been assigned as D and the compounds with
the same relative configuration are also assigned as D, & those with (-) glyceraldehyde are assigned as L.

Ex.
Sugars have several asymmetric carbons. A sugar whose highest numbered chiral centre (the penultimase
carbon) has the same configuration as D-(+)-glyceraldehyde (– OH group on right side) is designated as a D-
sugar, one whose highest numbered chiral centre has the same configuration as L-glyceraldehyde is designated
as an L-sugar.
CHO
HO H
H OH
Ex.
CH2OH
D-Threose
(II) R and S configurations in Fischer projection : (Absolute configuration)

Step I : The priorities of groups which are attached with the asymmetric C-atom are assigned by CIP rule.
Step II : The lowest priority group is brought to the bottom of Fischer projection by two or even simultaneous
exchanges.
Step III : Then an arrow is drawn from first priority group to second priority group to third priority group. If the
arrow is clockwise the configuration assigned to the projection is R & If it is anticlockwise the configuration
assigned is S.
Ex. (i) (ii) 
(iii) 
(iv) 
(III) R and S configurations in wedge-dash formula : (Absolute configuration)

Step 1 : Decide the priority of groups by sequence rule.
Step 2 : Bring the lowest prior group to dash by even simultaneous exchanges.
Step 3 : Draw an arrow from first prior group to second prior group till third prior group.
Step 4 : If the direction of arrow is clockwise the configuration is R and if anticlockwise it is S.

Converting a wedge-dash formula into Fischer projection formula :
Draw the Fischer projection formula having equivalent configuration to the wedge-dash formula.
(2)
COOH
(4) H R
C
Ex. (a) CH 3 
NH 2 (3)
(1)
Here the lowest prior group is already on dash, there is no need for exchanges.
(b)  
CF3 CF3 NHMe NHMe

R R S S
Cl CH3 Ph OH C
(c)  C CH3 (d)  OH
H Cl H Me Ph Me
Enantiomers :
Stereoisomers which are non-superimposable mirror images of each other are called enantiomers.
Ex. (a) 2-Chlorobutane : (b) Glucose :
Glucose Glucose
Enantiomers
Racemic mixture :
A mixture of equal amounts of enantiomers is called a racemic mixture or racemic modification. A racemic
modification is always optically inactive when enantiomers are mixed together, the rotation caused by a
molecule of one enantiomer is exactly cancelled by an equal and opposite rotation caused by a molecule of
its enantiomer.
The prefix (±) is used to specify the racemic nature of the particular sample.
e.g. (±) Lactic acid, or (d + l) Lactic acid.
Optical purity :
Sometimes we deal with mixture that is neither optically pure nor racemic mixture. In these cases we
specify the optical purity of the mixture. It is defined as the ratio of its rotation to the rotation of pure
enantiomer.
observed optical rotation
Optical purity = optical rotation of pure enantiomer × 100
Ex. If we have some 2-butanol with observed rotation of + 9.72, we compare this rotation with + 13.5 rotation of
the pure (+) enantiomer.
9.72
optical purity = × 100 = 72%.
13.5
That means 72% is pure (+) 2-Butanol and 28% is (± mixture)
Total (+) isomer = 72 + 14 = 86%, (–) isomer = 14%

Enantiomeric excess :
To compute the enantiomeric excess of a mixture we calculate the excess of predominant enantiomer as a
percentage of the entire mixture. The calculation of enantiomeric excess gives the same result as the
calculation of optical purity.
| d  | excess of one enantiomer over other

 Optical purity = Enantiomeric excess = × 100 = entire mixture × 100
d
Thus for above example optical purity = enantiomeric excess = d – l = 72 % & d + l = 100 %
so, 2d = 172  d = 86% & l = 14 % (composition of mixture)
Optical diastereomers :
The optical isomers which are neither mirror image nor superimposable to each other are called diastereomers.
Diastereomers have different physical and chemical properties and they can be easily separated by physical
methods.
Ex. Let us consider the stereoisomers of 3-chlorobutan-2-ol
There are 4 stereoisomers of 3-chlorobutan-2-ol. In which (I & II) & (III & IV) are enantiomeric pairs. (I & III)
or (I & IV) or (II & III) or (II & IV) all the isomers in each pair are neither mirror image nor superimposable
to each other. Therefore these pairs are optical diastereomers.
Properties of Enantiomers & Diastereomers :
Properties Enantiomers Diastereomers

(1) Molecular formula Same Same
(2) Structural formula Same Same
Stereochemical formula
(3) Different Different
(structure formula with orientation)
(4) Dipole moment Same Different

Physical properties (m.p., b.p., density,
(5) Same Different
solubility, refractive index etc.)
Different sign but
(6) Specific rotation Different
same magnitude
Chemical properties
(6) (a) with optically inactive compound Same Different
(b) with optically active compound Different Different
Meso compound :
A meso compound is one whose molecules are superimposable on their mirror images even though they
contain chiral centres. A meso compound is optically inactive since it has a plane of symmetry. A meso
compound is nonresolvable.

Ex. Let us consider the stereoisomers of 2, 3-Butanediol
In all the possible isomers I & II are enantiomers. But III & IV are not enantiomers since they have plane
of symmetry they are superimposable to each other (all symmetrical compounds are superimposable to
their mirror images).
Thus III & IV are identical & meso compounds.

Thus total stereoisomers of 2, 3-butanediol is 3. Two enantiomers and one meso isomer.
Number of optical isomers (Stereoisomers) :

Nature of compound No. of optical isomers
(n = no. of chiral centres)
n–1
III : Compounds having similar ends 2 n–1
n–1
with odd chiral centres n–1
(meso isomers = 2 2
& enantiomers = 2 – 22 )
Ex. Let us draw the total isomers of
Sol. n = 3 (odd chiral centres with similar ends.) so, Total isomers = 23–1 = 22 = 4
Reaction of chiral molecules with optically active reagent (optical resolution) :

Resolution refers to the method of separating a racemic mixture into its enantiomeric constituents.
Method : A racemic mixture is allowed to react with another optically pure compound. This changes a
racemic mixture into a mixture of diastereomers which have different melting and boiling point and solubilities.
These can be separated from one another by conventional method of separation of compounds. The separated
diastereomers is then broken down to give pure enantiomers.
Suppose a racemic mixture (±) A is to be separated. It is reacted with an optically pure compound (+) B.
Thus the schematic diagram for resolution will be.

Ex. Separation of racemic mixture of 2-Chloropropanoic acid.
Diastereomers (Separable)
CH3 Ph H Ph
- + - +
Cl COO NH3 CH3 Cl COO NH3 CH3
H H CH3 H
(S, R) (R, R)
+ +
H H
CH3 Ph H Ph
Cl COOH NH2 CH3 Cl COOH NH2 CH3
H H CH3 H
(S) (R) (R) (R)

Optical activity without asymmetric carbon :
(I) Case of allene :
(a) Allenes with even  bonds :
the orbital diagram of this structure will be
Since the groups at the end of allene are in perpendicular plane, it will not show geometrical isomerism. The
molecule lacks centre of symmetry as well as plane of symmetry. Overall the structure has molecular
dissymmetry which is the sufficient condition for optical activity. The molecule will exist in two enantiomeric
forms.
(b) Allenes with odd  bonds :
the orbital diagram of this structure will be
The groups at the end of allene structure lie in same plane (ZX plane). Therefore it will have a plane of
symmetry (ZX plane). The molecules lacks molecular dissymmetry & it will not show optical activity and
optical isomerism. But the compound will exist in two geometrical diastereomeric forms.
(II) Case of spiranes :

A similar case like allenes is observed in spiranes. The spiranes with even rings and different groups at
terminal carbons show optical activity & optical isomerism, while the spiranes with odd rings shows geometrical
isomerism.
(a) spiranes with even rings :
shows optical isomerism.
(b) spiranes with odd rings :
shows geometrical isomerism.

(III) Case of cycloalkylidene :
(IV) Case of ortho-ortho-tetrasubstituted biphenyls :
becomes non-planar at room temperature in order to have minimum electronic
repulsion among the substituent. In this orientation (phenyl planes perpendicular to each other) the free
rotation of C – C single bond is restricted and molecule shows optical activity due to molecular disymmetry.
Compounds having chiral centres other than carbon :

The tetrahedral atom with four different groups attached to it is a stereocentre (chiral centre). Thus when
atom like nitrogen, phosphorous, sulphur, silicon, germanium has four different groups attached with them
they are chiral and show optical activity & hence optical isomerism possible.
Asymmetric nitrogen : Amine inversion

Amine with all different groups attached to N-atom have chiral centre (R1R2R3N) as nitrogen atom. Since the
geometry of the molecule is tetrahedral it has molecular dissymmetry. It will exist as two enantiomers but
the two enantiomers of amines cannot be separated because they rapidly interconvert into each other.
Therefore they always exist as racemic mixture hence optically inactive.
..
Ex. Ethylmethyl amines CH3 NHC2H5 .
Interconvertible ethylmethylamine enantiomers (non resolvable)

2 Conformational Isomerism
Free rotation : For defining free rotation let us consider the bonding in ethane.
We find that the -bond joining the carbon atoms is cylinderically symmetrical about the line joining the two
carbon nuclei ; if the energy does not differ much in different arrangements the molecule can rotate about this
carbon-carbon  bond, we describe this freedom to change by saying that there is free rotation about the
carbon-carbon single bond.
Conformations :
Different arrangements of atoms that can be converted into one another by rotation about single bonds are
called conformations.
Conformational isomers :
There are infinite arrangement (conformations) which arise due to free rotation around carbon-carbon  bond,
out of them different conformations corresponding to energy minima are called conformational isomers. The
conformational isomerism arises due to free rotation along a bond.
Newman projection :
For conformational analysis, a special type of structural formula is convenient to use which is called newman
projection formula and another type is a sawhorse formula.
To write newman projection formula we imagine ourselves taking a view from one carbon atom directly along
the selected bond axis to the next atom. The front carbon and its other bonds are represented as and
those of the back carbon as
Dihedral angle :
The angle between C – X and C – Y in X – C – C – Y when it is visualised along C – C bond.
Staggered, eclipsed and skew conformations :

(I) The staggered conformation of a molecule is that conformation where the dihedral angle between the
bonds at each atom of carbon-carbon bond is 60°, 180°,300°.
(II) In the eclipsed conformation the atoms bonded to carbons at each end of carbon-carbon bond are
directly opposite to one another. The dihedral angle between them is 0°, 120°, 240°.
(III) Skew conformation : All conformations other than staggered or eclipsed are skew conformations.

Factors affecting stability of conformations :
(I) Angle strain :
Any deviation from "normal" bond angles are accompanied by angle strain. It is normaly present in the cyclic
structures but absent in the acyclic structures.
(II) Torsional strain :
Any pair of tetrahedral carbons attached to each other tend to have their bonds staggered for minimum
repulsion between their bonds. Any deviation from the staggered conformation are accompanied by torsional
strain.
(III) van der Waals strain :
Non bonded atoms or groups that just touch each other i.e. they are about as far apart as the sum of their van
der Waals raddii, attract each other. If brought any closer together they repel each other. Such crowding
together is accompanied by van der Waals strain.
Conformational analysis of ethane :

Ethane molecule contains a carbon-carbon  bond and each carbon is further attached to 3 H-atoms. It
exists in two extreme conformations i.e.
(i) eclipsed conformation (ii) staggered conformation
The potential energy barrier between the two conformations of ethane is about 12.5 kJ/mol.
The potential energy of ethane molecule is at a minimum for the staggered conformation, increase with
rotation and reaches a maximum at the eclipsed conformation. Most ethane molecules naturally exist in the
most stable staggered conformation. There are only three energy minima, that is ethane has only
three conformers. Since they are indistinguishable and degenerate.
Energy profile of Eclipsed and Staggered forms of ethane

Stability order : Staggered > Ecilpsed.
Conformational analysis of butane :
If we consider rotation about the C2 - C3 bond of butane, we find that there are six important conformations
shown as I - VI below :
Energy profile of conformations of butane :
Strains and stability in n-butane

Conformation dihedral Torsional
vander Waal strain Stability
of n-butane angle ( ) strain
I : Anti 180° Absent Absent Maximum
II : Partially eclipsed 120° Maximum Present (between – CH3 & – H grps) Intermediate - 1
III : Gauche 60° Absent Present (between two – CH3 grps) Intermediate - 2 (> Intermediate1)
IV : Fully eclipsed 0° Maximum Maximum (between two – CH3 grps) Minimum
The stability order will be : Anti > Gauche > Partially eclipsed > Fully eclipsed.
n-Butane exists as three conformational isomers one anti (IV) and two gauche (II & VI). The gauche
conformers II and VI are mirror images of each other and hence are conformation enantiomers. Gauche
conformations (II & VI) and anti conformation (IV) are not mirror images of each other and hence are
conformational diastereomer.
n-Butane spends the greater part of its time as the anti conformer, and divides the smaller part equally
between the two gauche conformers. As a result of the rapid inter conversion these isomers can't be separated.

Case of intramolecular hydrogen bonding :
In case of G – CH2 – CH2 – OH, where G = – OH, – NH2 , – F, – NR2, – NO2, – COOH, – CHO the Gauche form
is more stable than the anti form due to intramolecular hydrogen bonding i.e.
F ... H intramolecular F
H-bonding
H O H H
(i) Gauche form (ii) Anti form
H H H H
H OH
Stability order : Gauche form > Anti form > Partially eclipsed > Fully eclipsed.
3. Conformational analysis of cyclohexane :

(I) Chair form :
The most stable conformation of cyclohexane ring is the chair conformation. In this non-planar structure the
C–C bonds angles are all 109.5º. This conformation is free from all the strains (like angle strain and torsional
strain.)
Axial and equatorial bonds in chair form of cyclohexane :
The 12 hydrogen atoms of chair conformation of cyclohexane can be divided into two groups. Six of the
hydrogens, called axial hydrogens, hence their bonds parallel to a vertical axis that passes through the rings
centre. These axial bonds are directed up & down on adjacent carbons. The second set of six hydrogens
called equatorial hydrogens are located approximately along the equator of the molecule.
(II) Boat form :

Another conformation which is known as boat conformation has exactly eclipsed conformations.
In boat form of cyclohexane 6 hydrogens are equatorial, 4 hydrogens are axial and two hydrogens are
flagpoles. It is an unstable conformation of cyclohexane due to torsional strain among axial hydrogens
and due to van der waals strain caused by crowding between the "flagpole" hydrogens.

Conformational inversion (Ring flipping) in cyclohexane :
Like alkanes cyclohexane too is conformationally mobile. Through a process known as ring inversion, chair-
chair interconversion, or more simply ring flipping one chair conformation is converted to another chair through
the half chair, twist boat and boat form.
By ring flipping all axial bonds convert to equatorial and vice-versa. The activation energy for cyclohexane ring
inversion is 45 kJ/mol. It is a very rapid process with a half-life of about 10–5 sec. at 25°C.
The relative energy profile of various conformations of cyclohexane
because of the greater stability of the chair form, more than 99% of the molecules are estimated to be in a
chair conformation of any given moment. Twist boat form of cyclohexane is chiral.
Conformational analysis of monosubstituted cyclohexanes :

In ring inversion in methylcyclohexane the two chair conformations are not equivalent. In one chair the methyl
group is axial ; in the other it is equatorial. At room temperature 95% of the methylcyclohexane exist in
equatorial methyl group whereas only 5% of the molecule have an axial methyl group.

1, 3-diaxial repulsion :
A methyl group is less crowded when it is equatorial than when it is axial. The distance between the axial
methyl groups at C-1 and two hydrogens at C-3 & C-5 is less than the sum of their vander waal radii which
causes vander waal strain in the axial conformation this type of crowding is called 1, 3-diaxial repulsions.
When the methyl group is equatorial, it experience no significant crowding.
Ex. Draw the most stable conformation of (a) 1, 2-dimethylcyclohexane. (b) cyclohexane-1, 3-diol
Ans. (a) (b)

Type (I) : Very Short Answer Type Questions [01 Mark Each]
1. Write the definition of geometrical isomers & give one example.
2. Write the definition of enantiomer with example.
3. Write the definition of Diasteromer with one example.
4. Write the definition of meso compound with one example.
5. Draw the structural isomer of C3H6Cl2 which can exhibit enantiomerism.
6. Differentiate between chiral and achiral molecules.
7. Draw the structure of chair & boat form of cyclohexane.
8. Write the stablity order of conformation of ethylene glycol ?
9. Define the racemic mixture ?
Type (II) : Short Answer Type Questions [02 Marks Each]
10. Find the total number of geometrical isomers of following compounds.
(I) (II)
11. Indicate whether each of the following compound is 'E' or 'Z'.
(i) (ii)
(iii) (iv)
12. What is meant by specific rotation ?

13._ Find total number of chiral carbon atoms in the following compounds :
(I) (II)
(III) (IV)
14._ Find R/S configuration of following compounds.
(I) (II)
(III) (IV)

15._ Find relationship between the given pairs.
(I) and (II) and
16. Write the newman projection formula along C1–C2 bonds in staggered form of following compounds?
(I) (II)
Type (III) : Very Long Answer type Question [5 Marks Each]

17. Define with one example :
(a) Plane of symmetry (b) Centre of symmetry
(c) Axis of symmetry (d) Alternating axis of symmetry

Section (A) : Geometrical isomerism (Definition, Conditions & Examples across
C=C, C=N, N=N, Ring, Cycloalkene, Cycloalkylidene, Allene)
A-1. Which of the following compounds have restricted rotation and out of which can show geometrical isomerism?
(i) (ii) (iii) ClCH=CHCl (iv) Ph–N=N–Ph
(v) CH3CH=C(CH3)2 (vi) CH3CH=CH2 (vii) CH3CH=CHCH3 (viii) CH3–CC–CH3
A-2. Write the essential conditions for geometrical isomerism.

A-3. Which of the following can show geometrical isomerism.
(i) (ii) =CH–CH=CH–Ph
(iii) (iv)
A-4. Which of the following can show geometrical isomerism ?
H OH Cl
H H H
H C
(i) C = C=C (ii) C=N (iii) C (iv) CH3
Cl Cl CH3 CH3 Cl
Cl
Section (B): Number of geometrical centres, geometrical isomers & number of oximes
B-1. Find the number of geometrical isomers possible of the following compounds.
(i) (ii) (iii) (iv)
B-2. How many n-octene can show geometrical isomerism ?

B-3. For the structure of Hepta-2, 5-dienoic acid :
(i) How many carbon atoms are sp2 hybridised. (ii) How many geometrical isomers are possible.
(iii) Write the structure of its geometrical isomer in which all orientations are cis.
B-4. Which of the following carbonyl compound will give two products after reaction with NH2OH :
(i) (ii) (iii)
(iv) (v) (vi)
Section (C) : CIP Rules (E/Z Naming) & Physical Properties of G.I
C-1. Indicate whether each of the following compound is 'E' or 'Z'.
(i) (ii)
(iii) (iv)
C-2. (a) BrHC = CHBr exists as two diastereomers draw them and compare their dipole moment.
(b) trans-Butenedioic acid has higher melting point than cis-butenedioic acid. Why ?
(c) Draw the cis and trans structures of hex-2-ene. Which isomer will have higher b.p. and why ?
Section (D) : Chiral carbon (Chiral Centre and Stereo centre), Projection Formula (Fischer,
Wedge-dash, Newmann & Sawhorse),R/S & D/L Naming.
D-1. Number of chiral carbon atoms in the compound w, x, y and z respectively would be :
D-2. How many number of chiral centres present in the following compounds ?
CH2OH
O
H OH
H
OH H
HO
(i) H OH D(+)-Sucrose (ii)

O
HO H2C O
H H HO
CH2OH
OH H

D-3._ Find R/S configuration of following compounds.
(I) (II) (III) (IV)
D-4._ Find D/L configuration in the following molecules.
(I) (II) (III) (IV)
Section (E) : Element of Symmetry (POS, COS, AOS)

E-1._ Find plane of symmetry and centre of symmetry (if possible) in the following compounds.
(I) (II) (III)
(IV) (V) (VI)
Section (F) : Definition and Properties of Enantiomers, Diastereomers, Mesocompounds

F-1._ Find relationship between the given pairs.
(I) and (II) and
(III) and (IV) and
Section (G) : Calculation of no. of Stereoisomers

G-1._ For the given compound CH3 – CH – CH  CH – CH3 .
|
OH
(I) Total number of stereoisomers.
(II) Number of optically active stereoisomers.
(III)Total number of fractions on fractional distillation of all stereoisomers.
G-2. The total number of possible isomers with molecular formula C6H12 that contain a cyclobutane ring.

Section (H) : Plane polarized light, specific rotation, observed rotation, optical purity and
enantiomeric excess
H-1. What does D/L & d/l represent.
H-2. Write the definition of specific rotation.

H-3. Write the formula for optical purity & enantiomeric excess.
Section (I) : Racemic mixture, Optical Resolution

I-1. The total number of fractions (n) obtained in the following reaction is ..........
CH3 CH3 CH3 CH3


H
R–COOH + H OH + H OH  H OCOR + H OCOR
(±)
D C2H5 D C2H5
Section (J) : Optical active compounds without chiral carbon (Allene, Spirane, Biphenyl),
Psuedo chiral carbon and Amine inversion
J-1. Which of the following are chiral compound.
O CH3
O || Cl |+ H
(i) S (ii) P (iii) N
Me Et C2H5O Br Et D
Me CH3
| |+
H C
(iv) Si (v) C (vi) C2H5
Et Ph C2H5 H H CH3
Section (K) : Conformational isomers, strains and stability.

K-1. Write the most polar and most stable conformer of 1-nitropropane.
Section (L) : Conformational analysis of Ethane, Propane, Butane and Substituted butane
L-1. Which conformational state of n-butane lies in higher energy state when rotated along C2 – C3 bond ?
L-2. Draw the most stable conformation of meso-CH3CHD – CHDCH3
L-3. Consider all types of C – C bond rotation in following molecule.
CD 3
|
H3 C  C  CF3
|
CCl3
How many number of different types of eclipsed conformations are possible ? Draw newmann conformations
of all eclipsed form.
Section (M) : Conformational analysis of compound having intramolecular H-bonding.

M-1. Draw the most stable conformer of 3-hydroxypropanal.

* Marked questions may have more than one correct answers.
Section (A) : Geometrical isomerism (Definition, Conditions & Examples across C=C, C=N,
N=N, Ring, Cycloalkene, Cycloalkylidene, Allene)
A-1. Stereoisomers have different : .
(A) Molecular formula (B) Structural formula
(C) Configuration (D) Molecular mass
A-2*. What should be the minimum conditions to show geometrical isomerism ?
(A) Restricted rotation about double bond or ring.
(B) Groups which are responsible to show geometrical isomerism differ in their relative distance.
(C) Free rotation about single bond.
(D) Two different groups at both restricted atoms.
A-3. Which can show the cis-trans isomerism :

(A) ClCH2CH2Cl (B) Cl2C==CH2
(C) Cl2C==CCl2 (D) ClCH ==CHCl
A-4. Which of the following compounds will not show geometrical isomerism :
(A) Azomethane (B) 1-Bromo-2-chloroethene
(C) 1-Phenylpropene (D) 2-Methyl-2-butene
A-5. Which of the following compound can not show geometrical isomerism ?
(A) (B)
(C) (D)
A-6. The geometrical isomerism is shown by :-

CH2
CH2
(A) (B)
CHCI
CHCI
(C) (D)
Section (B) : Number of geometrical centre, geometrical isomers & no. of oximes
B-1. How many geometrical isomers are possible for the given compound.
Ph – CH = CH – CH = CH – COOH
(A) 3 (B) 4 (C) 2 (D) 1
CH3 – CH = CH – CH = CH – CH = CH2
(A) 2 (B) 4 (C) 6 (D) 8

(A) 2 (B) 4 (C) 6 (D) 8

B-4. No. of Geometrical isomers for following compound is :
(A) 8 (B) 16 (C) 32 (D) 10
B-5. Which of the following will form only one oxime on reaction with NH2OH solution ?
(A) I, II (B) II, III (C) I, IV (D) II, III, IV
B-6. The compounds X and Y in below reaction can be
Ph – NH . NH2 + (X) + (Y)
(A) CH3  CH2  C  CH3 + CH3  C  Ph (B) Ph  C  CH3 + CH3CHO

|| || ||
O O O
(C) CH2 = O + CH3CHO (D) CH2 = O + CH3  C  CH3

||
O
Section (C) : CIP Rules (E/Z Naming) & Physical Properties of G.I.
C-1. Identify (Z) - 2 - pentene :-
(A) (B) (C) (D)
C-2. The 'E'-isomer is/are :
(A) (B)
H C2H5
(C) C C (D)
||
H3C CH(CH3)2
C-3. The correct stereochemical formula of Trans-3-chloro-1-phenylbut-1-ene is
(A) (B)
(C) (D)

C-4. Which of the following is a syn isomer :-
(A) (B)
(C) (D)
C-5. The correct order/s for the given pair of isomers is
(A) > (Melting point)
(B) < (Dipole moment)
(C) > (Boiling point)
(D) > (Water solubility)
Section (D) : Chiral carbon (Chiral Centre and Stereo centre), Projection Formula (Fischer,
Wedge-dash, Newmann & Sawhorse) R/S & D/L Naming.
D-1. Chiral molecules are :
(A) Superimposable on their mirror image (B) Not superimposable on their mirror image
(C) unstable molecules (D) capable of showing geometrical isomerism
D-2. Number of chiral carbon persent in the following compound :
CH3 – CH – CH2 – CH – CH – CH3
| | |
OH Br C2H5
(A) 2 (B) 3 (C) 4 (D) 5
D-3. The compound which has maximum number of chiral centres is
(A) (B) (C) (D)
D-4. Which of the following is the structure of (S)-Pentan-2-ol is ?
(A) (B) (C) (D)
D-5. The configuration of the given compound is :
(A) E (B) R (C) S (D) Z

D-6. Which Fisher projection represents the given wedge dash structure :
(A) (B) (C) (D)
D-7. Which of the following have same configuration.

F Br H
C H C Cl C Br
Cl Br H F F Cl
I II III
(A) I & II (B) II & III (C) I & III (D) All
D-8. Which has D configuration.
CH3 OH
(A) HO H (B) H COOH
COOH CH3
CH3 COOH
(C) H OH (D) H2N H
CHO CH3
D-9. D-Fructose (C6H12O6) has IUPAC name (3L,4D, 5D)1, 3, 4, 5, 6-Pentahydroxyhexan-2-one. Its last asymmetric
carbon atom (C*5) has D-configuration. The correct stereochemical formula of D-Fructose is
(A) (B) (C) (D)
Section (E) : Elements of Symmetry (POS, COS, AOS)

E-1. Which statement is wrong about symmetry ?
(A) Plane of symmetry is an imaginary plane which bisects the molecule in two equal halves in such a way
that each half of the molecule is the mirror image of the other half.
(B) Centre of symmetry is the point in a molecule through which if the straight line is drawn from any part of
the molecule and if then this line encounters identical groups at equal distances in opposite direction.
(C) A molecule which does not possess any element of symmetry is called asymmetric molecule.
(D) A molecule which does not possess any element of symmetry is called symmetric molecule.

E-2. Which of the following compound posses plane of symmetry ?
(A) (B)
(C) (D)
E-3. Which of the following compound posses centre of symmetry ?
O
H
H N–C CH3
(A) (B) H C C–N H
3
H
O
CH3
(C) H OH (D)
OH H
CH3
E-4. Which of them contains C1 axis of symmetry ?
(A) (B)
(C) CH4 (D) All
E-5 . which axis of symmetry exists along the given axis.
(A) C2 (B) C3 (C) C4 (D) All of the above
E-6. In which C2 axis of symmetry is present along the given axis ?
(A) (B) (C) (D)

E-7. Which of the following are chiral :
(1) (2) (3) (4)
(A) 1, 2, 3 (B) 1, 2, 4 (C) 2, 3, 4 (D) 1, 3, 4

E-8. Which of the following molecule is chiral :
(A) (B)
(C) (D)
Section (F) : Definition and Properties of Enantiomers, Diastereomers, Mesocompounds

F-1. Which of the following statements is not correct :
(A) Enantiomers are Eessentially chiral and optically active
(B) Diastereomers are not neccesarily chiral and optically active
(C) All geometrical isomers are diastereomers
(D) All diastereomers are chiral and optically active
F-2. Which is not the pair of enantiomers ?
(A) (B)
(C) (D)
F-3. Which of the following pairs of compounds are enantiomers :

CH3 CH3 CH3 CH3
OH and HO H H OH HO H
(A) H (B) and
OH H H OH HO H HO H
CH3 CH3 CH3 CH3

CH3 CH3 CH3
H OH HO H HO H
(C) and (D) H OH and HO
H OH H
CH3 CH3 CH3

F-4. Stereoisomers which are not mirror image of each other, are called : -
(A) Enantiomers (B) Tautomers (C) Meso (D) Diastereomers
F-5. Which one among the following is not diastereomeric pair.
(A) I and III (B) I and II (C) II and III (D) I and IV
F-6. Which of the following is a meso isomer ?
(A) (B) (C) (D)
F-7. How are compounds I and II related ?
(A) Enantiomer (B) Diastereomers

(C) Constitutional isomer (D) Identical molecules
F-8. and are
(A) Enantiomers (B) Optical inactive diastereomers

(C) Optical active diastereomers (D) Identical
Section (G) : Calculation of no. of Stereoisomers

G-1. Total number of stereoisomers of compound is :
CH3  CH  CH  CH3
| |
OH Br
(A) 2 (B) 4 (C) 6 (D) 8
G-2. Total number of optically active stereoisomers of tartaric acid is

(A) 2 (B) 4 (C) 3 (D) 0
G-3. How many stereoisomers are possible for ?
(A) 128 (B) 64 (C) 32 (D) 16

G-4. Number of fractions on fractional distillation of mixture of :
(A) 2 (B) 3 (C) 4 (D) 1
G-5. The total number of ketones (including stereo isomers) with the molecular formula C6H12O is :
(A) 4 (B) 5 (C) 6 (D) 7
Section (H) : Plane polarized light, specific rotation, observed rotation, optical purity and
enantiomeric excess
H-1. The instrument which can be used to measure optical activity, i.e., specific rotation:
(A) Refractometer (B) Photometer (C) Voltmeter (D) Polarimeter
H-2. (+) tartaric acid has a specific rotation of + 12 unit when measured in 12 cm polarimeter tube and 2g/ml
concentration at given temperature and light. When it is diluted to half the concentration, length of tube and
other parameters being same, the specific rotation will be
(A) + 6 unit (B) + 12 unit (C) – 6 unit (D) + 24 unit
H-3. If optical rotation produced by is + 36º then that produced by is
(A) –36º (B) 0º (C) +36º (D) unpredictable
H-4. The enantiomeric excess and observed rotation of a mixture containing 6 gm of (+)-2-butanol and 4 (gm) of
(–)-2-butanol are respectively (If the specific rotation of enantiomerically pure (+)-2-butanol is + 13.5 unit).
(A) 80%, + 2.7 unit (B) 20%, – 27 unit (C) 20%, + 2.7 unit (D) 80%, – 27unit
Section (I) : Racemic mixture, Optical Resolution
I-1. The racemic mixture of Alanine can be resolved by using,
(1) (+)-2-Butanol (2) (l)-2-Chlorobutanoic acid

(3) (±) -2-Butanol (4) (dl mix)-2-Chlorobutanoic acid
(A) 1 & 2 only (B) 1 & 3 only (C) 2 & 4 only (D) 3 & 4 only
I-2. The major product (ester) of the following reaction is
H SO
+ 2 
4

(A) A single stereoisomer (optically active) (B) A mixture of diastereomers (both optically active)
(C) A racemic mixture (optically inactive) (D) A mixture of four stereoisomers (two racemic mixtures)
I-3. Which of the following pair of isomers can not be separated by fractional crystallisation or fractional distillation:
(A) Maleic acid and Fumaric acid (B) (+)-Tartaric acid and meso-tartaric acid
(C) CH3  CH  COOH and H2N–CH2–CH2–COOH (D) (+)-lactic acid and (–)-lactic acid
|
NH2

Section (J) : Optical active compounds without chiral carbon (Allene, Spirane, Biphenyl),
Psuedo chiral carbon and Amine inversion
J-1*. Which of the following compounds will show optical activity ?
(A) (B) (C) (D)
J-2. Which of the following amine is optically active ?

(A) CH3NH2 (B) CH3NHC2H5
(C) CH3CH2CH2– (D) sec-Butylamine
J-3. The following molecules are :

H CH3
C=C=C
H3C H
(A) Enantiomers (B) Diastereomers (C) Identical (D) Conformers
J-4. The given compound (X) has :
(A) chirality (B) superimposability on its mirror image isomer

(C) plane of symmetry (D) C2 axis of symmetry
J-5. Total number of optically active stereoisomers of CH3 – CH – CH – CH – CH3

| | |
Cl Cl Cl
(A) 2 (B) 4 (C) 6 (D) 8
J-6. How many spatial orientations are possible in the following compound ?
(A) 2 (B) 8 (C) 6 (D) 4
J-7. Total number of optical active stereoisomers of the following compound is :

CH3 – CH = CH – CHCl – CH = C = CH – CH = CH – CH3
(A) 8 (B) 6 (C) 16 (D) 10
Section (K) : Conformational isomers, strains and stability.

K-1.* Which statement (s) is/are true :
(A) When value of dihedral angle is 180º then this conformation is called anti conformation.
(B) When  = 60º then this conformation is called gauche.
(C) When  = 0º then this conformation is called eclipsed conformation.
(D) Other than staggered and eclipsed conformation are called skew conformations.
K-2. The eclipsed and staggered conformation of ethane is due to –

(A) Free rotation about C–C single bond (B) Restricted rotation about C–C single bond
(C) Absence of rotation about C–C bond (D) None of the above

K-3. Which of the following is associated with Torsional strain ?
(A) Repulsion between bond pair of electrons (B) Size of the groups present at adjacent atoms
(C) Bond angle strain (D) Attraction of opposite charges
K-4. The Baeyer’s angle strain is expected to be maximum in

(A) Cyclodecane (B) Cyclopentane (C) Cyclobutane (D) Cyclopropane
K-5. The minimum torsional strain developed in butane is at dihedral angle(s)

(A) 0º, 108º (B) 120°, 240º (C) 60°, 180°, 300° (D) 60°, 120°, 180°
Section (L) : Conformational analysis of Ethane, Propane, Butane and Substituted butane
L-1. In the following the most stable conformation of n-butane is :
(A) (B) (C) (D)
L-2. Which of the following is correct P.E. diagram for propane and butane respectively ?
P.E. P.E.
(I) (II)
Dihedral angle Dihedral angle
P.E. P.E.
(III) (IV)
Dihedral angle Dihedral angle
(A) I & II (B) I & III (C) II & IV (D) IV & II
L-3. The dipole moment of 1, 2-Dichloroethane is 1.12 D. Which statement is correct about this compound.
(A) It exists mainly in fully eclipsed conformation.
(B) It exists only in anti conformation.
(C) The polarity is due to gauche (skew) conformation.
(D) The anti conformation has highest dipole moment.
L-4. Which of the following is an achiral molecule?
(A) (B) (C) (D)
L-5. The newman projection formula of 2,3-dimethylbutane is given as
X,Y respectively can be :

(A) –CH(CH3)2 and H (B) –CH3 and –C2H5 (C) –C2H5 and –CH3 (D) H and –CH(CH3)2

Section (M) : Conformational analysis of compound having intramolecular H-bonding.
M-1. In 2-Fluoroethanol which conformer will be most stable ?
(A) Eclipsed (B) Skew (C) Gauche (D) Staggered
M-2. Which of the following statement regarding the populations of different conformations of optically active
butane-2, 3- diol is true
(A) The most populated conformer will have the hydroxy group at anti-position.
(B) All staggered conformations will be equally populated and are major.
(C) The most populated conformer will have hydroxyl groups at guache position.
(D) Relative populations of different conformers are not predictable.
M-3. The least stable staggered conformation of optically inactive isomer of butan-2, 3-diol is
(A) (B) (C) (D)
M-4. The true statement about the following corformation is :
(A) It has maximum angle strain.

(B) It does not have eclipsing strain (tortional strain).
(C) It does not have any intramolecular hydrogen bonding.
(D) It has maximum vander waal strain.
M-5. The structures I and II are
COOH COOH
H OH H COOH
H OH H OH
COOH OH
I II
(A) Conformational diastereomers (B) Configurational enantiomers

(C) Configurational diastereomers (D) Identical
M-6. and are
(A) Enantiomers (B) diastereomers

(C) Identical compounds (D) Conformers

DIRECTIONS :
(E) Both Statements are False.
1. Statement-1 : The boiling point of Cis–1,2–dichloroethene is higher than corresponding trans-isomer.
Statement-2 : Because the cis isomer of 1,2–dichloroethene is more polar than trans.
2. Statement-1 : lactic acid shows gemetrical isomerism.
Statement-2 : Because it has not chiral carbon.
3. Statement-1 : Meso tartaric acid is optically inactive
Statement-2 : Because it has plane of symmetry.
4. Statement-1 : All the hydrogen atoms in but-2-ene lie in one plane.
Statement-2 : Because only one carbon atom is sp2 hybridized in it.

1. Define stereoisomerism, and distinguish between Configurational isomerism & Conformational isomerism ?
2. How many minimum carbon atoms are required to show geometrical isomerism in a hydrocarbon ?
3. Define restricted rotation and give one example each of acyclic and cyclic compound, which can show
geometrical isomersm.
4._ How many cyclic and acyclic structural isomers of C5H10 can show geometrical isomerism?
5. Carbonyl compounds react with NH2OH forming oximes which represents geometrical isomersm. Which
smallest carbonyl compounds forms oxime but does not show geometrical isomerism ?
6. How many oximes are formed when 3-Phenylprop-2-enal reacts with NH2OH
7. Draw all the geometrical isomers of CH3 – CH = CH – CH = N – OH

8. Find the number of geometrical isomers possible in following compounds :
(i) (ii)
(iii) (iv) (v)
9. Write the stereo chemical formula for each of the following compounds.
(i) (E)-4-Methylhex-4-en-1-yne (ii) (Z)-1-Cyclopropylpent-1-ene
(iii) (2E, 4E) hexa-2, 4-diene (iv) (2E, 4Z) hexa-2, 4-diene
10. How many structure with molecular formula C6H14 are chiral?
11. Write the correct fisher projection formula and D or L configuration for the following compounds.
(1) (2) (3)

12. No. of chiral atoms in D-fructose & D-glucose are respectively :
13. Write down IUPAC name of following molecule with their stereochemical representation.
(a) (b)
14. The R/S configuration of following compounds are :
(a) (b) (c) (d)
15. Find plane of symmerty, centre of symmerty and axis of symmetry (if possible) in the following molecules.
Cl Cl
(i) (ii) (iii)
H H
Br H
(iv) (v) (vi)
H Br
CH3 Ph
H CH3
H H3C
(vii) H (viii) (ix)
H CH3 H
Ph H
H CH3 CH3 H H CH3

C C C
16.
Cl Br Br Cl Cl Br
I II III
(i) Total number of fractions on fractional distillation of I, II and III.
(ii) Optical active compounds.
(iii) Relation between I and II.
(iv) Relation between I and III.

17. Observe the com pound 'M'
M=
If in this compound
X = Total number of asymmetric C* atoms
Y = Number of similar asymmetric C* atoms
Z = Number of optically active stereoisomers
W = Number of opticaly inactive isomers
R = Number of geometrical orientations in space
report your answer in the order :
18. (+)-Mandelic acid has a specific rotation of + 158 unit. What would be the observed specific rotation of each
of the following mixture ?
(a) 25% (–)-mandelic acid and 75% (+)-mandelic acid
(b) 50% (–)-mandelic acid and 50% (+)-mandelic acid
(c) 75% (–)-mandelic acid and 25% (+)-mandelic acid.
19. Give the relationship between the following pairs of compounds.

Compounds Relationship
(a) and ........................
(b) and ........................
(c) and ........................
(d) and ........................
20._ Write the newman projection formula of the following compounds

(I) Cl–CH2–CH2–CH3 in its most polar form.
(II) HO–CH2–CH2–OH in its most stable form.
(III) HOOC–CH2–CH2–COOH in its least stable staggered form.

21. Convert the following Fischer projection into Newmann & Sawhorse projection and identify which is optically
active or not.
(A) (B)
22._ Draw the most stable newman projection formula along C1–C2 bonds of following compounds.
(i) (ii) (iii)
(iv) (v) (vi)
23. Which one is more stable and why ?

Single choice type
1. Which of the following will not show geometrical isomerism ?
(A) CH3 – N  N – CH = CH2 (B)

(C) CH3 – CH = N – OH (D) Cl–CH=C=CH–Cl
2. Which of the following statement is false about the following compounds ?
(A) () and () are identical (B) () and () are geometrical diastereomers
(C) () and () are structural isomers. (D) () and () are structural isomers.
3. Total number of geometrical isomers in the given compound is
C = CH – DC = CD – HC = C
(A) 2 (B) 4 (C) 6 (D) 8

4. Total number of geometrical isomers in the given compound is :
(A) 3 (B) 6 (C) 8 (D) 16
5. Which of the following is not true for maleic acid and fumaric acid.
(A) Configurational isomers (B) Stereo isomers (C) Z and E isomers (D) Constitutional isomers
6. Which of the following is incorrect statement :

(A) Geometrical isomers are not mirror image isomer.
(B) A compound having double bond (restricted bond) always show geometrical isomerism.
(C) Acyclic organic compoubd having single bond does not show geometrical isomerism.
(D) Cyclodecene can show cis & trans form.
7. Which is incorrect statement about geometrical isomers.
(A) Geometrical isomers can be separated by fractional distillation.
(B) In two geometrical isomers the distance between two particular groups at the ends of the restricted bond
must be changed.
(C) In cycloalkenes, geometrical isomerism exist across C=C with ring size equal to or greater than 8 carbon
atom.
(D) does't show geometrical isomerism because it has only 7 C atoms in ring.
8. Indicate the number of chiral carbon atoms in the following molecule.
HO
(A) 6 (B) 7 (C) 8 (D) 9
9. Which pair is identical ?
(A) H and H (B) and

Cl Cl
Br Br
C C
(C) and (D) H CH3 and H3C H
Cl Cl
10. The correct IUPAC name of D-Glucose is :
(D-Glucose)
(A) (2D, 3D, 4L, 5D) 2, 3, 4, 5, 6-pentahydroxyhexanal (B) D-2, 3, 4, 5, 6-pentahydroxyhexanal

(C) 6-oxo-(2D,3L,4D,5D)-2, 3, 4, 5, 6-pentahydroxohexane (D)(2D,3L,4D,5D)-2, 3, 4, 5, 6-pentahydroxyhexanal

11. Which of the following sawhorse representation is correct for the given newman projection.
(A) (B)
(C) (D)
12. Which of the following Newmann representation is incorrect for the given structure ?
(A) (B) (C) (D)
13. Which has both plane of symmetry and centre of symmetry ?
F O
CH3 CH3 H
| H N–C CH3
I  C  Cl
(A) (B) (C) | (D) H C C–N H
3
CH3 CH3 (trans)
(cis) Br H
O
14. Which of the following compound has plane of symmetry (POS) but not centre of symmetry (COS) ?
(A) (B) (C) (D)
15. Which one of the following compounds will show enantiomerism ?
(A) CH3 –– –– CH3 (B) H3C – – CH3
O O
(C) –– OH (D) –– OH
O
––
HO – H2C

16. Which of the following statement regarding the projections shown below is true ?
(A) ‘a’ and ‘b’ both represent the same configuration

(B) Both ‘a’ and ‘b’ are optically active
(C) ‘b’ alone is optically active
(D) ‘a’ alone is optically active
17. The relation between compounds I and II is ?
(A) Enantiomer (B) Diastereomers

(C) Constitutional isomer (D) Identical molecules
18. How many stereoisomers of shikonin (a drug for healing of wounds) are possible & how many of them are
optically active ?
(A) 4, 2 (B) 4, 4 (C) 8, 4 (D) 16, 4

19. Total number of stereoisomers possible of the given structure excluding the configuration mentioned is :
(A) 8 (B) 31 (C) 16 (D) 12
20. Total D stereoisomers (open chain only) for the given structure will be :
CH2(OH)CH(OH)CH(OH)CH(OH)CHO
(A) 6 (B) 4 (C) 2 (D) 8
21. Which of the following species will be optically active ?

C 2H5
|
(A) (B) H3 C  N  C 3H7
(C) (D)

22. Total number of stereoisomer of compound is :
CH3  CH  CH  CH  CH  CH  CH3
|
Cl
(A) 2 (B) 4 (C) 6 (D) 8
23. Total number of stereoisomers and optically active stereoisomers of CH3 – CH – CH  CH – CH – CH3 .
| |
Cl Cl
(A) 6, 6 (B) 6, 4 (C) 2, 4 (D) 8, 8
24. Which of the following statement is not true ?
(A) The different arrangements formed by rotations about a single bond are called conformations.
(B) The repulsion felt by the bonding electrons of one substituent as they pass close to the bonding electrons
of another substituent is called steric strain.
(C) The strain arises due to repulsion between electron clouds of the interacting atoms or groups is called
steric strain.
(D) The study of the various conformations of the compound and their relative stabilities is called conformational
analysis.
25. Newman projection of Butane is given,C-2 is rotated by 120º around C2 -C3 bond in anticlockwise direction
the conformation formed is :
(A) anti (B) fully eclipsed (C) gauche (D) partially eclipsed
26. Which statement is incorrect about anti conformation of 1-Chloropropane ?
(A) It is the most polar form (B) It has maximum torsional strain
(C) It has minimum steric strain (D) It has minimum torsional strain
27. The structures represents
&
(A) Geometrical isomers (B) positional isomers

(C) Conformational isomers (D) configurational isomers

28. Which of the following will show geometrical isomerism.
(A) (B)
(C) (D)

29. Which of the following compound has cis configuration at each double bond ?
(A) (B)
(C) (D)
30. Which carbonyl compounds can give two oximes on reaction with hydroxyl amine ?
(A) HCHO (B) CH3CHO (C) PhCHO (D) CH3COPh
31. Select the correct options for molecular formula C2H2Cl2

(A) The total number of isomers is 4. (B) Only two compounds are geometrical isomers.
(C) All isomers have 5 bonds and one  bond. (D) Its has linear shape.
32. The incorrect order with respect to the properties mentioned for the following pair of compounds is :
(A) < (Stability)
(B) < (Stability)
(C) > (Boiling point)
(D) > dipole moment ()
33. Indigotin has following isomers I and II. The correct statements for these isomers are :
(A) Diastereomers.
(B) Constitutional isomer.
(C) II is more stable than I due to intramolecular hydrogen bonding.
(D) II is more polar than I.
34. Which is/are not the structure of 3-Methyl butan-2-ol.
(A) (B)
(C) (D)

35. Correct representation of configuration for the following compound is/are:
(A) 2R, 3S (B) 2S, 3R (C) 2L, 3L (D) 2D, 3D
36. Which of the following compounds will have C2 axis of symmetry ?
(A) (B) (C) (D)
37. is :
(A) optically active molecule. (B) having plane of symmetry.

(C) having axis of symmetry. (D) having centre of symmetry
38. The meso compounds are :
(A) (B)
(C) (D)
39. Given are the four isomeric dimethyl cyclopropane ?
(I) (II)
(III) (IV)
The true statement about (I, II, III and IV) are
(A) I and II are diastereomers (B) II and III are diastereomers
(C) III and IV are enantiomers (D) IV and II are diastereomers

40. The correct relation between compounds I and II is ?
(I) (II)
(A) identical. (B) diastereomers.

(C) enantiomers. (D) configurational isomers
41. In which compounds the psuedo chiral centre is present.
(A) CH3 – CH – CH – CH – CH3 (B) CH3  CH  CH  CH  CH  CH  CH3

| | | |
Cl Cl Cl OH
(C) CH3 – CH – CD – CH – CH3 (D)

| | |
Cl Br Cl
42. Which statement is/are correct.

(A) All conformational isomers of ethane are degenerate.
(B) All conformational isomers of n-butane are degenerate.
(C) Conformational energy of ethane is more than that of n-butane.
(D) Most stable conformational isomer of HOCH2CH2OH is Gauche.

1. Match the column-I with column-II
Column-I Column-II
(A) (p) Chiral Molecule
(B) (q) Achiral Molecule
(C) (r) Plane or centre of symmetry present
(D) (s) Axis of symmetry present (except C1).

2. Match the compounds of column-I with the characteristics of column-II.
Column-I Column-II
(A) (p) Bromo-chloro cyclohexane and can show stereoisomerism.
(B) (q) Dibromo-dichloro cyclohexane and can show stereoisomerism.
(C) (r) Optically active substituted cyclohexane.
(D) (s) Substituted cyclohexane showing geometrical isomerism.
(t) Substituted cyclohexane not showing any stereoisomerism.

Column-I Column-II
(A) and (p) Ist is more stable in the given form.
(B) and (q) I, II are conformational diastereomers.
(C) and (r) IInd is more stable in the given form.
(D) and (s) dipole moment of I is more than II.
(t) I, II are configurational diastereomers.

Column-I Column-II
(A) (p) Conformation with minimum vander-waal strain
(B) (q) Conformation with maximum vander waal strain
(C) (r) Conformation of maximum torsional strain
(D) (s) Conformation with minimum torsional strain
Comprehension #
Observe the following compound :
CH3 – CH = CH
1. Which of the following cannot be its functional isomer,
(A) CH3 – CH = CH (B) CH3 – CH = CH
(C) CH3 – CH = CH (D) CH – CH = CH2
2. The total number of its geometrical isomers is :

(A) 2 (B) 4 (C) 8 (D) 16
3. The number of chiral (asymmetric) carbon atoms and optical active stereo isomers are respectively.
(A) 3, 8 (B) 2, 8 (C) 1, 2 (D) 4, 16


* Marked Questions are having more than one correct option.
1. An enantiomerically pure acid is treated with racemic mixture of an alcohol having one chiral carbon. The
ester formed will be : [IIT-JEE-2003(S), 2/84]
(A) Optically active mixture (B) Pure enantiomer
(C) Meso compound (D) Racemic mixture
2. A recemic mixture of (±) 2-phenylpropanoic acid on esterification with (+) 2-butanol gives two ester. Mention
the stereochemistry of the two esters produced. [IIT-JEE-2003(M), 2/60]
3. Give the Newman projection formula of the least stable staggered form of n–butane. Which of the following
reasons is the causes of its unstability ? [IIT-JEE-2004, 2/60]
(i) Vander–Waal’s strain (ii) Torsional strain (iii) Combination of both.
4. Newman projection of Butane is given,C-2 is rotated by 120º along C-2 & C-3 bond in anticlockwise direction
the conformation formed is : [IIT-JEE-2004, (S) 2/84]
(A) staggered (B) fully eclipsed (C) gauche (D) partially eclipsed
5. It is given that for conformational isomers, the net dipole moment is [IIT-JEE-2005, 6/60]
obs =  ixi
where obs = obsereved dipole moment of the compound
i = dipole moment of the stable conformational isomers
xi = mole fraction of stable conformers
for the compound Z – CH2 – CH2 – Z draw the Newman projection formula of all the stable conformational
isomers, if obs = 1D, and xanti = 0.82, and find gauche. Now draw the Newman projection formula of the most
stable conformation of meso Y – CHD – CHD – Y
(a) If Y is CH3 (rotation about C2 – C3 bond) (b) If Y is OH (rotation about C1 – C2 bond)
6. Statement-1 : Molecules that are not superimposable on their mirror images are chiral. because
Statement-2 : All chiral molecules have chiral centres. [IIT-JEE-2007, 3/162]
7.* The correct statement(s) about the compound given below is (are) [IIT-JEE-2008, 4/163]
(A) The compound is optically active

(B) The compound possesses centre of symmetry
(C) The compound possesses plane of symmetry
(D) The compound possesses axis of symmetry
8.* The correct statement(s) about the compound H3C(HO)HC–CH=CH–CH(OH)CH3 (X) is(are) :
[IIT-JEE-2009, 4/160]
(A) The total number of stereoisomers possible for X is 6.
(B) The total number of diastereomers possible for X is 3.
(C) If the stereochemistry about the double bond in X is trans, the number of enantiomers possible for X is 4.
(D) If the stereochemistry about the double bond in X is cis, the number of enantiomers possible for X is 2.

9. The total number of cyclic structural as well as stereo isomers possible for a compound with the molecular
formula C5H10 is [IIT-JEE-2009, 4/160]
10.* In the Newman projection for 2, 2-Dimethylbutane [IIT-JEE-2010, 3/163]
X and Y can respectively be :

(A) H and H (B) H and C2H5 (C) C2H5 and H (D) CH3 and CH3
11.* Amongst the given options, the compound(s) in which all the atoms are in one plane in all the possible
conformations (if any), is (are) [JEE-2011, 4/180]
(A) (B) H–C 
(C) H2C=C=O (D) H2C=C=CH2 [IIT-JEE-2011, 4/180]
12. The number of optically active products obtained from the complete ozonolysis of the given compound is:
[IIT-JEE- 2012, 3/136]
(A) 0 (B) 1 (C) 2 (D) 4

13. When the following aldohexose exists in its D-configuration, the total number of stereoisomers in its pyra-
nose form is : [IIT-JEE- 2012, 4/136]
14.* Which of the given statement(s) about N, O, P and Q with respect to M is (are) correct ?
[IIT-JEE- 2012, 4/136]
(A) M and N are non-mirror image stereoisomers (B) M and O are identical
(C) M and P are enantiomers (D) M and Q are identical

PART - II : AIEEE PROBLEMS (LAST 10 YEARS)
* Marked Questions are having more than one correct option.
1. Racemic mixture is formed by mixing two [AIEEE 2002]
(A) Isomeric compounds (B) Chiral compounds
(C) Meso compounds (D) Optical isomers
2. Which of the following does not show geometrical isomerism ? [AIEEE 2002]
(A) 1,2-Dichloro-1-pentene (B) 1,3-Dichloro-2-pentene
(C) 1,1-Dichloro-1-pentene (D) 1,4-Dichloro-2-pentene
3. Among the following four structures I to IV. [AIEEE 2003]
CH3 O CH3
| || |
C2H5 – CH – C3H7 CH3 – C – CH – C2H5
(I) (II)
it is true that
(A) All four are chiral compounds (B) Only I and II are chiral compounds
(C) Only III is a chiral compound (D) Only II and IV are chiral compounds
4. Which of the following will have a meso-isomer also ? [AIEEE 2004]

(A) 2-Chlorobutane (B) 2,3-Dichlorobutane
(C) 2,3-Dichloropentane (D) 2-Hydroxypropanoic acid
5. Amongst the following compounds, the optically acitve alkane having lowest molecular mass is
(A) CH3–CH2–CH2–CH3 (B) [AIEEE 2004]
(C) (D) CH3–CH2–CCH
6. Which of the following compounds is not chiral ? [AIEEE 2004]

(A) 1–Chloropentane (B) 2-Chloropentane
(C) 1-Chloro-2-methylpentane (D) 3-Chloro-2-methylpentane
7. Which type of isomerism is shown by 2,3-dichlorobutane ? [AIEEE 2005]

(A) diastereomerism (B) optical-isomerism
(C) geometric-isomerism (D) structural-isomerism
8. Increasing order of stability among the three main conformations (i.e. eclipse, anti, gauche) of 2-fluoroethanol
is [AIEEE- 2006]
(A) eclipse, gauche, anti (B) gauche, eclipse, anti
(C) eclipse, anti, gauche (D) anti, gauche, esclipse
9. Which of the following molecules is expected to rotate the plane of polarized light? [AIEEE 2007, 3/120]
(A) (B)
(C) (D)

10.* Which one of the following conformations of cyclohexane is chiral? [AIEEE-2007, 3/120]
(A) Chair (B) Boat (C) Twist boat (D) Rigid
11. The absolute configuration of is [AIEEE 2008, 3/105]
(A) R, R (B) R, S (C) S, R (D) S, S
12. The alkene that exhibits geometrical isomerism is : [AIEEE 2009, 4/144]
(A) 2-methyl propene (B) 2-butene
(C) 2-methyl-2-butene (D) propene
13. The number of stereoisomers possible for a compound of the molecular formula CH3–CH=CH–CH(OH)–Me
is: [AIEEE 2009, 4/144]
(A) 2 (B) 4 (C) 6 (D) 3
14. Out of the following, the alkene that exhibits optical isomerism is. [AIEEE 2010, 4/144]
(A) 3-methyl-2pentene (B) 4-methyl-1-pentene
(C) 3-methyl-1-pentene (D) 2-methyl-2-pentene
PART - III : CBSE PROBLEMS (LAST YEARS)

1. Define optical active substance with dextrorotatory and levorarotory. [CBSE, 1 M]
2. What is meant by chiral or asymmetric carbon atom ? [CBSE, 1 M]
3. How are enantiomers different from diastereomers? Give one example of each. [CBSE, 2 M]
4. Answer the following questions : [CBSE, 1 M]
What is meant by chirality of a compound ? Give an example. [CBSE, 1 M]
5. How many chiral atom and how many total stereoisomers are in given molecule ? [CBSE, 2 M]
CH3–CHOH–CHCl–COOH
6. Draw the stable conformer of 1, 2–-dichloro ethane. [CBSE, 1 M]
7. Draw the trans-trans conformation of the following compound. [CBSE, 1 M]

CH(Cl) = CH – CH = CH(Cl)
8. Find out the no. of geometrical isomers in [CBSE, 2 M]

C6H5–CH=CH–CH=CH–Cl
9. Identify whether the following pairs of compounds are structural or geometrical isomers: (CBSE-2007)
H CH3 H H
(i) (ii)
H3C H H3C CH3
10. What is chiral compound explain it by giving example. [CBSE 2012]


1. Two compounds having same structural formula but different orientation of atoms or groups in space due to
restricted rotation of bonds are known as geometrical isomers.
Ex.
2. Stereoisomers which are non-superimposable mirror images of each other are called enantiomers.
Ex.
3. The optical isomers which are neither mirror image nor superimposable to each other are called diastereomers.
Ex.
4. A meso compound is one whose molecules are superimposable on their mirror images even though they
contain chiral centres. A meso compound is optically inactive since it has a plane of symmetry.
Ex. plane
5.

6. A chiral molecule is one that is not superimposable on its mirror image. these molecules contain one
asymmetric or chiral carbon atom. For example : Butan-2-ol.
An achiral molecule, on the other hand, is one which is superimposable on its mirror image. For example :
Propan-2-ol.
7.
8. Gauche > Anti > Partially eclipsed > Fully eclipsed

9. A mixture of equal amounts of enantiomers is called a racemic mixture or racemic modification. A racemic
mixture is always optically inactive due to external compensation.
10. (I) Geometrical centres = 2, so total geometrical isomers = 22 = 4
(II) Geometrical centre = 1, so total geometrical isomers = 21 = 2
11. (i) Configuration = E (ii) Configuration = E (iii) Configuration = E (iv) Configuration = Z
12. Specific roation is the number of degree of rotation observe, if a 1 dm tube is used for 1 g/ml concentration of
the substance.

[] =
 d
Observed rotation (deg ree)
Specific rotation = length (dm)  conc.(g / ml)
13._ (I) 1 (II) 2 (III) 3 (IV) 5

14._ (I) R (II) S (III) R (IV) (R, R)
15._ (I) Enantiomers (II) Positional isomers
16. (I) (II)
17. (a) Plane of symmetry () : Plane of symmetry is an imaginary plane which bisects the molecule in two
equal halves in such a way that each half of the molecule is the mirror image of the other half.
(b) Centre of symmetry (i) : Centre of symmetry is the point in a molecule through which if a straight line is
drawn from any part of the molecule this line encounters identical groups at equal distances in opposite
direction.
(c) Axis of symmetry (Cn) : It is an imaginary axis about which the molecule can be rotated by 360°/n and
there by produce a molecule indistinguishable from the original molecule.

(d) Alternating axis of symmetry (Sn) : If an orientation indistinguishable from the original is obtained,
when molecule is rotated Q degree around an axis passing through the molecule and the rotated molecule is
reflected in a mirror that is perpendicular to the axis of rotation. This type of axis is also known as improper
axis
180 º
 
rotation
here Q = 180°, so S2 is present.
EXERCISE - 1
PART - I
A-1. Restricted rotation present in all the options but geometircal isomersim shown by ii, iii, iv, vii.
A-2. Essential conditions for geometrical isomerism are
(1) Restricted rotation must present
(2) Two different groups must be present on both respicted atoms.
(3) Groups responsible to show geometrical isomerism must be nearly in the same plane.
A-3. (ii) and (iv) A-4. (ii) (iii) & (iv)
B-1. (iii), (ii), (ii), (viii) B-2. 3 (oct-2-ene, oct-3-ene, oct-4-ene)

B-3. CH3–HC=CH–CH2–CH=CH–COOH
(i) Five carbon atoms are sp2 hybridised (ii) Four geometrical isomers are possible
(iii)
B-4. (ii, iii, iv, v ) C-1. (i) = E (ii) = E (iii) = E (iv) = Z
C-2. (a)
dipole moment : II > I

(b) Because of good packing of trans isomers.
(c)
Cis has higher boiling point due to more polarity.
D-1. W has 3, X has zero, Y has 2 and Z has only one chiral centres.
D-2. (i) =9 (ii) =8

D-3._ (I) R (II) S (III) R (IV) (R, R)
D-4._ (I) D (II) (2D, 3D)
(III) Equivalent fischer projection is and configuration L.
(IV) Equivalent fischer projection is and configuration (2D, 3L).
E-1._ (i) Plane of symmetry and Centre of symmetry. (ii) Plane of symmetry.
(iii) Plane of symmetry. (iv) Plane of symmetry.
(v) Plane of symmetry and Centre of symmetry. (vi) Centre of symmetry.
F-1._ (I) Enantiomers (II) Position isomers (III) Identical (IV) Diastereomers
* *
CH3 – C H – CH  CH – CH3
G-1._ (I) |
OH
Number of stereocentres = 2 so total number of stereoisomers = 22 = 4
(II) All 4 isomers are optically active.
(III) Total enantiomeric pairs are 2, hence number of fraction will be 2.
Me H
G-2. Total=7 H Me
H-1. D/L represent nomenclature (relative configuration) while d/l represents direction of optical rotation.
H-2. Specific rotation is the number of degrees of rotation observed if a 1-dm (10-cm) tube is used and the
compound has concentration 1 gm/mL. Thus specific rotation [] is

[]t =
 C
[] = Specific rotation ;  = observed angle of rotation (degree)
l = Pathlength (dm) ; C = concentration (gm/ml)
 = wavelength (nm) ; t = temperature (25°C)
observed optical rotation
H-3. % Optical purity = optical rotation of pure enantiomer × 100
| d  | excess of one enantiomer over other

% Enantiomeric excess = × 100 = entire mixture × 100
d
I-1. 4 J-1. i, ii, iii, iv, vi
CH3
H H
K-1. antiform, it is most polar & stable. L-1. Fully Eclipsed
H H
NO2

L-2. L-3. 4
CHO intramolecular
H H-bonding
CH2CH2CH=O H O
M-1. ;
OH H H
H
PART - II
A-1. (C) A-2*. (A,B,D) A-3. (D) A-4. (D) A-5. (A)
A-6. (D) B-1. (B) B-2. (B) B-3. (B) B-4. (B)
B-5. (B) B-6. (D) C-1. (A) C-2. (D) C-3. (D)
C-4. (C) C-5. (D) D-1. (B) D-2. (B) D-3. (C)
D-4. (C) D-5. (B) D-6. (A) D-7. (A) D-8. (A)
D-9. (D) E-1. (D) E-2. (C) E-3. (B) E-4. (D)
E-5 . (B) E-6. (B) E-7. (A) E-8. (B) F-1. (D)
F-2. (D) F-3. (A) F-4. (D) F-5. (A) F-6. (B)
F-7. (B) F-8. (B) G-1. (B) G-2. (A) G-3. (A)
G-4. (C) G-5. (D) H-1. (D) H-2. (B) H-3. (B)
H-4. (C) I-1. (A) I-2. (A) I-3. (D) J-1*. (C,D)
J-2. (D) J-3. (A) J-4. (A) J-5. (A) J-6. (B)
J-7. (C) K-1.* (A,B,C,D) K-2. (A) K-3. (A) K-4. (D)
K-5. (C) L-1. (A) L-2. (B) L-3. (C) L-4. (A)
L-5. (D) M-1. (C) M-2. (C) M-3. (B) M-4. (B)
M-5. (C)
PART - III
1. (A) 2. (E) 3. (A) 4. (E)
EXERCISE - 2
PART-I
1. Stereoisomerism : Compounds which have same connectivity but different orientation of atoms or groups
in the space. Stereoisomers classified into Configurational isomers & Conformational isomers.
Configurational isomers : They are non interconvertible into each other at room temperature and can be
isolable/resolvable.
Conformational isomers : They are interconvertible into each other at room temperature and can not be
isolable/resolvable.
2. 4 (CH3–CH=CH–CH3)
3. The bond across which atoms cannot rotate with out breaking the bonds is called restricted rotation. e.g.
C=C, C=N, ring etc. (a  b, d  e)

4._ Only .and . 5.
NH OH
6. Ph–CH=CH–CH=O 2
Ph–CH=CH–CH=N–OH
Total geometrical centers = 2. So total geometrical isomers = 22 = 4
7. The number of geometrical isomers is four
(I) (II)
(III) (IV)
8. (i) 3 (ii) 16 (iii) 2 (iv) 3 (v) 4
9. (i) (ii)
(iii) (iv)
10. 0
11. (1) (2) (3)
12. 3, 4
13. (a) (3S) 3-amino pentanoic acid (b) (3S, 4S) 3, 4-dihydroxy hexanoic acid
14. RRRR
15. (i) POS present and COS, AOS absent. (ii) POS present and COS, AOS absent.
(iii) POS, AOS present and COS absent. (iv) POS, COS present and AOS absent.
(v) POS present and COS, AOS absent. (vi) POS present and COS,AOS absent.
(vii) POS present and COS, AOS absent. (viii) POS, COS and AOS absent.
(xi) POS, COS absent and AOS present.
Compound has a single chiral centre which has no plane of symmetry..
16. (i) Mixture of I, II and III give two fraction on fractional distillation. (ii) I, II and III all are optically active
(iii) I and II are pair of enantiomers (iv) I and III are optical diastereomer.
17.
18. (a) 79 unit (b) 0 (c) – 79 unit

19. (a) functional isomers (b) Identical (c) Geometrical isomers (d) Diastereomers
20._ (I) (II) (III)
21. Newmann Sawhorse

COOH
H OH
(A)
HO H
COOH
CH3
H OH
(B) H OH
CH3
B is optically active
22._ (i) (II) (iii)
(iv) (v) (vi)
23. First is more stable because of less steric repulsion between groups at equitorial position.
PART-II
1. (D) 2. (A) 3. (B) 4. (B) 5. (D)
6. (B) 7. (D) 8. (C) 9. (A) 10. (D)
11. (D) 12. (D) 13. (B) 14. (C) 15. (C)
16. (C) 17. (B) 18. (B) 19. (B) 20. (B)
21. (C) 22. (B) 23. (B) 24. (B) 25. (C)
26. (B) 27. (D) 28. (A,C) 29. (B,D) 30. (B,C,D)
31. (B,C) 32. (C,D) 33. (A,C) 34. (C,D) 35. (A,C)
36. (A,B,C,D) 37. (A,C) 38. (A,C,D) 39. (B,C,D) 40. (C,D)
41. (A,B,C) 42. (A,D)

PART-III
1. (A - p,s) ; (B - p,s) ; (C - p,s) ; (D - q,r) 2. (A - q,s) ; (B - t) ; (C - p,r,s) ; (D - t)
3. (A - p,q, s) ; (B - p,q,s) ; (C - r,s,t) ; (D - p,q, s) 4. (A - r) ; (B - q, r) ; (C - p, s) ; (D - s)
PART-IV
1. Given compound contains phenolic functional group, where as (A) and (B) option have alcoholic functional
group and C is ether.
2. CH3 – CH = CH
22 = 4
3. The no. of chiral carbon atom
CH3 – CH = CH =2
Total stereocentres = 3, so that stereoisomers = 23 = 8
EXERCISE - 3
PART - I
1. (A)
2. +
3. Least stable staggered form of n–butane is
This is due to Vander Waal’s strain developed between the methyl groups at C2 & C3. There is no torsional
strain in the staggered form at torsional angle 60º .

5.
obs = 1D xgauche = 0.18

1
 obs = ixi  1 = gauche × 0.18 + 0.82 × 0  gauche = 0 .18 = 5.55 D
meso
(a) If Y is CH3 , the Newman projection is
(b) If Y is OH, the Newman projection is
6. (C) 7.* (A,D) 8.* (A,D) 9. 7 10.* (B,D)
11.* (B,C) 12. (A) 13. 8 14.* (A,B,C)
PART - II
1. (D) 2. (C) 3. (B) 4. (B) 5. (C)
6. (A) 7. (B) 8. (C) 9. (C) 10. (C)
11. (A) 12. (B) 13. (B) 14. (C)
PART - III
1. If the subtance rotates the plane of polarized light, it is said to be opticallly active subtance.
If rotation of plane is clockwise, the substance is dextrorotatory (d).
If rotation of plane is counter clockwise, the substance is levorotatory (l).
2. A sp3 hybridized carbon attached with four different nature of atoms or groups is called chiral carbon .
3. Enantiomers : Compounds which are non-super imposable mirror image of each other are called enantiomers.
Pair of enantiomers
Diastereomers : Stereoisomers which are non mirror image of each other are called diastereomers.
4. Substance that is non-super imposable on its mirror image is chiral and this property is known as chirality.
Ex. hand, shoes, glyceraldehyde, glucose, lactic acid etc.

5. * *
CH 3–CHOH–CHCl–COOH
Total chiral carbon = 2, total stereoisomers = 22 = 4.
6. Anti (staggared) conformation is stable
Cl
H H
H H
Cl
Cl H
C=C H
H C=C
7. H Cl
Trans Trans
8. Ends are different. Thus the no of geometrical isomers are = 2n. = 22 = 4

9. (i) The given two compounds are geometrical isomers as the relative orientations of their atoms or groups
in space are different.
(ii) The given two compounds are structural isomers as they have different structures.
10. A compound which is non-superimposable to its mirror image is called chiral while a compound which is
superimposable to its mirror image is called achiral. All dissymmetric (or asymmetric) compounds are
chiral.
*
Example: 2-chlorobutane CH3  C H  C 2H5
|
Cl
b
C2H5
a
CH3
Cl – C
H
II


1. The number of isomers for the compound with molecular formula C2BrClFI is : [IIT-JEE-2K(S), 1/35]
(A) 3 (B) 4 (C) 5 (D) 6
2. Which of the following will show geometrical isomerism.
(A) (B)
(C) (D)
3. Which of them will not show geometrical isomerism.
CH3
CH3
(A) (B) C
H
CH3
(C) (D)
4. Which of them will not show geometrical isomerism.
(A) (B)
(C) (D)
5. In which option the configurational naming is not correctly mached with the respective structure.
(A) (2E, 4E) (B) (2Z, 4E)
(C) (2E, 3Z) (D) (2E, 4E)

6. Write all carbonyl compounds with molecular formula C3H6O and then on reaction with excess of NH2OH.
How many total isomeric oximes are formed.
(A) 2 (B) 3 (C) 4 (D)6
7. Which of the following compounds exhibits stereoisomerism ? [IIT-JEE-2002(S), 3/90]

(A) 2-methylbutene-1 (B) 3-methylbutyne-1
(C) 3-methylbutanoic acid (D) 2-methylbutanoic acid
8. Chiral centres present in the given structures will be :
(i) (ii)
(A) 5 & 9 (B) 6 & 8 (C) 4 & 3 (D) 4 & 7
9. Which of the following molecule is chiral.
Cl
Cl H H
Cl Cl Cl Cl
H H
(A) (B) H (C) (D)
Br
H H Cl Cl Cl
Br
10.
Which of the following statement is incorrect for the above compounds ?

(A) the compound I possesses an axis of symmetry.
(B) the compound II possesses a centre of symmetry.
(C) compound I and II both are optically active and enantiomers of each other.
(D) Diastereomers of both compounds are identical and meso.
11. The chiral molecules are :
H Br
(1) (2) (3)
Br H
(A) 1, 2 (B) 2 ,3 (C) 1 , 3 (D) 1, 2 ,3

12. Which of the following is chiral ?
(A) (B)
(C) (D)
13. In which of the following spatial representation of group/atoms is different from the given strucuture P.
Cl
P = H3C
H
D
Cl
CH3 CH3 D CH3
D CH3
(A) Cl (B) D (C) (D)
D H Cl
H H
H Cl
H
OH
C2H5 C
14. H C
OH
CH3
Fischer projection formula of this compound can be represented as :
(A) (B) (C) (D)
15. How many structures of hydroxycarboxylic acid (molecular formula C4H8O3) can show optical actvity?
(A) 1 (B) 2 (C) 3 (D) 4
16. The total number of isomeric (including stereo) Bromo-chloro-fluoro-iodopropadienes is :
(A) 2 (B) 4 (C) 6 (D) 12
17. The sum of total stereoisomers and fractions on the fractional distillation of 2, 3- Dichloropentane is.
(A) 5 (B) 8 (C) 6 (D) 10
18. Which points on the potential energy diagram

represent the eclipsed conformation of ethane and
staggered conformation of propane respectively ?
(A) P, R
(B) Q, R
(C) S, P
(D) R, Q

19*. Amongst the given options, the compound(s) in which all the atoms are in one plane in all the possible
conformations (if any), is (are) :
(A) (B)
(C) (D)
20. Identify the structure in which all the OH groups at equitorial positions.
OH
OH HO O
HO O HO
HO
(A) -(D)-glucose (B) -(D)-glucose
OH OH
OH
OH
OH
OH CH2OH OH
O CH2OH
O
(C) -(D)-Idose (D) HO -(D)-galactose
OH
OH OH
OH

1. Explain the following :
does not show geometrical isomerism.
2. Observe the fischer projection of Tartaric acid and comment on plane of symmetry, centre of symmetry, axis
of symmetry and optical activity for the given structure.
3. Find R/S configuration of following compounds.
(I) (III)
(III) (IV)

4. Chlorination of (R)-2-chlorobutane yields a mixture of dichloro isomers with the molecular formula
C4H8Cl2.
(i) The total number of isomers formed is x.
(ii) The total number of fractions obtained after fractional distillation of product mixture is y.
(iii) The number of optically active isomers is z.
Identify x, y and z
5. For the given molecular formula C3H4FClO2, find out the following :
(i) Number of structural isomers of carboxylic acids = (X).
(ii) Number of optically active carboxylic acids = (Y).
(iii) Number of fractions obtained on distillation of mixture of all isomeric acids = (Z).
(iv) Number of acids having 2 chiral C* atoms = (W).
Report your answer as follows :
6. Various isomeric alkynes have molecular formula C3FClBrI. For such alkynes if
p = Number of positional isomers
q = Number of optically active isomers
r = Number of fractions obtained on fractional distillation of a mixture of all possible alkynes
s = Number of diastereomeric pairs
then report your answer as :
7. An organic compound P exists in two enantiomeric forms, which have specific optical rotation values [] = ±
100°. The optical rotation of a mixture of these two enantiomers is – 50°. Calculate the percentage of that
enantiomer which is in lower concentration in the mixture.
8. Draw the stereoisomers of following compound by writing correct stereochemical formula

Cl  CH  CH  CH  CH  CH  Cl
|
Cl
CHO CH2OH
CHOH CHOH
9. H2 / Ni

CHOH CHOH
CHOH CHOH
CH2OH CH2OH
(All possible (Products)
optical isomers)
How many optical isomers of reactant convert into products as meso isomers.
10. Identify the pairs of enantiomers and diastereomers from the following compounds I, II and III :
[IIT-JEE-2K(M), 2/100]
(I) (II) (III)
11. Write down the C2–C3 bond, and draw Newman projection formula for the most stable conformation of
2,2–dimethylbutane

12. Identify the relation between molecules given in Newman and Fischer projections.
13. Which of the following has/have potential energy diagram for conformations closely resembling to ethane.
(I) 2,2-Dimethylpropane (II) 2,3-Dimethylbutane
(III) 2,2,3-Trimethylbutane (IV) 2,2-Dimethylbutane
14. For the compound A – CH2 – CH2 – A draw the newman projection formula of all the stable conformational
isomers if obs = 2D and Xanti = 0.75 then find  gauche .(If A = NO2)
15. How many total cyclic isomers with molecular formula C3H3Cl2Br are possible.
16. Which of the following combination of axial & equitorial bonds show Cis or trans orientation in 1,2-dimethyl
cyclohexane.
(i) 1e, 2e (ii) 1e, 3e (iii) 1e, 4e (iv) 1e, 2a (v) 1e, 3a (vi) 1e, 4a (vii) 1a, 3a

PART - I
1. (D) 2. (B) 3. (D) 4. (A) 5. (C)
6. (B) 7. (D) 8. (A) 9. (D) 10. (B)
11. (D) 12. (C) 13. (D) 14. (A) 15. (C)
16. (C) 17. (C) 18. (C) 19*. (B) 20. (A)
PART - II
3. (I) S (II) R (III) R (IV) R
4. x = 5, y = 5, z = 3 5.
6. 9. 4
10. Enantiomeric pair  (I & III)

 (I & II), (II & III)
11.
12. I and III are identical, II and IV are enantiomers, I & IV and II & III are diastereomers.
13. I, III, IV 14.  gauche = 8 Debye 15. 10
16. (i) trans (ii) cis (iii) trans (iv) cis (v) trans (vi) cis (vii) cis

STEREOISOMERISM
EXERCISE # 1
PART - I
CH3 CH3 CH3 CH3
I-1. R–COOH + H OH + H OH  H OCOR + H OCOR

(±)
D C2H5 D C2H5
2-Diastereomer 2-Diastereomer
PART - II
A-1. Stereoisomers have same connectivity of atoms but different orientations (configurations) in space.
A-3. Follow conditions of geometrical isomerism.
B-1. Unsymmetrical compound with 2 stereocentres has 4 geometrical isomers (22 = 4).
B-2. Unsymmetrical compound with 2 stereocentres has 4 geometrical isomers.
B-3. Unsymmetrical compound with 2 stereocentres has 4 geometrical isomers.
B-4. Number of geometical centres (n) = 4. So, total G.I. = 24 = 16
B-5. (I) +
(II) + H2NOH
(III)
(IV) +
B-6. Since total two products are formed hence both carbonyl should be symmetrical.
C-1. (Z) -2-pentene
[Senior groups at same side of restricted rotation]

C-2. E-isomers have senior groups on anti-orientation.
C-3. trans-3-chloro-1-phenyl but-1-ene.
* * *
D-2. CH3 – C H – CH2 – C H – C H – CH3 has three chiral carbons.
| | |
OH Br C 2H5
D-3. Four chiral carbon atoms
D-4. the arrow is clockwise but least priority group is on horizontal line of fischer projection.
D-5. R.
D-6. First decide the (R/S) configuration in wedge-dash and then draw fischer projection for same configuration.
D-9. (D-Configuration)
E-4. C1 axis of symmetry is always present in all the molecules.
E-5 . which axis of symmetry exists along the given axis.
E-6. In meso compound C2 axis of symmetry is generally absent.
E-8. (A) Plane of symmetry; (B) C2 axis symmetry; (C) Centre of symmetry ; (D) Plane of symmetry

F-3.
non-super imposible mirror image stereoisomers.

F-6. Meso compound has atleast 2-chiral carbon.
G-1. Unsymmetrical compound with 2 chiral centres has 22 = 4 stereoisomers.
G-2. Number of optically active stereoisomers of tartaric acid = 2.
G-5. C6H12O
D.U. = 1
 Total no. of ketones = 7

H-2. (B) +12 unit Since specific rotation [] is independent of l, C.
H-3.
Excess of one enantiomer over other 6–4

H-4. % Enantiomeric excess = × 100 = × 100 = 20%
Entire mixture 64
[ ] observed [] observed

% optical purity = [ ] pure × 100  20 = × 100  [] observed = + 2.7
13 .5
I-1. + two diastereomeric esters

+ two diastereomeric amides
(–) –2–chlorobutanoicacid
Racemic mixture can be resolved by using optically active compounds.
I-2.
Since carbocation does not form any chiral carbon in this reactions hence racemic mixture can not form.
I-3. Enatiomers have same physical properties so they can not be separated by any physical method which
diastereomers have different physical properties.
J-1*. and are chiral and optically active.
*
J-2. CH3 – CH – CH2 – CH3 has chiral carbon.
|
NH2
J-4. chirality
J-5. Number of optically active stereoisomers = 2.
J-6. Have 8 spatial orientation due to chiral C, bond & along 2, 2, 6, 6 biphenyl.
J-7. Total no. of stereocentres (n) = 4

Total no. of optical isomers = 2n = 24 = 16
K-1.*
K-2. The eclipsed and staggered conformation of ethane is due to free rotation about C — C single bond.
K-4. Deviation in normal bond angles increases the angle strain. In cyclopropane deviation in bond angle is
maximum.

L-1. Anti form of butane is more stable because of less strains.
L-3. Cl – CH2 – CH2 – Cl has two staggered conformations.
Only Gauche form is polar. Anti form is nonpolar.

L-4. (A) is meso form so it is achiral molecule

L-5. X = Hydrogen
M-1.
Although steric repulsion exist but hydrogen bonding as shown above, gives stability to the gauche form.
M-2. Gauche form of butane-2,3-diol has intramolecular H-bonding. So it is most stable.
M-6. Both are meso compounds (achiral) and identical with its mirror image.
PART - III
1. The boiling point of Cis–1,2–dichloroethene is higher than corresponding trans-isomer because dipole
moment of cis isomer is higher than trans.
3. Meso tartaric acid is optically inactive and it has plane of symmetry.
EXERCISE - 2
8. Symmetrical compound with 2 stereocentres has 3 stereoisomers. [2n – 1 + 2(n – 2)/2]
17. M has following orientations
Total geometrical orientations = 3

d–
18. Enantiomeric excess =
d
[]observed
Optical purity =
[]pure
158  50
(a) 50% (+) mandelic acid [] = = 79 unit
100
(b) Racemic mixture, so [] = 0
158  50
(c) 50% (–) mandelic acid [] = = – 79 unit
100
PART-II
1. Follow conditions of geometrical isomerism.

2. I and II have different positions of -bond, these are positional isomers. Similarly II and III are also positional
isomers.
I and III are geometrical isomers.
3. Unsymmetrical compound with 2 stereocentres has 4 geometrical isomers.
n 1
4. Geometrical isomers for symmetrical compounds = 2 n–1
+ 2 2
n = 3, total G.I. = 6
8.
CH3
9. Both are identical species H3C CH Cl in A, there is no asymmetric 'C' atom present.
B, C, D have pairs of compounds which have chiral carbon and are non superimposible on each other.
10. When –OH is present at right side of horizontal line & high priority at the top than it is consider as D & if left
side then L.
11. 
Option D is identical with newman projection (both are meso).
14. This structure has plane of symmetry across 1-3 but there is no centre of symmetry..

15. Compound which has chiral carbon can show enantiomerism.
16. 180 º 
 

18. There are two stereocentres in the compound, so total stereoisomers = 22 = 4.

All 4 will be optically active.
19. There are five stereocentres in the compound total stereoisomers = 25–1 = 31.
20. Number of D stereoisomers = 4.
21. 2, 2`6, 6` tetra substituted biphenyls are optically active
23. Number of optically active stereoisomers = 4 and total stereoisomers = 6.

24. The repultion felt by the bonding electrons of one substituent as they pass close to the bonding electrons of
another substituent is called torsional strain.
26. Anti conformation is stable & polarity is present in one direction.
28*. Follow conditions of geometrical isomerism.
31. ,
Total no. isomers are 3.

C is sp2 hybridised in each isomer, therefore geometry is trigonal planar.
33. I and II are geometrical isomers. II has intramolecular H-bonding, it is non polar.
37.  
38. In B chiral carbon is not present.

40. (I) and (II) are enantiomers

PART - IV
1. Given compound contains phenolic functional group, where as (A) and (B) option have alcoholic functional
group and C is ether.
2. CH3 – CH = CH
22 = 4
3. The no. of chiral carbon atom
CH3 – CH = CH =2
Total stereocentres = 3, so that stereoisomers = 23 = 8
EXERCISE - 3
PART - I
1. When optically active acid reacts with racemic mixture of an alcohol, it forms two types of isomeric esters.
In each the configuration of the chiral centre of acid will remain the same. So the mixture will be optically
active.
2. +
3. Least stable staggered form of n–butane is
This is due to Vander Waal’s strain developed between the methyl groups at C2 & C3. There is no torsional
strain in the staggered form at torsional angle 60º .

5.
obs = 1D xgauche = 0.18

1
 obs = ixi  1 = gauche × 0.18 + 0.82 × 0  gauche = 0 .18 = 5.55 D
meso
(a) If Y is CH3 , the Newman projection is
(b) If Y is OH, the Newman projection is
8.* (X) has configurations

(1) R Z R (2) S Z S (3) R Z S (4) R E R (5) S E S (6) R E S
9.
CH3 CH3
| |
10.*  CH3 – C – CH2 – CH3 ,  CH3 – C – C 2H5
| |
CH3 CH3
11. In (B) and (C) CH2 == C == O all atoms are always in same plane.
O3 / Zn / H2O
12.   2CH3–CHO + 2CH3  CH  CHO

|
CHO
All optically inactive products

13.
Total stereoisomers = 23 = 8
14.
PART - II
1. An equimolar mixture of two i.e., dextro and laevorotatory optical isomers is termed as racemic mixture or
dl form or (±) mixture.
2. Cl2–C=CH–CH2–CH2–CH3
Identical groups (CI) on C - I will give only one compound.
3. A chiral object or compound can be defined as the one that is not superimposable on its mirror image, or
we can say that all the four groups attached to a carbon atom must be different. only I and II are chiral
compounds.
CH3 CH3
| |
(I) C2H5 – C – C3H7 (II) CH3CO – C – C2H5
| |
H H
4.
2,3-dichlorobutane have meso isomer due to the presence of plane of symmetry.

5. Optically active due to presence of chiral carbon atom .
6. To be optically active the compound or structure should possess chiral or asymmetric centre but in the
rest of the structure it is present.
7. Due to presence of two asymmetric carbon atoms in 2, 3-dichlorobutane,
it exhibits optical isomerism.
8. CH 2– CH 2
F OH
2-fluoroethanol
Gauche form is more stable due to intramolecular H-bonding
9.
Due to the presence of chiral carbon atom it is optically active, hence it is expected to rotate plane of
polarized light.

10. The twist boat conformation of cyclohexane is optically active as it does not have any plane of symmetry
11. According to CIP rule first decide the seniority of groups and than decide the configuration.
12. CH3–CH=CH–CH3
2-butene
13. Total possible isomers are four..
cis – R
trans – R
cis – S
trans – S
14.
It is optical active since it has chiral carbon atom.
PART - I
1. Molecule C2BrClFI shows geometrical isomerism as E & Z-isomers.
=2
=2
=2
Hence total isomers are six.
2.
It has two C = C bonds which can exhibit geometrical isomerism.

5. (C) 1E, 3Z

O O
|| || NH2OH
6. CH3  C  CH3 + H  C  C2H5    +
7.
8. (i) (5 chiral Carbon) (ii) (9 chiral Carbon)
Tetracycline
9. These molecules except D have at least one plane of symmetry. So these are symmetric achiral molecules.
11. All compounds 1,2,3 are dissymmetric and chiral.
12. (A) plane of symmetry so it is achiral
(B) plane of symmetry so it is achiral
(C) optical active because both phenyl rings in the perpendicular plane.
(D) plane of symmetry so it is achiral
15. (1) (2) (3)
Br F Cl F Cl F
16. C=C=C ; C=C=C ; C=C=C
 Cl  Br Br 
(±) (±) (±)
Fractional
17. + + +     Fraction (I+II) + fraction (III + IV).
Distillation 1 2
(I) (II) (III) (IV)

18. Propane has more conformational energy as compare to ethane. Eclipsed conformation of ethane has more
Vander waal strain and torsional strain so it lies upper side in the P.E. diagram and staggered conformation
of propane has less Vander waal strain and torsional strain so it lies lower side in P.E. diagram.
19*. Due to SIR effect of Bromine COO– group of benzoate ion goes out of the plane.
PART - II
1. The compound is non planar and the groups at the terminal ends of allene are in perpendicular planes. The
distance between groups at the terminal ends does not change in any other structure. Therefore different
relative orientations are not possible.
2. It has plane of symmetry so compound is meso, hence optically inactive but centre of symmetry and axis of
symmetry are absent.
Cl
CH2  CH2  CH  CH3 |
4. Cl2 ,h + CH3  CH2  C  CH3 ,
CH3  CH2  CH  CH3    | |
| Cl Cl |
(R ) Cl
Cl
CH3 CH3
H Cl Cl H
CH3  CH2  CH  CH2 H Cl
| | H Cl
+ (S ) Cl Cl + + CH3
CH3
(R,S) meso (R,R)
5. M.F. = C3H4FClO2
D.U. = 1 (Saturated, acylic acids)
X=4 Y=8
Z=4 W=0
6. All alkyne isomers of M.F. C3FClBrI are
(I) (II) (III) (IV)
Number of positional isomers (I, II, III, IV) = 4

Number of all optically active isomers = 8
Number of fractions obtained on fractional distillation = 4
No diastereomers possible with one asymmetric C* atom.
observed rotation 50

7. Enatiomeirc excess = specific rotation of pure enantiomer = × 100 = 50%
– 100
% of laevorotatory isomer = 50 + 25%
% of dextrorotatory isomer = 25% Ans. 25%

8.
or
CHO CHO
H OH H OH
H OH and HO H
9. will form meso products.
H OH HO H
H OH H OH
CH2OH CH2OH
(±) (±)
2 2
P.E.
13. All have the P.E. diagram like
Dihedral angle
14.
The following values are given in the Question : obs = 2D, Xanti = 0.75, so Xgauche = 1– 0.75 = 0.25
By using the formule obs =  X i i
obs = gauche × Xgauche + anti × Xanti
2 = gauche × 0.25 + 0.75 × 0

2
gauche = = 8D
0.25
Cl Cl H
Cl Br Cl Cl Cl H
Cl H Br Cl H H Cl Cl Br
15.
Cl H Br H Br Cl
H H H Br H H

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Chemistry Booklet No 4 Engineering

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CHEMISTRY

IUPAC NOMENCLATURE &

KEY CONCEPTS (b) C + O2 Room

1. Introduction (c) CO + 2H2 Room

The branch of physical chemistry which deals

t concentration at time t2 & t1 respectively

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So rate constant is defined as rate of reaction 4.2 Units of rate constant :

Note :– Above factors will be discussed after

4.3 Difference between rate of reaction and rate

Rate of reaction Reaction rate constant

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6.1 Pseudo unimolecular reactions : 1  1 1 

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(ii) 2HI gold

[hetrogeneous A reaction is called first order if its rate is

(v) Enzyme catalyzed reactions (i) H2O2  H2O + ½O2

dx 7.3.3 Half life (t½) :

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(a) (a) 2A 

7.6 First order growth reaction :

(iii) If v0, vt or v is not given directly rt = angle of rotation at t = 't'

Ptotal = P0 – P´ + P´ + 2P´ time

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8.4 Vant Hoff's differential method : collision. For a collision to be effective

From the given diagram we can

(b) Physical size of reactants – As we

Arrhenious suggested an equation k1

where 11.2 Successive reactions :

Ea = activation energy Consider A converted into B according

(a) Presence of positive catalyst lower down

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TEST YOUR UNDERSTANDING

[ R]1 103 [ R]2 103 t2 t1 rav 103  [ R2  R1 ] 103

(b)If C is very-very low 1 + K 2 C  K

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It has the units of a second order reaction.

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Ex.8 The reaction : CH3COF + H2O CH3COOH + HF

Sol. Let rate = k (cCH 3COF ) a (cH 2O )b

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a V and x Vt

where V is the number of ml of potassium permagnate required to react with a

Ex.12 Conversion of N–chloro acetanilide into p–chloroacetanilide

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Ex.13 Study of acid hydrolysis of an ester.

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Equation (i) – (ii).

Sol. H = Eaf – Eab > 0 (for endothermic)

3.1761 2.303  2  523  423

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E = 5.4 × 10 3 × 2.303 × 1.987 = 24.624 cal mol – 1

Ex.22 Calculate rate law

Ex-23 2O3  3O2

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Sol. r = k3 [Br–] [H2NO2+]