PHYSICAL CHEMISTRY

CLASS-XII

CHEMICAL KINETICS

" A SPECIALLY DESIGNED KIT FOR LEARNING."

THE KEY  Basic principles of subjects. An outline of the topics to be
discussed in class lectures.
THE ATLAS  Basic layout of subject. A route map correlating different
subtopics in coherent manner.
GLOSSARY  A list of important terms in brief
SHORT NOTES  Important Formula
EXERCISE I  Introductory problems based on JEE to get first hand
experience of problem solving.
EXERCISE II  A collection of good problems.
QUESTION BANK  Test your objective skill.
EXERCISE III  A collection of previous 15 years JEE problems.
 THE KEY
CHEMICAL KINETICS :
It is a branch of physical chemistry which deals with the "Rate of Chemical Reactions" including the effect of
temperature, pressure, concentration, etc., on the rates, and the mechanism by which the reaction takes place.

RATE OF CHEMICAL REACTION is defined as the change in concentration of a reactant (or a product) in a particular
time interval. Type of rate of reaction (i) Average (ii) Instantaneous

Average rate. The rate of reaction measured over a long time interval is called average rate of reaction. It is
equal to x/t as shown in fig.(a) and (b).

Instantaneous and average rate of reaction

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 as shown in fig. (a) and (b).

Rate law Expression :

For a general reaction : aA + bB  cC + dD,

d[A]
The rate of disappearance of A = –
dt

d[B]
Rate of disappearance of B = –
dt

d[C]
Rate of appearance of C =
dt

d[D]
Rate of appearance of D = .
dt

The positive sign shows that concentrations of C and D increases with time and the negative sign indicating
that concentrations of A and B decrease with time.Thus the rate of general reaction.

1 d[A] 1 d[B] 1 d[C] 1 d[D]

Rate of reaction : – =– = = .
a dt b dt c dt d dt

Unit of Reaction Rate are unit of concentration divided by the unit of time
(mol L–1s–1 or mol L–1min–1 or so on).

[2]
FACTORS AFFECTING REACTION RATES :
(i) Nature of reactants and products.
(ii) Concentration
(iii) Catalyst
(iv) Reaction temperature

Besides these, pressure of gaseous reactants and surface area (if a reactant or a catalyst is a solid)
exposure to radiation, nature of solvent also affect the reaction rates.

RATE LAW AND RATE CONSTANT :

An expression which relates the rate of a reaction to the concentration of the reactants is called the Rate
Equation or Rate Law. Rate  [A]m · [B]n or Rate = k [A]m [B]n. The constant of proportionality, k is known as
the Rate Constant (specific reaction rate) and may be defined as the rate at unit concentrations of the reactants.
k depends on the temperature and is independent of the initial concentrations of the reactants. At a fixed
temperature, k is constant characteristic of the reaction. Larger value of k indicates fast reaction and small k
indicates slow reactions.

MOLECULARITY :
Molecularity of a reaction is defined as the numbers of particles (atoms, ions, molecules) of reactants
actually taking part in a single step chemical reaction.

Molecularity of a reaction is :
(i) Always a whole number (not zero) and never a fraction or negative.
(ii) The value of molecularity of a simple or one step reaction does not exceed 3.

ORDER OF REACTION :
It is defined as the sum of the exponents (powers) of the molar concentrations of the reactants in the
experimentally determined rate equations.
If rate of reaction  [A]p [B]q [C]r or Rate of reaction = k [A]p [B]q [C]r
order of reaction = p + q + r & the order w.r.t. A, B & C are p, q & r respectively.
For a "Reaction of nth order", the order of the reaction is n and the rate equation (or Rate law) is
rate  [A]n = k [A]n.
The order of a reaction is obtained from the experimentally determined rate and may be zero, an integer or a
fraction. In a multi-step complex reaction, the order of the reaction depends on the slowest step.

ZERO ORDER REACTION :

A reaction is said to be of zero order if the rate is independent of the concentration of the reactants.
A  products
Rate = k [A]° = k mol L–1 s–1

EXAMPLES :

h hot Pt. 1
(i) H2(g) + Cl2 (g)  2HCl (g) (ii) N2O(g) 
 N2 (g) + O (g)
Surface 2 2

Mo or W Au
(iii) 2NH3 (g)  N2 + 3H2 (iv) 2HI (g) 
 H2 (g) + I2 (g)
surface surface

[3]
CHARACTERISTICS OF ZERO ORDER REACTION :
(1) Concentration of reactant decreases lineraly with time. [A]t = [A]0 – kt.
(2) Unit of k is, mol –1 time–1.
[ A ]0
(3) Time required for the completion of reaction t100% =
k
0.5 [ A ] 0
(4) t1/2 =
k
FIRST ORDER REACTION :
A reaction is said to be of first order if its rate is proportional to the concentration of one reactant only.
A  Products.
at time t = 0 a (or C0) 0
at time t = t a – x (or Ct) x
Rate  [A]
Rate = k [A]
dx
or = k (a – x) (1 st order differential equation)
dt
2.303 a
Integrated first order rate equation is k = log .
t ax
kt
Exponential form of first order equation is Ct = C0 e
Characteristics of First Order Reaction :

(1) Unit of rate constant is time–1.

0.693 1
(2) t1/2 = ; Average life() = = 1.44 t1/2 ;
k k
k
(3) log (a – x) v/s t is a straight line with slope =  .
2.303

EXAMPLES :

(i) Radioactive disintegration is a first order reaction.

H catalysed hydrolysis
(ii) C12H22O11 + H2O        
 C6H12O6 + C6H12O6.
Inversion
(glucose) (fructose)
(iii) Mineral acid catalyzed hydrolysis of esters.
(iv) Decomposition of H2O2 in aqueous solution.

SECOND ORDER REACTION :

(i) For the reaction : A products or for the reaction A + B  products.
dx
If differential rate equation is = k(a – x )2
dt
1 x
Integrated rate equation will be k= .
t a(a  x )

1 1
kt =  .
ax a

[4]
(ii) When the initial concentrations of the two reactants are different;
A + B  products
t=0 a b –
t a–x b–x x

dx
differential rate equation = k2 (a – x) (b – x).
dt

2.303 b(a  x )
Integrated rate equation k2 = log10
t(a  b) a(b  x )

CHARACTERISTICS OF SECOND ORDER REACTION :

(i) Unit of rate constant L mol–1 time –1.

(ii) Numerical value of k will depend upon unit of concentration.
(iii) t1/2  a–1 (In general t1/2  a(1–n); n = order of reactions).
(iv) 2nd order reaction becomes first order when one of the reactant in excess.

EXAMPLES :

(i) Saponification (hydrolysis of esters catalysed with alkali).

CH3COOC2H5 + NaOH  CH3COONa + C2H5OH

(ii) Hydrogenation of ethene C2H4+ H2 100

 C
 C2H6.
(iii)2 O3 
3 O2.
th
n ORDER REACTION.
A  Product

dx
If  k n [A]n
dt

1  1 1 
knt = n  1    [n  1]
 a  x n1 an1 

1  2n1  1
t1/2 = k (n  1) .  n1 
n  a 

t1/2

1/(a–x)n–1

1/an–1
n–1
t 1/a

METHODS OF DETERMINATION OF ORDER OF REACTIONS :

A few methods commonly used are given below :

1. Hit & Trial Method : It is method of using integrated rate equations, where the experimental values of a, x &
t are put into these equations. One which gives a constant value of k for different sets of a, x & t correspond
to the order of the reaction.

[5]
2. Graphical Method :
(i) A plot of log (a – x) versus 't' gives a straight lines for the First order reaction.
(ii) A plot of (a – x)– (n–1) versus 't' gives a straight line any reaction of the order n (except n = 1).
3. Half Life Method : The half life of nth order reactions is related with a0 as :

1
t1/2  .
an–1
0

By experimental observation of the dependence of half life on initial concentration we can determine n, the

log t 2  log t1
order of reaction. n = 1 + .
log a1  log a 2

4. Initial rate method. Initial rate method is used to determine the order or reaction in cases where more than
one reactant is used. It involves the determination of the order of different reactants separately. A series of
experiments are performed in which concentration of one particular reactant is varied whereas conc. of other
reactants are kept constant. In each experiment the initial rate is determined from the plot of conc. vs. time,
e.g., if conc. of A is doubled, and initial rate of reaction is also doubled, order of reaction is l.

CALCULATION OF FIRST ORDER RATE CONSTANT USING DIFFERENT PARAMETERS

(I) In terms of pressure

A(g)  B(g) + C(g)

2.303 P0
k= log
t 2P0 – PT

where
P0 = Initial partial pressure of A
PT = Total pressure of gaseous system at time 't'

(II) Decomposition of H2O2 in aqueous solution (In terms of volume of reagent KMnO4 required in
titration against H2O2).
H2O2  H2O + O2

2.303 V
k= log 0
t Vt

where
V0 = Volume of KMnO4 required in titration of H2O2 sample taken initially
Vt = Volume of KMnO4 required in titration of same volume of at H2O2 sample at time 't'.

(III) Acid catalysed hydrolysis of ester (In terms of volume of reagent NaOH required in titration)

H
CH3COOC2H5 + H2O 
 CH3COOH + C2H5OH
NaOH reacts with H+ and CH3COOH.

2.303  V – V0 
k= log   

t  V – Vt 

where
V0 = volume of NaOH required in titration when reacted with H+ (at start)
Vt = volume of NaOH required in titration when reacted with H+ and CH3COOH at time 't'.
V = volume of NaOH required in titration when reaction is completed

[6]
(IV) Inversion of cane sugar (In terms of angle of rotation)

H catalysed hydrolysis
C12H22O11 + H2O         C H O + C H O .
6 12 6 6 12 6
Inversion
(glucose) (fructose)

2.303 r –r 
k= log  0  

t  rt – r 
where
r0 = initial angle of rotation of the sample
rt = angle of rotation after time t
r = angle of rotation after completion of reaction

FIRST ORDER MISCELLANEOUS REACTIONS :

(i) Reversible reaction
kf
A B
kb

At time t = 0 a b
At time t = t a–x x
At time t = teq a – xeq xeq

1 
x eq 
(kf + kb) = n  x  x 
t  eq 

kf [B] x eq
At equilibrium Keq = k = = ax
b [A] eq

*(ii) Parallel or concurent reaction :

B
k1
A
k2
C

[A]0
(k1 + k2) t = n
[A]t

 (k  k )t
[A]t = [A]0 e 1 2
[A]0 = [A]t + [B]t + [C]t

k1[ A ]0
[B] = k  k (1  e(k1 k2 )t )
1 2

k1[ A ]0
[C] = k  k (1  e(k1 k2 )t )
1 2

[7]
 [B] k1

[C] k 2

k1
% of B = k  k × 100
1 2

k2
% of C = k  k × 100
1 2

THRESHOLD ENERGY AND ACTIVATION ENERGY :

For a reaction to take place the reacting molecules must colloid together, but only those collisions, in which
colliding molecules possess certain total minimum energy is called threshold energy (ET).

ACTIVATION ENERGY (Ea ) :

The extra energy needed for the reactant molecules to be able to react chemically is known as Activation
energy.
ET = Threshold energy
b
Ea = Activation energy of forward reaction
Eb= Activation energy of backward reaction
P1 = Potential energy of reactants
P2 = Potential energy of products

INFLUENCE OF TEMPERATURE ON REACTION RATES :

TEMPERATURE COEFFICIENT :
The temperature coefficient of a chemical reaction is defined as the ratio of the reaction rates at two temperatures
differing by 10°C.

k T 10
Temperature coefficient = k T . Its value usually lies between 2 & 3.

ARRHENIUS EQUATION :
A quantitative relationship was proposed by Arrhenius
k = A. e–Ea/RT
Where,
k = rate constant
A = frequency factor (or pre exponential factor);
R = gas constant
T = Temperature (Kelvin)
Ea =Activation energy.

k2 Ea  1 1
The Logarithmic expressions are log10    
k1 2.303R  T1 T2 

[8]
GRAPHICAL REPRESENTATIONS :

MECHANISM OF REACTIONS :

The path way which reactants are converted into the products is called the reaction mechanism. It should be
clear that experimentally determined rate expression cannot be predicted from the stoichiometry of the
reaction. For example for the reaction ;

NO2(g) + CO (g)  CO2(g) + NO(g), the rate expression is ; rate = k[NO2]2 ,

i.e. the expression has no dependence of CO (g) concentration.
The reason is that the reaction occurs by a series of elementary steps.
The sequence of elementary processes leading to the overall stoichiometry is known as the "Mechanism of
the reaction". In a sequence of reactions leading to the formation of products from reactants, the slowest
step is the rate determining step.
The mechanism proposed for the above reaction is a two step one.

NO2 + NO2  NO + NO3 (step 1 : slow)

NO3 + CO  CO2 + NO2 (step 2 : fast)

The sum of the two gives the stoichiometry & the slow step decided the rate expression.

[9]
 THE ATLAS

Some basic concept

1.Rate of reaction.
2.Rate of reaction in terms
of extent of reaction.
3.Average and instantaneous
rate of reaction.
4.Dependence of rate of reaction
on concentration, pressure,
temperature and catalyst.
5.Rate law expression.
6.Order and molecularity of reaction.

CHEMICAL
KINETICS

Experimental Theoretical
Aspects Aspects

1.Determination of order of reaction. 1. Temperature depedence

(a) Graphical method. of rate of reaction
(b) Initial rate method. 2. Collision theory of rate
(c) Oswald's isolation method. of reaction
(d) Half life method. 3. Transition state theory for
2. Differential and integerated rate of reaction
expressions for 4. Mechanism of reaction
(a) Zero order and steady state approximation
(b) First order
(c) nth order reaction
(d) t1/2 of a reaction.
(e) Rate constant expression in which
conc. terms is replaced by other
variables like pressure, volume of
reagent, absorbance etc..
(f) Branching Decay
(g) Consecutive or sequential Decay
(h) Mechanism of reaction
3. Radioactivity.

[10]
 IMPORTANT TERMS AND DEFINITIONS
1. Rate of reaction. It is defined as the change in concentration of reactant (or product) in a particular time
interval. Its unit is mol L–1s–1. If time is in minutes, then units are mol L–1 min–1 and so on.

2. Rate law or rate equation. It is the expression which relates the rate of reaction with concentration of the
reactants. The constant of proportionality 'k' is known as rate constant.

3. Rate constant. When concentration of both reactants are unity, then the rate of reaction is known as rate
constant. It is also called specific reaction rate.

4. Molecularity. Total number of 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.

5. Order of a reaction. The sum of the powers of the concentration of reactants in the rate law is termed as
order of the reaction. It can be in fraction. It can be zero also.

6. Zero order reaction. In zero order reaction the rate of reaction does not change with the concentration of
the reactants, i.e., rate = k[A]0

7. First order reaction. In first order reaction the rate of reaction is directly proportional to the concentration of
reacting substance. Rate constant of first order reaction is

2.303 a 2.303 [A]0

k= log or k = log
t ax t [A]

where 'a' is initial concentration, (a–x) is the concentration of reactants after time 't'. The unit of 'k' is s–1 or
min–1. A plot between ln [A] vs. t is a straight line with slope equal to –k. [A] is concentration of reactants
after time t.

8. Half–life of a reaction. The time taken for a reaction when half of the starting material has reacted is called
half–life of a reaction. For first order reaction

0.693
t1/2 = , where k is rate constant.
k

9. Second order reaction. The reaction in which sum of powers of concentration terms in rate law or rate
equation is equal to 2, e.g.,

dx
= k[A]1[B]1
dt

10. Third order reaction. The reaction in which sum of powers of concentration terms in rate law or rate
equation is equal to 3, e.g.,

dx
= k[A]x[B]y where x + y = 3
dt

11. Specific rate constant (k). It is defined as equal to rate of reaction when molar concentration of reactant is unity.

12. Initial rate. The rate at the beginning of the reaction when the concentrations have not changed
appreciably is called in initial rate of reaction.

13. Elementary processes. Some reactions occur by a series of elementary steps and such simple steps are
called elementary processes.

[11]
14. Pseudo first order reaction. The reaction in which one reactant is in excess so order is one is called
Pseudo first order reaction, e.g., acidic hydrolysis of ester.

CH3COOC2H5 + H2O (excess) CH3COOH + C2H5OH

15. Arrhenius equation of reaction rate. It gives the relation between rate of reaction and temperature.

K  Ae Ea /RT
where k = rate constant, A = frequency factor, Ea = energy of activation
R = gas constant, T = temperature in kelvin.
ln k = ln A – Ea/RT

Ea
log k = log A –
2.303 RT

16. Threshold energy. The total minimum energy that reacting species must possess in order to undergo
effective collision to form product molecules is called threshold energy.

17. Activation energy. It is extra energy which must be possessed by reactant molecules so that collision
between reactant molecules is effective and leads to formation of product molecules.

18. Activated complex. It is formed between reacting molecules which is highly unstable and readily changes
into product.

19. Effective collision (f). Those collisions which lead to the formation of product molecules are called effective
collisions. Rate of reaction = f × z where 'z' is collision frequency and 'f' is fraction of collisions, which are
effective.
Rate constant 'k 'at (T  10) K
20. Temperature coefficient = ; usually T = 25°C
Rate constant 'k 'at T K
It lies between 2 and 3.

21. Mechanism of reaction. The sequence of elementary processes leading to the overall stiochiometry of a
chemical reaction is known as mechanism of a reaction.

22. Rate determining step. The slowest step in the reaction mechanism is called rate determining step.

23. Photochemical reactions. Those reactions which take place in the presence of light are called photochemical
reactions. Photosynthesis is an example of photochemical reaction.

24. Thermochemical reactions. Those reactions initiated by heat energy are called thermochemical reactions.
They can occur in dark. Temperature coefficient is generally high because rate of reaction increases with
increase in temperature. G is – ve for such reactions.

25. Thermodynamic stability. A mixture of substances may not undergo reaction although thermodynamic
predict the reaction to be spontaneous. Such substances are thermodynamically unstable at ordinary
temperature but may not be kinetically unstable.

26. Kinetic stability. The reaction occurs only when the reactant crosses energy–barrier. Once it occurs, it
becomes kinetically unstable because the reaction is spontaneous. The energy evolved helps the other
reactants to cross energy–barrier. Thus, reactants should be thermodynamically as well as kinetically unstable
so as to change into products at a particular temperature.

[12]
 SHORT NOTES FOR CHEMICAL KINETICS
 Rate of chemical reaction :

 [c ]   d [c ] 
(i) Average    (ii) Instantaneous   
 t   dt 

 Units of Reaction Rate : = mol L–1 s–1 or mol L–1 min–1 (concentration time–1).
 Expressions of the rate :
For a general reaction : aA + bB  cC + dD,

d[ A ] d[B]
Rate of disappearance of A = – ; Rate of disapperance of B = – ;
dt dt

d [ C] d [D]
Rate of appearance of C = & Rate of appearance of D = .
dt dt

The positive sign shows that ceoncentrations of C and D increases with time and the negative sign indicating
that concentrations of A and B decrease with time.

1 d[ A ] 1 d [B] 1 d[C] 1 d[D]

Instantaneous rate of reaction : – –  
a dt b dt c dt d dt

1 [ A ] 1 [B] 1 [C] 1 [D]

Average rate of reaction : – –  
a t b t c t d t

Rate of disappeara nce of reac tan t Rate of appearance of product

Rate of reaction (ROR) = Stoichiome try coefficient of reac tan t  Stoichiome try coefficient of product

 Rate law and rate constant :

Rate  [A]a . [B]b or Rate = k[A]a [B]b.
The constant of proportionality, k is known as the Rate constant (specific reaction rate) and may be defined
as the rate at unit concentrations of the reactants.
 k depends on the temperature and is independent of the concentration of the reactants.
 At a fixed temperature, k is constant characteristic of the reaction. Larger value of k indicates fast reaction
and small k indicates slow reactions.
 Molecularity :
It is always a whole number (not zero) and never a fraction. Its value does not exceed 3 & it has no meanining
for a complex reaction.
 Order of reaction :
aA + bB  cC
Rate of reaction = k[A]m [B]n
Order of reaction = m + n & the order w.r.t. A, B are m, n respectively.
 The order of reaction is obtained from the experimentally determined rate and may be zero, integeral or a
fraction. In a multi-step complex reaction, the order of the reaction can determined with the help of slowest
step.
 In elementry reaction stoichiometric coefficient of reactants is equal to order of reaction : m + n = a + b.

[13]
 Differential Integrated Straight Half
Order Units of k Example
rate law rate law line plot life
–1
0 d[R]/dt = –k kt=[R]0–[R] [R]0 vs t [R]0/2k conc time H2(g) + Cl2(g) h 2HCl(g)
–1 –1
or mole L s 2HI(g) Au H2(g) + I2(g)
surface
–kt –1 –1
1 d[R]/dt = –k[R] [R] = [R]0e ln[R] vs t (ln 2)/k time or s * Decomposition of H2O2
or or in aqueous solution
kt=ln{[R]0/[R]} 0.693 * C12H22O11 + H2O
k +
H
C6H12O6 + C6H12O6
(glucose) (fructose)
* Radioactive disintegration
1
d[R]/dt = –k[R] kt = 1 1 1
2 –1 –1
2 vs t mol L s * CH3COOC2H5 + NaOH
[R] [R]0 [R] k[R]0
CH3COONa + C2H5OH
* C2H4+H2 100°C C2H6

 Important Graphical Representation :

r (a–x) t1/2
Zero order Zero Zero
order order
a0 t a0

t1/2
First
1
log (a–x) order
(a–x) First First
order order
a0
1 t a0

1 t1/2
r
(a–x) Second Second Second
order order order
2
t a0 1
a0

where a0 = Initial Concentration of reactant

 Some useful relationships between times for different fractions of reaction of first order to complete
r3/4 or t75% = 2t1/2
t87.5% = 3t1/2
t99.9%  10t1/2

A0
 Amount of the substance left after n half-lives = .
2n

[14]
 nth Order reaction :
A  Product

1  1 1 
k  t = n – 1 –  [n  1, n = order]
 (a – x )n –1 an –1 

1  2n–1 – 1
t1/2 .
= k(n – 1)  n –1 
 a 

kf
 Reversible reaction : A B
kb

1  x eq  kf [B] x eq
(kf + kb) = n  x  x  ; At equilibrium Keq = k =
[A]
= ax
t  eq  b eq

 Side/Parallel reaction :

B
k1
[ A ]0 [B] k 1
A ; n  (k 1  k 2 ) t ; [C]  k
[A]t 2
k2
C

k1 k2
% Yield of B =  100 and % Yield of C = k  k  100
k1  k 2 1 2

k T 10
 Temperature coefficient () = kT

 Arrhenius Equation
k = Ae–Ea/RT
where k = Rate constant
A = Pre exponential factor T = Temperature in kelvin
Ea = Activation Energy

 Logarithmic expression :

k  Ea  1 1 
log10  2    – 
 k1  2.303 R  T1 T2 

[15]
 Energy profile for exothermic process & endothermic process :

Eaf Eab
Eab Eaf
P.E. P.E.

H H

Reaction coordinate Reaction coordinate

H = Eaf – Eab = – ve ( Eaf < Eab) H = Eaf – Eab = + ve ( Eaf > Eab)
Exothermic process Endothermic process

 Threshold Energy = Activation Energy + Energy possesed by reactant molecules.

 Activation energy diagram for two step reaction :

(A) (i) Ist step – Slow (B) (i) Rapid equilibrium

(ii) IInd step – Fast (ii) Slow

E1 E2 E1 E2
Energy

Energy

Progress of reaction Progress of reaction

 Factors affecting reaction rates : Concentration of reactants and Reaction temperature. Besides these,

presence of catalyst and surface area (if a reactant or a catalyst is a solid) exposure to radiation also affect

the reaction rates.

[16]
 EXERCISE-I
RATE OF REACTION AND STOICHIOMETRIC COEFFICIENT
1. For the reaction
2NH3  2N2 + 3H2 0.6
a curve is plotted between [NH3] vs time as shown

[NH3]
0.4
calculate
(a) rate of disappearance between 5 to 10 sec 0.2
(b) rate of disappearance between 10 to 20 sec
5 10 15 20
Time (sec.)
2. For the reaction 3BrO—  BrO3— + 2Br— in an alkaline aquesous solution, the value of the second order
[BrO – ]
(in BrO—) rate at 80°C in the rate law for – was found to be 0.056 mol L–1 s–1. What is the rate when
t
[BrO3– ] [Br – ]
the rate law is written for (a) , (b) ?
t t
3. Dinitropentaoxide decomposes as follows :
1
N2O5(g)  2NO2(g) + O (g)
2 2
Given that –d [N2O5] / dt = k1[N2O5]
d [NO2] / dt = k2[N2O5]
d [O2] / dt = k3[N2O5]
What is the relation between k1, k2 and k3?

4. The reaction 2A + B + C  D + E is found to be first order in A second order in B and zero order in C.
(i) Give the rate law for the reaction in the form of differential equation.
(ii) What is the effect in rate of increasing concentrations of A, B, and C two times?

5. For the elementary reaction 2A + B2  2AB. Calculate how much the rate of reaction will change if the
volume of the vessel is reduced to one third of its original volume?

6. Ammonia and oxygen reacts at higher temperatures as

4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)
In an experiment, the concentration of NO increases by 1.08 ×10–2 mol litre–1 in 3 seconds. Calculate.
(i) rate of reaction.
(ii) rate of disappearance of ammonia
(iii) rate of formation of water

7. In the following reaction 2H2O2  2H2O + O2

rate of formation of O2 is 3.6 M min–1.
(a) What is rate of formation of H2O?
(b) What is rate of disappearance of H2O2?

8. The reaction A(g) + 2B(g)  C(g) + D(g) is an elementary process. In an experiment, the initial partial
pressure of A & B are PA = 0.6 and PB = 0.8 atm, if PC = 0.2 atm then calculate the ratio of rate of reaction
relative to initial rate.

[17]
 ZERO ORDER

9. In the following reaction, rate constant is 1.2 × 10–2 M s–1 A  B. What is concentration of B after 10 and
20 min., if we start with 10 M of A.

10. For the following data for the reaction A  products. Calculate the value of k.
Time (min.) [A]
0.0 0.10 M
1.0 0.09 M
2.0 0.08 M

11. The rate constant for a zero order reaction is 2 × 10–2 mol L–1sec–1, if the concentration of the reactant after
25 sec is 0.25 M, calculate the initial concentration.

12. A drop of solution (volume 0.10 ml) contains 6 × 10–6 mole of H+, if the rate constant of disappearance of H+
is 1 × 107 mole litre–1 sec–1. How long would it take for H+ in drop to disappear?

13. A certain substance A is mixed with an equimolar quantity of substance B. At the end of an hour A is 75%
reacted. Calculate the time when A remained 10% unreacted. (Given: order of reaction is zero)

FIRST ORDER

14. A first order reaction is 75% completed in 72 min. How much time will it take for
(i) 50% completion (ii) 87.5% completion

15. A first order reaction is 20% complete in 10 min. calculate (i) the specific rate constant , (ii) the time taken
for the reactions to go to 75% completion. (n5 = 1.6, n2 = 0.7)

16. A first order reaction has a rate constant 1.4 × 10–3 sec–1. How long will 5.0 g of this reactant take to reduced
to 1.25 g. (n2 = 0.7)

17. A drug is known to be ineffective after it has decomposed 30%. The original concentration of a sample
was 500 units/m l. W hen analyzed 15 m onths later, the concentration was found to be
420 units/ml. Assuming that decomposition is of first order, what will be the expiry time of the drug?
(n2 = 0.7, n3 = 1.1, n5 = 1.6, n7 = 1.95)

18. A viral preparation was inactivated in a chemical bath. The inactivation process was found to be first order in
virus concentration. At the beginning of the experiment 10 % of the virus was found to be inactivated per
minute . Evaluate k for inactivation process. (n2 = 0.7, n3 = 1.1, n5 = 1.6)

19. Consider the reaction : A  B + C. Initial concentration of A is 1 M. 20 minutes are required for
completion of 20 % reaction. (n2 = 0.7, n5 = 1.6)

d[B]
If = k[A], then calculate half life (t1/2 ) of reaction
dt

20. The reaction SO2Cl2(g)  SO2(g) + Cl2(g) is a first order gas reaction with k = 2.0 × 10–4 sec–1 at 320°C.
What % of SO2Cl2 is decomposed on heating this gas for 92 min. (n3 = 1.1)

[18]
 ORDER OF REACTION & RATE LAW
21. At 800° C the rate of reaction
2 NO + H2  N2 + H2O
Changes with the concentration of NO and H2 are

1 d[NO]
[NO] in M [H2] in M  in M sec–1
2 dt
(i) 1.5 × 10–4 4 × 10–3 4.4 × 10–4
(ii) 1.5 × 10–4 2× 10–3 2.2 × 10–4
(iii) 3.0 × 10–4 2 × 10–3 8.8 × 10–4
(a) What is the order of this reaction?
(b) What is the rate equation for the reaction?
(c) What is the rate when

[H2] = 1.5 ×10–3 M and [NO] = 1.1 × 10–3M?

22. The data below are for the reaction if NO and Cl2 to form NOCl at 295 K

Concentration of Cl2 [M] Concentration of NO Initial Rate (M s–1)

0.05 0.05 1 × 10–3
0.15 0.05 3 × 10–3
0.05 0.15 9 × 10–3

(a) What is the order w.r.t NO and Cl2 in the reaction.

(b) Write the rate expression
(c) Calculate the rate constant
(d) Determine the reaction rate when concentration of Cl2 and NO are 0.2 M & 0.4 M respectively.

23. The catalytic decomposition of N2O by gold at 900°C and at an initial pressure of 200mm is 50% completed
in 56 minutes and 73% completed in 104 minutes. (n2 = 0.7, n3 = 1.1, n5 = 1.6)
(i) What is the order of the reaction?
(ii) Calculate the velocity constant.
(iii) How much of N2O will decompose in 104 min. at the same temperature but at initial pressure of 600 mm?

24. The pressure of a gas decomposing at the surface of a solid catalyst has been measured at different times
and the results are given below
t (sec) 0 100 200 300
Pr. (Pascal) 4× 103 3.5 × 103 3× 103 2.5 × 103
Determine the order of the reaction, its rate constant.

25. The half life period for decomposition of a compound is 50 minutes. If the initial concentration is halved, the
half life period is reduced to 25 minutes. What is the order of reaction?

26. At 600°C, acetone (CH3COCH3) decomposes to ketene (CH2 = C = O) and various hydrocarbons. Given the
initial rate data in the table:
(a) What is the order? (b) Write rate law (c) Calculate rate constant
(d) Calculate the rate of decomposition when the acetone concentartion is 1.8 ×10–3 M
Experiment Initial [CH3COCH3] Rate M s–1
1. 6.0 × 10–3 M 5.2 × 10–5
2. 9.0 × 10–3 M 7.8 × 10–5
3. 1.8 × 10–3 M ?

[19]
 HALF LIFE
27. The half life period of a first order reaction is 50 min. How much time will a take for 90% completion?

28. A first order reaction has k = 1.5 × 10–6 per second at 200°C. If the reaction is allowed to run for
10 hrs., what percentage of the initial concentration would have changed into the product? What is the half
life of this reaction?

29. The half time of the first order decomposition of nitramide is 2.1 hour at 15°C.
NH2NO2 (aq.)  N2O (g) + H2O ()
If 6.2 g of NH2NO2 is allowed to deompose, calculate (i) time taken for NH2NO2 to decompose 99%, and (ii)
volume of dry N2O produced measured at 1 atm & 273 K. (n2 = 0.7, n5 = 1.6)

30. 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 concentartions of A and B are equal initially, how long
will it take for the concentration of A to be four times that of B?

31. Two substances A (t1/2= 5 mins) & B (t1/2 = 15 mins) follow first order kinetics are taken in such a way that
initially [A] = 4[B]. Calculate the time period after which the concentration of both the substance will be
equal.

CONCENTRATION REPLACED BY OTHER QUANTITIES IN FIRST ORDER

INTEGRATED RATE LAW
32. In this case we have
A B + C
Time t 
Total pressure of A + B+C P2 P3
Find k.

33. A B + C
Time t 
Total pressure of ( B+C) P2 P3
Find k.

34. A B + C
Time 0 t
Volume of reagent V1 V2
The reagent reacts with A, B and C. Find k. [Given : n-factor of all substances are equal]

35. A 2B + 3C
Time t 
Volume of reagent V2 V3
Reagent reacts with all A, B and C. Find k. [Given : n-factor of all substances are equal]

36. S G + F
Time t 
Rotation of Glucose & Fructose rt r
Find k.

[20]
37. At 27°C it was observed during a reaction of hydrogenation that the pressure of hydrogen gas decreases from
2 atmosphere to 1.1 atmosphere in 75 minutes. Calculate the rate of reaction (in M sec–1) and rate of
reaction in terms of pressure.

38. At 100°C the gaseous reaction A  2B + C was observed to be of first order. On starting with pure A it is
found that at the end of 10 minutes the total pressure of system is 180 mm. Hg and after a long time 270 mm
Hg. From these data find (a) initial pressure of A (b) the pressure of A at the end of 10 minutes (c) the specific
rate of reaction and (d) the half life period of the reaction? (n2 = 0.7)

39. The decomposition of N2O5 according to the equation 2 N2O5 (g)  4 NO2(g) + O2(g) is a first order
reaction. After 40 min. from start of decomposition in a closed vessel the total pressure developed is
found to be 300 mm Hg. On complete decomposition, the total pressure is 600 mm Hg. Calculate the
rate constant of the reaction. (n2 = 0.7, n3 = 1.1, n5 = 1.6)

40. A definite volume of H2O2 under going spontaneous decomposition required 24 c.c. of standard
permanganate solution for titration. After 10 and 22 minutes respectively the volumes of permanganate
required were 15 and 8 c.c. (n2 = 0.7, n3 = 1.1, n5 = 1.6)
(a) Find order of reaction. How may the result be explained?
(b) Calculate the time required for the decomposition to be half completed.
(c) Calculate the fraction of H2O2 decomposed after 32 minutes.

41. The following data were obtained in experiment on inversion of cane sugar.
Time (minutes) 0 60 120 180 360 
Angle of rotation (degree) +13.1 + 11.6 + 10.2 +9.0 +5.87 –3.8
Show that the reaction is of first order. After what time would you expect a zero reading in polarimeter?

42. In the pseudo first order hydrolysis of propyl acetate in the presence of dilute hydrochloric acid in dilute
aqueous solution the following data were recorded : (n2 = 0.7, n3 = 1.1, n5 = 1.6,)
Time from start in minutes 50 300
Percentage of ester decomposed 20 70
Calculate the time in which half the ester was decomposed.

43. Hydrogen peroxide solution was stored in a mild steel vessel. It was found, however, that the hydrogen
peroxide decomposed on the walls of the vessel (a first order reaction). An experiment with 100 ml of a
solution gave 10 ml oxygen (corrected to 1 atm & 273 K) after 5 days under similar storage conditions. Find
how long the peroxide can be stored before the loss of 20.00 ml oxygen occurs (per 100 ml solution) if
complete decomposition of the sample to H2O2 gave 45 ml oxygen. (n3 = 1.1, n5 = 1.6, n7 = 1.95)

44. The reaction given below, rate constant for disappearance of A is 7 × 10–3 sec–1. Calculate the time required for
the total pressure in a system containing A at an initial pressure of 0.1 atm to rise to 0.145 atm and also find the
total pressure after 100 sec. (n2 = 0.7, n5 = 1.6, n7 = 1.95)
2A (g) 4B(g) + C(g)
45. An optically active compound A upon acid catalysed hydrolysis yield two optically active compound B and
C by pseudo first order kinetics. The observed rotation of the mixture after 20 min was 5° while after
completion of the reaction it was –20°. If optical rotation per mole of A, B and C are 60°, 40° and
–80°. Calculate half life of the first order reaction
A  B + C

[21]
 PARALLEL REACTION

[x]t
46. For a first order parallel reaction , calculate the value of ratio, at any given instant t.
[y]  [z]

[C]
47. k1 = x hr–1; k1 : k2 = 1 : 10. Calculate after one hour from the start of the reaction.
[A]

Assuming only A was present in the beginning.

48. A substance undergoes first order decomposition. The decomposition follows two parallel first order reactions

as ; k1 = 1.26 × 10–4 sec–1 and k2 = 3.6 × 10–5 sec–1. Calculate the % distribution of B & C.

k1 B
49. A For first order parallel reaction k1 and k2 are 8 and 2 min–1 respectively at 300 K. If the activation
k2 C
energies for the formation of B and C are 20 and 28.314 kJ/mol respectively find the temperature at which B
and C will be obtained in molar ratio of 2 : 1.
[Given : n 4 = 1.4]

TEMPERATURE DEPENDENCE OF RATE (ACTIVATION ENERGY)

50. In gaseous reactions important for understanding 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 = 77 kJ mol–1, then calculate Ea for the
bimolecular recombination of 2 OH radicals to form H2O & O at 500 K

51. The energy of activation of a first order reaction is 107.9 kJ mole–1 and pre-exponential factor (A) is
5 × 1013 sec–1. At what temperature, will the reaction have a half life of 7 minute?
(n2 = 0.7, n3 = 1.1, n5 = 1.6, R = 8.3 J/mol K)
52. The specific rate constant for a reaction increases by a factor of 4, if the temperature is changed from 27°C
to 47°C. Find the activation energy for the reaction.

53. The energy of activation and specific rate constant for a first order reaction at 27°C are 100 kJ/ mole and
3.5 × 10–5 sec–1 respectively. Determine the temperature at which half life of the reaction is 2 hours.

 100 
(n2 = 0.7, n3 = 1.1, n5 = 1.6)  Consider  12 
 8.314 

54. A first order reaction is 50% complete in 30 minutes at 27°C and in 10 minutes at 47°C. Calculate the
(a) rate constant for the reaction at 27°C & 47°C and (n2 = 0.693, n3 = 1.1, R = 8.3 J/mol K)
(b) energy of activation for the reaction.

55. A catalyst lowers the activation energy for a certain reaction from 75 kJ to 25 kJ mol–1. What will be the

 50 
effect on the rate of reaction at 27°C, after things being equal.  Consider  6
 8.314 

[22]
56. At 380°C, the halflife period for the first order decomposition of H2O2 is 360 min.The energy of activation of
the reaction is 200 kJ mol1. Calculate the time required for 75% decomposition at 4500C.

MECHANISM OF REACTION
57. The reaction 2NO + Br2  2NOBr, is supposed to follow the following mechanism

(i) NO + Br2 NOBr2

slow
(ii) NOBr2 + NO  2NOBr
Suggest the rate of law expression.

58. For the reaction 2H2 + 2NO N2 + 2H2O, the following mechanism has been suggested:
2NO N2O2 equilibrium constant K1 (fast)
K
N2O2 + H2 
2
 N2O+ H2O (slow)
K
N2O + H2 
3
 N2 + H2O (fast)
Establish the rate law for given reaction.

59. Reaction between NO and O2 to form NO2 is 2NO + O2  2NO2 follows the following mechanism
k1
NO + NO N2O2 ( in rapid equilibrium)
k–1

K
N2O2 + O2 
2
 2NO2 (slow)

1  d[NO2 ] 
Show that the rate of reaction is given by   = K[NO]2[O2]
2  dt 

60. Deduce rate law expressions for the conversion of H2 and I2 to HI at 400°C corresponding to each of the
following mechanisms:
(a) H2 + I2  2HI (one step) (b) I2 2I
2I + H2  2HI (slow)
(c) I2 2I
I + H2 IH2
IH2 + I  2HI (slow)

(d) Can the observed rate law expression rate = k[H2][I2] distinguish among these mechanisms?
(e) If it is known that ultraviolet light causes the reaction of H2 and I2 to proceed at 200°C with the same
rate law expression, which of these mechanisms becomes most improbable? Are any of these
mechanisms proved?

[23]
 EXERCISE -II
1. A solution of A is mixed with an equal volume of a solution of B containing the same number of moles, and the
reaction A + B  C occurs. At the end of 1hr, A is 75 % reacted. How much of A will be left unreacted at the
end of 2 hr if the reaction is (a) first order in A and zero order in B; (b) zero order in both A and B ?

2. The approach to the following equilibrium was observed kinetically from both directions:
PtCl42 + H2O [Pt(H2O)Cl3] + Cl at 25°C, it was found that

 [PtCl24 ]  [4.0  105 sec 1 ][PtCl24 ]  [2.0  103 L.mol1 sec 1 ]  [Pt(H2O)Cl3 ] [Cl ]
t
What is the value of equilibrium constant for the complexation of the fourth Cl by Pt(II)?

3. The complex [Co(NH3)5F]2+ reacts with water according to the equation.

[Co(NH3)5F]2+ + H2O  [Co(NH3)5(H2O)]3+ + F
The rate of the reaction = rate const. x[complex]ax[H+]b. The reaction is acid catalysed i.e. [H+] does not
change during the reaction. Thus rate = k[Complex]a where k’ = k[H+]b, calculate ‘a’ and ‘b’ given the
following data at 250C.
[Complex]M [H+]M T1/2hr T3/4hr

0.1 0.01 1 2
0.2 0.02 0.5 1

4. 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?

5. The decomposition of a compound P, at temperature T according to the equation

2P(g)  4Q(g) + R(g) + S(l)
is the first order reaction. After 25 minutes from the start of decomposition in a closed vessel, the total
pressure developed is found to be 332.5 mm Hg and after a long period of time the total pressure observed to
be 632.5 mm Hg. Calculate the total pressure of the vessel after 87.5 mintute, if volume of liquid S is
supposed to be negligible. Also calculate the time fraction t7/8.
Given : Vapour pressure of S (l) at temperature T = 32.5 mm Hg. (n2 = 0.7, n3 = 1.1, n5 = 1.6)

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+ & 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. Decomposition of H2O2 is a first order reaction. A solution of H2O2 labelled as "16.8 V" was left open. Due
to this, some H2O2 decomposed. To determine the new volume strength after 2.303 hours, 20 mL of this
solution was diluted to 100 mL. 25 mL of this diluted solution was titrated against 37.5 mL of 0.02 M KMnO4
solution under acidic conditions [Given : STP is 1 atm and 273 K]
Calculate the rate constant (in hr–1) for decomposition of H2O2

8. A metal slowly forms an oxide film which completely protects the metal when the film thickness is
4.0 × 10–3 inch. If the film thickness is 1.6 × 10–3 inch in 6 weeks, After how many weeks film thickness will
be 2.5 × 10–3 inch? The rate of film formation follows first order kinetics. (n2 = 0.7, n3 = 1.1, n5 = 1.6)

[24]
9. A vessel contains dimethyl ether at a pressure of 0.4 atm. Dimethyl ether decomposes as
CH3OCH3(g)  CH4(g) + CO(g) + H2(g). The rate constant of decomposition is 2.3 ×103 min1. Calculate
the ratio of initial rate of diffusion to rate of diffusion after 5.0 hours of initiation of decomposition. Assume the
composition of gas present and composition of gas diffusing to be same. (log2 = 0.3, n = 2.3 log)

10. At room temperature (27°C) orange juice gets spoilt in about 64 hours. In a referigerator at 7°C juice
can be stored five times as long before it gets spoilt. Estimate (a) the activation energy of the reaction
that causes the spoiling of juice. (b) How long should it take for juice to get spoilt at 47°C? (n2 = 0.7,
n3 = 1.1, n5 = 1.6, R = 8.3 J mol–1 K–1)

11. A first order reaction, A  B, requires activation energy of 61.44 kJ mol1. When a 20% solution of A was
kept at 27°C for 20 minutes, 25% decomposition took place. What will be the percent decomposition in 21.4
minutes in a 30% solution maintianed at 47°C? Assume that activation energy remains constant in this
range of temperature. (n2 = 0.7, n3 = 1.1, n5 = 1.6, R = 8 J mol–1 K–1)

12. Two reations (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 the same temperature 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. (n2 = 0.693)

13. The reaction

cisCr(en)2(OH)+2 transCr(en)2(OH)+2

is first order in both directions. At 25°C the equilibrium constant is 0.16 and the rate constant k 1 is
3.5 × 10 4s 1. In an experiment starting with the pure cis form, how long would it take for half the equilibrium
amount of the trans isomer to be formed ? (n2 = 0.7)

14. For the system A(g) B(g), H for the forward reaction is –33 kJ/mol (Note : H = E in this case).

[B]
Show that equilibrium constant K = = 5.572 × 105 at 300 K. If the activation energies Ef & Eb are in the
[A]

ratio 20 : 31, calculate Ef and Eb at this temperature. Assume that the pre-exponential factor is the same for
the forward and backward reactions.

k k
15. For the two parallel reactions A 
1
B and A 
2
 C, show that the activation energy E for the
disappearance of A is given in terms of activation energies E1 and E2 for the two paths by

k1E1  k 2E 2
E = k1  k 2

[25]
 QUESTION BANK
1. The rate of a reaction is expressed in different ways as follows :
1 d[C] 1 d[D] 1 d[ A ] d[B]
   
2 dt 3 dt 4 dt dt
The reaction is:
(A) 4 A + B  2C + 3D (B) B + 3 D  4 A + 2 C
(C) A + B  C + D (D) B + D A + C

2. In the reaction xA(g)  yB(g)

 d[ A ]   d[B] 
log   log   0.699
 dt   dt 
Then, x : y is
(A) 8 : 1 (B) 5 : 1 (C) 3 : 1 (D) 2 : 1
3. In a reaction A  B Half life is independent to the initial conc of reactant, which is correct graph for the
reaction?

rate [A] rate

of A of B
(A) (B) (C) (D)

time time time

time
4. For a hypothetical reaction,
A + 3B  P H = – 2 x kJ/mole of A
& M  2Q + R H = + x kJ/mole of M
If these reactions are carried simultaneously in a reactor such that temperature is not changing. If rate of
disappearance of B is y M sec–1 then rate of formation (in M sec–1) of Q is :

2 3 4 3
(A) y (B) y (C) y (D) y
3 2 3 4

5. Units of rate constant for first and zero order reactions in terms of molarity (M) are respectively
(A) sec–1, M sec–1 (B) sec–1, M (C) M sec–1, sec –1 (D) M, sec–1

6. Gaseous reaction A  B + C follows first order kinetics. Concentration of A changes from 1 M to 0.25 M
is 138.6 minutes. Find the rate of reaction when concentration of A is 0.1 M.
(A) 2 × 10–3 M min–1 (B) 10–3 M min–1
(C) 10–4 M min–1 (D) 5 × 10–4 M min–1

7. A first order reaction is 87.5% completed in 30 min. The time taken for 75% completion of reaction is (in min.)
(A) 10 (B) 15 (C) 20 (D) None of these

8. Which graph represents zero order reaction [A(g)  B(g)].

d[B] t1/2 t3/4

[B]
(A) (B) dt (C) (D)

t t [A]0 [A]0

[26]
9. Consider the reaction A  B, graph between half life (t1/2) and initial concentration (a) of the reactant is

t1/2

a
d[ A ]
Hence graph between – and time will be
dt

d[ A ]
d[ A ] 
 dt d[ A] d[ A]
(A) dt (B) (C)  (D) 
dt dt
t
t t
10. If decomposition reaction A(g)  B (g) follows first order kinetics then the graph of rate of formation (R)
of B against time t will be
R R R R

(A) (B) (C) (D)

t t t t
k 1[ A ]
11. Statement-1 : The half life of reaction with rate law, rate of reaction = is depend on initial
1  k 2 [A]
concentration of reactant A at very high concentration.
Statement-2 : The reaction is first order at very low concentration of A.
(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 NOTcorrect explanation for Statement-1
(C) Statement-1 is true, Statement-2 is false
(D) Statement-1 is false, Statement-2 is true
d[ A ]
12. For the reaction A  B, the rate law expression is – = k [A]1/2. If initial concentration of A is [A]0, then
dt
2
(A) The integerated rate expression is k = ( A10/ 2  A1/ 2 )
t

A
(B) The graph of A Vs t will be

t
K
(C) The half life period t1/2 =
2[ A ]10/ 2

[ A ]0
(D) The time taken for 75% completion of reaction t3/4 =
k

13. The rate constant for the forward reaction A (g) 2B(g) is 1.5 × 10–3 s–1 at 100 K. If 10–5 moles of A and
100 moles of B are present in a 10 litre vessel at equilibrium then rate constant for the backward reaction at
this temperature is
(A) 1.50 × 104 L mol–1 s–1 (B) 1.5 × 1011 L mol–1 s–1
(C) 1.5 × 1010 L mol–1 s–1 (D) 1.5 × 10–11 L mol–1 s–1

[27]
 1 1

14. Reaction A + B  C + D follow's following rate law : rate = k [A] 2 [B] 2 . Starting with initial conc. of 1 M
of A and B each, what is the time taken for concentration of A of become 0.25 M.
Given : k = 2.303 × 10–3 sec–1.
(A) 300 sec. (B) 600 sec. (C) 900 sec. (D) none of these
15. Consider the following first order competing reactions:
k 2 k
X  1 A + B and Y  C+D
if 50% of the reaction of X was completed when 96% of the reaction of Y was completed, the ratio of their rate
constants (k2/k1) is
(A) 4.06 (B) 0.215 (C) 1.1 (D) 4.65

16. Consider a reaction A(g)  3B(g) + 2C(g) with rate constat 1.386 × 10–2 min–1. Starting with 2 moles of
A in 12.5 litre vessel intially, if reaction is allowed to takes place at constant pressure & at 298K then find the
concentration of B after 100 min.
(A) 0.04 M (B) 0.36 M (C) 0.09 M (D) None of these

–
17. For the reaction H2O2 + 2I + 2H+  2 H2O + I2
– –
obsereved rate law is r = k1[H2O2] [I ] + k2 [H2O2] [I ] [H+]. Order of the reaction is :
(A) 2 (B) 3 (C) 5 (D) Not defined

Question No. 18 to 19 (2 questions)

Oxidation of metals is generally a slow electrochemical reaction involving many steps. These steps involve
electron transfer reactions. A particular type of oxidation involve overall first order kinetics with respect to
fraction of unoxidised metal (1– f ) surface thickness relative to maximum thickness (T) of oxidised surface,
when metal surface is exposed to air for considerable period of time

df
Rate law : = k(1 – f ), where f = x/T,,
dt

x = thickness of oxide film at time 't'

& T = thickness of oxide film at t = 
A graph of ln(1 – f ) vs t is shown in the adjacent figure.

18. The time taken for thickness to grow 50% of 'T' is

(A) 23.1 hrs (B) 46.2 hrs (C) 100 hrs (D) 92.4 hrs

19. The exponential variation of 'f ' with t(hrs) is given by

3t/200 3t/200 3t/200
(A) [1  e3t/200 ] (B) e 1 (C) e (D) e

Question No. 20 to 21 ( 2 questions)

k1 1
For a hypothetical elementary reaction where k  2
2

Initially only 2 moles of A are present.

20. The total number of moles of A, B & C at the end of 50% reaction are
(A) 2 (B) 3 (C) 5 (D) None

21. Number of moles of B are

(A) 2 (B) 1 (C) 0.666 (D) 0.333

[28]
22. 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 catalyst lowers the activation energies of both (forward and reverse)
reactions by 100 kJ mol–1. The magnitude of enthalpy change of the reaction (A2 + B2  2AB) in the
presence of catalyst will be (in kJ mol–1).
(A) 300 (B) 120 (C) 20 (D) 380

23. Consider the reaction,

–1

A, B and C all are optically active compound. If optical rotation per unit –2 min B
10
6. 93×
concentration of A, B and C are 60º, –72º, 42º and initial concentration of k 1=
A is 2M then select correct statement(s). A
k2 =1
(A) solution will be optically active and dextro after very long time 3.86
×10 –2
(B) solution will be optically active and levo after very long time min –1
C
(C) half life of reaction is 15 min
(D) After 75% conversion of A into B and C angle of rotation of solution will be 36º
24. Which of the following is/are correct statement ?
(A) Stoichiometry of a reaction tells about the order of the elementary reactions
(B) For a zero order reaction, rate and the rate constant are identical.
(C) A zero order reaction is controlled by factors other than concentration of reactants
(D) A zero order reaction is always elementary reaction
25. The rate of a chemical reaction doubles for every 10°C rise of temperature. If the temperature is raised by
50°C, the rate of the reaction increases by about :
(A) 10 times (B) 24 times (C) 32 times (D) 64 times

26. A first order reaction is 50% completed in 20 minutes at 27°C and in 5 min at 47°C. The energy of activation
of the reaction is
(A) 43.85 kJ/mol (B) 55.14 kJ/mol (C) 11.97 kJ/mol (D) 6.65 kJ/mol

27. For the first order reaction A — B + C, carried out at 27 ºC if 3.8 × 10–16 % of the reactant molecules exists
in the activated state, the Ea (activation energy) of the reaction is
(A) 12 kJ/mole (B) 831.4 kJ/mole (C) 100 kJ/mole (D) 88.57 kJ/mole
28. The rate constant, the activation energy and the Arrhenius parameter (A) of a chemical reaction at 25°C are
3.0 × 10–4 s–1, 104.4 kJ mol–1 and 6.0 × 1014s–1 respectively. The value of the rate constant at T   is
(A) 2.0 × 1018 s–1 (B) 6.0 × 1014 s–1 (C) infinity (D) 6 × 10–4 s–1
29. The reactions of higher order are rare because
(A) many body collisions involve very high activation energy
(B) many body collisions have a very low probability
(C) many body collisions are not energetically favoured.
(D) many body collisions can take place only in the gaseous phase.
30. The following mechanism has been proposed for the exothermic catalyzed complex reaction.
1 k k
A+B I AB  AB + I  2 P+A
If k1 is much smaller than k2. The most suitable qualitative plot of potential energy (P.E.) versus reaction
coordinate for the above reaction.

(A) (B) (C) (D)

[29]
31. The mechanism of enzyme catalysed reaction is given by
Kf
Step-1 : E + S E + S (fast)
Kb

K2
Step-2 : ES P + E (slow)
Choose the correct set of identifications.

(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
32. Select incorrect statement(s) :
(A) Unit of pre-exponential factor (A) for second order reaction is mol L–1 s–1
(B) A zero order reaction must be a complex reaction.
(C) Molecularity is defined only for RDS in a complex reaction
(D) Rate constant of reaction is affected by concentration of reactant.

Assertion & Reason :

33. Statement-1 For zero order reaction A B, successive half life of reaction decreases with the progress
of the reaction.
Statement-2 Concentration of reactants in zero order reaction is constant.
(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 the correct explanation for Statement-1
(C) Statement-1 is true, Statement-2 is false
(D) Statement-1 is false, Statement-2 is true

34. Statement-1 The temperature coefficient of a single step reaction may be negative.
Statement-2 For reactions activation energy may be negative.
(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 the correct explanation for Statement-1
(C) Statement-1 is true, Statement-2 is false
(D) Statement-1 is false, Statement-2 is true

[30]
35. For the reaction of type A(g)  2B(g)
Column-I contains four entries and Column-II contains four entries. Entry of Column-I are to be
matched with ONLY ONE ENTRY of Column-II
Column I Column II

d[B] d[ A ]
(A) vs – (P)
dt dt

(B) ] vs t for first order (Q)

(C) ] vs t for first order (R)

(D) ] vs t for zero order (S)

Subjective :
36. The initial rate of zero order reaction of the gaseous reaction A(g)  2B(g) is 10–2 M min–1. If the initial
concentration of A is 0.1 M and concentration of B after 60 sec. is x × 10–2 M. What is the value of x ?

37. For the reaction A + B  C; starting with different initial concentration of A and B, initial rate of reaction
were determined graphically in four experiments.

S.No. [A]0/M (Initial conc.) [B]0/M (Initial conc.) rate/(M sec–1)

1 1.6 × 10–3 5 × 10–2 10–3
2 3.2 × 10–3 5 × 10–2 4 × 10–3
3 1.6 × 10–3 10–1 2 × 10–3
4 3.2 × 10–3 10–1 8 × 10–3

Calculate overall order of reaction ?

38. At certain temperature, the half life period in the thermal decomposition of a gaseous substance as follows:
P(mmHg) 500 250
t1/2 (in min.) 235 940
Find the order of reaction.

39. In a gaseous state reaction, A2 (g)  B(g) + (1/2)C (g). The increase in pressure from 100 mm to 120 mm
is notices in 5 minutes. What is the rate of disapearance of A2 in (mm min–1) ?

40. How many times the rate of reaction will change if temperature is increased from 20°C to 40°C, when
temperature coefficient is 2.

[31]
 EXERCISE-III
OBJECTIVE PROBLEM
1. Plots showing the variation of the rate constant (k) with temperature (T) are given below. The plot that follows
Arrhenius equation is [JEE 2010]

k k k
(A) (B) (C) k (D)

T T T T
2. The concentration of R in the reaction R P was decreased as a function of time and the following data
is obtained: [JEE 2010]
[R] (molar) 1.0 0.75 0.40 0.10
T (min.) 0.0 0.05 0.12 0.18
The order of reaction is

3. For the first order reaction , 2N2O5(g)  4NO2(g) + O2(g) [JEE 2011]
(A) the concentration of the reactant 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

4. 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]
(A) 60.5 kJ mol–1 (B) 53.6 kJ mol–1 (C) 48.6 kJ mol–1 (D) 58.5 kJ mol–1

 
5. 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 Advance 2013]

[Q]0
[Q]

Time

(A) 2 (B) 3 (C) 0 (D) 1

6. For the elementary reaction M  N, the rate of disappearance of M increases by a factor of 8 upon doubling
the concentration of M. The order of the reaction with respect to M is [JEE Advance 2014]
(A) 4 (B) 3 (C) 2 (D) 1

7. Higher order (> 3) reactions are rare due to [JEE Main 2015]
(A) Loss of active species on collision
(B) Low probability of simultaneous collision of all the reacting species
(C) Increase in entropy and activation energy as more molecules are involved
(D) Shifting of equilibrium towards reactants due to elastic collisions

[32]
8. Decomposition of H2O2 follows a first order reaction. In fifty minutes the concentration of H2O2 decreases
from 0.5 to 0.125 M in one such decomposition. When the concentration of H2O2 reaches 0.05 M, the rate of
formation of O2 will be : [JEE Main 2016]
(A) 6.93 × 10–2 mol min–1 (B) 6.93 × 10–4 mol min–1
(C) 2.66 L min–1 at STP (D) 1.34 × 10–2 mol min–1

9. According to the Arrhenius equation, [JEE Advance 2016]

(A) A high activation energy usually implies a fast reaction.
(B) Rate constant increases with increase in temperature. This is due to a greater number of collisions
whose energy exceeds the activation energy.
(C) Higher the magnitude of activation energy, stronger is the temperature dependence of the rate constant.
(D) The pre-exponential factor is a measure of the rate at which collisions occur, irrespective of their energy.

10. Two reactions R1 and R2 have identical pre-exponential factors. Activation energy of R1 exceeds that of R2 by
10 kJ mol–1. If k1 and k2 are rate constants for reactions R1 and R2 respectively at 300 K, then ln(k2 / k1) is
equal to (R = 8.314 J mol–1 K–1) [JEE Main 2017]
(A) 4 (B) 8 (C) 12 (D) 6

11. In a bimolecular reaction, the steric factor P was experimentally determined to be 4.5. The correct option(s)
among the following is(are) [JEE Advance 2017]
(A) The value of frequency factor predicted by Arrhenius equation is higher than that determined experimentally
(B) The activation energy of the reaction is unaffected by the value of the steric factor
(C) Since P = 4.5, the reaction will not proceed unless an effective catalyst is used
(D) Experimentally determined value of frequency factor is higher than that predicted by Arrhenius equation

12. At 518°C, the rate of decomposition of a sample of gaseous acetaldehyde, initially at a pressure of 363 Torr,
was 1.00 Torr s–1 when 5% had reacted and 0.5 Torr s–1 when 33% had reacted. The order of the reaction is:
[JEE Main 2018]
(A) 0 (B) 2 (C) 3 (D) 1

13. For a first order reaction A(g) 2B(g) + C(g) at constant volume and 300 K, the total pressure at the
beginning (t = 0) and at time t are P0 and Pt, respectively. Initially, only A is present with concentration [A]0,
and t1/3 is the time required for the partial pressure of A to reach 1/3rd of its initial value. The correct option(s)
is(are)
(Assume that all these gases behave as ideal gases) [JEE Advanced 2018]
Rate constant
ln(3P0–Pt)

ln(P0–Pt)

t1/3
(A) (B) (C) (D)

Time [A]0 Time [A]0

[33]
14. Which of the following plots is (are) correct for the given reaction ? [JEE Advanced 2020]
([P]0 is the initial concentration of P)

CH3 CH3
H3C ——– Br + NaOH H3C ——– OH + NaBr
CH3 CH3
P Q

Initial rate
t1/2
(A) (B)

[P]0 [P]0

[Q]  [P] 
(C) [P] (D) ln 
0  [P]0 
time time

15. For the following reaction

k
2X + Y  P

d[P]
the rate of reaction is  k[X] . Two moles of X are mixed with one mole of Y to make 1.0 L of solution. At
dt
50 s, 0.5 mole of Y is left in the reaction mixture. The correct statement(s) about the reaction is(are)
(Use ; ln 2 = 0.693) [JEE Advanced 2021]
(A) The rate constant, k, of the reaction is 13.86 × 10–4 s–1.
(B) Half-life of X is 50 s.

d[X]
(C) At 50 s, –  13.86  10 3 molL1s1
dt

d[Y]
(D) At 100 s, –  3.46  103 molL1s1
dt

[34]
16. Match the rate expressions in LIST-I for the decomposition of X with the corresponding profiles provided in
LIST-II. Xs and k are constants having appropriate units. [JEE Advanced 2022]
List-I List-II

Half life (t1/2)

k[X]
(I) Rate = X  [X] (P)
s

Initial concentration of X

under all possible initial concentrations of X

Half life (t1/2)

k[X]
(II) Rate = X  [X] (Q)
s

Initial concentration of X

where initial concentrations of X are much less than Xs

k[X] Rate
(III) Rate = X  [X] (R)
s

Initial concentration of X

where initial concentrations of X are much higher than Xs

[X]

k[X]2
(IV) Rate = (S)
Xs  [X]

Time

where initial concentrations of X are much higher than Xs

In[X]

(T)

Time

The correct option is :

(A) (I)  (P); (II)  (Q); (III)  (S); (IV)  (T) (B) (I)  (R); (II)  (S); (III)  (S); (IV)  (T)
(C) (I)  (P); (II)  (Q); (III)  (Q); (IV)  (R) (D) (I)  (R); (II)  (S); (III)  (Q); (IV)  (R)

[35]
 SUBJECTIVE PROBLEM

17. An organic compound undergoes first-order decomposition. The time taken for its decomposition to 1/8 and

[t t / 8 ]
1/10 of its initial concentration are t1/8 and t1/10 respectively. What is the value of  10 ?
[ t1/ 10 ]

(take : log102 = 0.3) [JEE 2012]

18. In dilute aqueous H2SO4, the complex diaquoudioxalatoferrate(II) is oxidized by MnO4–. For this reaction, the
ratio of the rate of change of [H+] to the rate of change of [MnO4–] is [JEE Advanced 2015]

1
19. The plot of log kf versus for a reversible reaction A(g)  P(g) is shown.
T

log kf

0.002 –1
1/T(K )

Pre-exponential factors for the forward and backward reactions are 1015 s–1 and 1011 s–1, respectively. If the
value of log K for the reaction at 500 K is 6, the value of |log kb| at 250 K is ___________.
[K = equilibrium constant of the reaction ; kf = rate constant of forward reaction ; kb = rate constant of
backward reaction] [JEE Advanced 2023]

[36]
 ANSWER KEY
EXERCISE-I
RATE OF REACTION AND STOICHIOMETRIC COEFFICIENT
1. (a) 0.04 (b) 0.02 2. (a) 0.019 mol L–1 s–1, (b) 0.037 mol L–1 s–1
dx
3. 2k1 = k2 = 4k3 4. (i) = k[A][B]2, (ii) rate increases by 8 times
dt
5. rate increase by 27 times
1 d[NO]
6. (i) r = = 9 × 10–4 mol litre–1 sec–1, (ii) 36 × 10–4 mol litre–1sec–1, (iii) 54 × 10–4 mol litre–1sec–1
4 dt
7. (i) 7.2 mol litre–1min–1, (ii) 7.2 mol litre–1 min–1 8. 1/6

ZERO ORDER
9. (i) 7.2 M, (ii) Think 10. K = 0.01 M min–1

11. 0.75 M 12. 6 × 10–9 sec 13. 1.2 hr

FIRST ORDER

14. (i) 36 min., (ii) 108 min. 15. (i) 00.02 min–1, (ii) 70.00 min 16. 1000.00 sec
17. expiry time = 35 months 18. 1.67 × 103 s1 19. 70.00 min 20. 66.7%

ORDER OF REACTION & RATE LAW

21. (a) Third order, (b) r = k[NO]2[H2], (c) 8.85 ×10–3 M sec–1.

22. (a) order w.r.t NO = 2 and w.r.t Cl2 = 1, (b) r = K[NO]2[Cl2], (c) K = 8 L2mol–2s–1, (d) rate = 0.256 mole L–1s1]

23. (i) first order (ii) k = 1.25 × 102 min1 (iii) 73%

24. (i) Zero order, (ii) k = 5 Pa/s

dx
25. Zero order 26. (a) n =1, (b) = k[CH3COCH3], (c) 8.67 × 10–3 s–1, (d) 1.56 × 10–5 M s–1
dt

HALF LIFE
27. 166.6 min 28. 5.26% , 4.62 × 105 sec 29. (i) t = 13.8 hrs, (ii) 2.218 litre
30. 54 min 31. 15 min

CONCENTRATION REPLACED BY OTHER QUANTITIES IN FIRST ORDER INTEGRATED RATE LAW

1 P3 1 P3 1 V1
32. k = t n 2(P  P ) 33. k = t n (P  P ) 34. k = t n (2 V  V )
3 2 3 2 1 2

1 4 V3 1 r
35. k = t n 5( V  V ) 36. k = t  n (r  r ) 37. 8.12 × 10–6 Ms–1, 0.012 atm min–1
3 2  t

38. (a) 90 mm, (b) 45 mm, (c) 7 × 10–2 min–1, (d) 10 min. 39. k1 = 2.5 × 103 min1
40. (a) first order, (b) 14 minutes, (c) 0.8 41. 966 min 42. 175 min
43. 12 days 44. 50 sec, 0.175 atm 45. 20 min

[37]
 PARALLEL AND SEQUENTIAL REACTION

1 [C] 10 11x
46. 47. = (e 1x – 1) 48. 77.7, 22.3 49. 379.75 K
e(K1  K 2 )t  1 [A] 11

TEMPERATURE DEPENDENCE OF RATE (ACTIVATION ENERGY)

50. 5 kJ mol–1 51. 343 K 52. 55.33 kJ mole–1 53. 307.7 K

54. (a) 2.31 × 10–2 min–1, 6.93 × 10–2 min–1, (b) 43.824 kJ mole–1
55. rate of reaction increases 4.85× 108 times 56. t = 20.4 minutes

MECHANISM OF REACTION

57. r = K' [NO]2[Br2] 58. r = K [NO]2 [H2], where K = k2 × K1

60. (d) No, (e) mechanism (a) is incorrect

EXERCISE-II
1. (a) 6.25 ; (b) 0% 2. 50.00
3. a=b=1 4. 2 × 102 min1
5. Pt = 452.5 mm Hg, t7/8 = 262.5 min 6. 0.0207 min–1
1
7. 0.60 8. 12 week 9.
2 2
10. (a) 55.776 kJmol-1, (b) 16.00 hour 11. % decomposition = 80 %
12. k = 0.0327 min–1 13. 4.6 mins
14. Ef = 6 × 104J; Eb = 9.3 × 104J

QUESTION BANK
1. B 2. B 3. C 4. C 5. A 6. B 7. C
8. D 9. C 10. C 11. B 12. ABD 13. D 14. B
15. D 16. C 17. D 18. B 19. A 20. B 21. C
22. C 23. AD 24. ABC 25. C 26. B 27. C 28. B
29. B 30. A 31. B 32. ACD 33. C 34. D
35. A  S ; B  R ; C  P ; D Q 36. 2 37. 3 38. 3 39. 8
40. 4

EXERCISE-III
OBJECTIVE PROBLEM
1. A 2. 0 3. ABD 4. B 5. D 6. B 7. B
8. B 9. BCD 10. A 11. BD 12. B 13. A,D 14. A
15. B,C,D 16. A
SUBJECTIVE PROBLEM
17. 9 18. 8 19. 5.00

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