1

C-04:- Chemical Kinetics

1.

The branch of physical chemistry which deals with the rate at which the chemical reactions occur, the mechanism by which the
chemical reactions take place and the influence of various factors such as concentration, temperature, pressure, catayst, etc. on the
reaction rats, is called the chemical kinetics.
On the basis of rates, the chemical reactions are broadly divided into three categories.
1.1 Very fast or instantaneous reactions: These reactions take about

1014 to 1016 seconds for completion. It is almost

impossible to determine the rates of these reactions. Some such examples are:

1.2 Very slow reactions: It is also difficult to study the kinetics of such reactions as their competion takes days, months or years.
Some examples are:
i) Reaction between hydrogen and oxygen at room temperature

2 H 2 +O2 room temperature 2 H 2 O

(very slow reaction)

ii) Rusting of iron occurs very slowly.

1.3 Moderate reactions: Between the above two extremes, there are a number of reactions which take place at moderate and
measurable rates at room temperature and it are those reactions which are studied in chemical kinetics.
i) Decomposition of hydrogen peroxide.

2 H 2 O2 2 H 2 O+O 2

ii) Decomposition of nitrogen pentoxide.

2 N 2 O5 2 N 2 O4 + O2

iii) Hydrolysis of an ester.

iv) Inversion of cane sugar in aqueous solution

2. RATE OF REACTION (AVERAGE AND INSTANTANEOUS RATE)

Rate=

Change some quantity X

=
Time taken for thechange t

The rate measured over a long time interval is called average rate and the rate measured for an infinitesimally small time interval is
called instantaneous rate. For a reaction,

n1 A +n2 B m1 C+

1 d [ A ] 1 d [B ] 1 d [C] 1 d [D ]
=
=
=
m2 D , the instantaneous rate may be expressed as r inst =
n1 dt
n2 dt
m1 dt
m 2 dt
Here negative sign shows that concentration of reactant decreases with the time.
2.1 Experimental determination of instantaneous rate of reaction: A curve is plotted betweeen concentration and time. A tangent is
drawn to the curve at the point corresponding to time interval t. The slopw of this tangent gives the instantaneous rate of reaction.
Instantaneous rate of reaction = Slope of curve =

Intercept along ordinate X

=
Intercept along abscissa t

Sinc the concentrations of the reactants keep on decreasing with time, the rate of reaction correspondingly decreases with time.

3. FACTORS AFFECTING RATE OF REACTION

3.1 Law of mass action (Given by Guldberg and Waage) : At a given temperature, the rate of a reaction at a particular instant is
proportional to the product of the active masses of the reactants at that instant raised to powers which are numerically equal to the
numbers of their respective molecules in the stoichiometric equation describing the reaction.
Active mass = molar concentration of th substance

number of gram mols of the substance

volume of litres

w/ M n
=
V
V

Where w = mass of substance in grams and M is the molecular mass in grams, n is the number of moles and V is the volume in
litres.
RATE CONSTANT

A B.

Consider a simple reaction

If CA is the molar concentration or active mass of A at a particular instant, then

dx
dx
C A =kC A
dt
dt

Where k is a proportionally constant, called velocity constant or rate constant or specific reaction rate.
At a fixed temperature, if

Rate=

C A =1, then

dx
=k
dt

(i)

Let us consider a general reaction.

aA+ bB product
a

A [b]
dx
Rate=

dt

( )

Rate=K [ A ]a [ B]b
When

.(ii)

[ A ] =[ B ] =1 mol/litre , then
Rate=k

Rate of a reaction at unit concentration of reactants is called rate constant.

3.2 Molecularity of Reaction: Molecularity of simple reactions is equal to the sum of the number of molecules of reactants involved in
the balanced stoichiometic equation.

PCl5 PCl3 +Cl 3

2 Hl H 2 +l 2

(Unimolecular)
(Bimolecular)

2 SO 2 +O2 2 SO 3

(Trimolecular)

NO+O2 NO 2+O 2
2CO 2 +O2 2CO 2

(Bimolecular)
(Trimolecular)

2 FeCl 3+ O2 FeCl 4 +2 FeC 2

(Trimolecular)

The minimum number of reacting particles (molecules, atoms or ions) that come together or collide in rate determining step to form
product or products is called the molecularity of a reaction.

1
H 2 O 2 H 2 O+ O2
2

Step 1: H 2 O2 H 2 O+[O]

(Overall reaction)
(Slow)

Step 2: [ O ] +[O]O2

(Fast)

The slowest step is rate-determining step. Thus from step 1, reaction appears to be unimolecuar important
Important
i) Molecularity is a theoretical concept.
ii) Molecularity cannot be zero, ve, fractional, infinite and imaginary
iii) Molecularity normally not be greater than three because more than three molecules rarely collide with each other.
3.3 Rate Law or Rate Equation: The determination of the rate la expression of a complex reactions is not an easy task. Its
determination requires,
i) Information about the number of moles of reactants consumed during the reaction.
ii) A knowledge of the intermediates produced during the reaction and ho much they accumulate during the early period of reaction.
iii) The rate data to be supplemented by different techniques so that the certain elementary steps are verified to the maximum.
In complex reactions thus the rate expression written on the basis of the overa balanced equation has no significance at all. It merely
represents a theoretical expression. The true rate expression for such complex reactions can be evaluated on the basis of the
experimental data ony. For example, in the reaction between NO2 and F2 to yield nitrosyl fluoride (NO2F), i.e.

2 NO 2 ( g )+ F 2 ( g ) 2 NO 2 F ( g)
the rate expression on the basis of law of Mass Action is

NO 2

F
[ 2 ]
rate=k

Experimentally, it has been observed that the rate of this reaction is proportional to the product of single concentration term of NO 2
and F2. Thus, exprimental rate of the reaction or the actua rate of reaction is given as

NO
F
[ 2].
[ 2]
rate=k

A mathematical expression that gives the true rate of a reaction in terms of concentration of the reactants, which actually infuence the
rate, is cale Rate Law.
3.4 Rate Controlling Step: As pointed out that the complex reaction proceeds through more than one steps. Let us now understand that
which of these steps can be used to write the rate expression. Out of various steps of the reaction the slowest step will decide the rate
of overall reaction because the reaction cannot take place faster than the slowest step. Thus, the sowest step of the complex reaction is
caed the Rate Controlling Step or Rate Determining Step. A few examples given below will illustrate the above point (s) more easily:
Reactions Involving Slow Steps
Therma decomposition of nitrous oxide

2 N 2 O 2 N 2+ O 2
On the basis of experimental data it is observed that the rate of this reaction depends on the single power of concentration of

N 2 O . Thus, a possible mechanism of the reaction may be proposed as:

Step:1.

N 2 O slow step N 2 +O

N 2 O+O fast step N 2 +O2

Step:II.

2 N 2 O 2 N 2 +O2 Overall reaction

Thus, the rate law expession for the reaction can be written as

Rat=k [ N 2 O ]
The above postulated mechanism is consistent with the rate law expression.
3.5 Order of a reaction: Thus, the order of reaction is defined as the sum of the powers to which the concentration terms are raised in
the rate law expression. The power of the concentration of a particular reactant in the rate law is called the order of the reaction with
respect to that reactant.
Thus, if the rate of reaction

aA+ bB+cC Product

is given by the rate law as:-

Rat=

dx
q
r
p
=K [ A ] [ B ] [ C ]
dt

Then, the order of reaction, n is n = p+q+r

Where p, q and r are the orders with respect to individual reactants and overall order of reaction is sum of these exponents i.e. p + q + r
When n = 1, the reaction is said to be first order, if n = 2, the reaction is said to be second ode reaction and so on.
Reactions of different orders
i) Reaction of first order
Decomposition of Nitrogen pentoxide (N2O5)

1
N 2 O5 ( g ) 2 NO2 ( g )+ O2 ( g)
2
Rate=k [ N 2 O 5]

Order = 1
ii) Reaction of second order
Decomposition of nitrogen peroxide

2 NO 2 2 NO +O 2
NO 2 2
Rate=k
Order=2

iii) Reaction of thid order

Reaction between nitric oxide and oxygen

2 NO +O2 2 NO 2
2

Rate=k [ NO ] [ O 2 ]

Order=3
iv) Reaction of Fractional order
Decomposition of acetaldehyde is a fractional order reaction

CH 3 CHO CH 4 +CO
CH

CHO
3

Rate=k
3
Order= 1.5
2
v) Zero-order reaction
A number of zero order reactions are known in which the rate of the reaction is independent of the concentration of the reactants.
For example,
The rate decomposition of ammonia at the surface of metals like gold, platinum etc,, is zero order reaction.

2 NH 3 Platinum N 2+ 3 H 2

It has been observed that the rate of the reaction is independent of the concentration of ammonia.
0

NH 3 Rat =k
dx
i. e . Rate=
=k
dt
order = 0
3.6 Pseudo-order reactions: Reactions whose actual order is different from that expected using rate law expression is called pseudoorder reactions,
i) Hydrolysis of esters
'

'

RCOOR + H 2 O RCOOH + R OH

follow first order kinetics: Rate =k [RCOOR]

ii) Inversion of cane sugar in aqueous solution

C
follow first order kinetics: Rate=k [ 12 H 22 O 11 ]

3.7
MOLECULARITY
1. It is the total number of reacting species (molecules, atoms or
ions) which bring the chemical change.
2. It is always a whole number.
3. It is a theoretical concept.
4. It is meaningful only for simple reactions or individual steps of
a complex reaction. It is meaningless for overall complex
reaction.

ORDER OF REACTION
1. It is the sum of powers of molar concentration of the reacting
species in the rate law equation of the reaction.
2. It may be a whole number, zero, fractional, positive or negative
3. It is determined experimentally.
4. It is meant for the reaction and not for its individual steps.

3.8 Units of rate constant:

Unit of rate constant =

mol/litre

n1

litre
sec =
mol
1

n1

]
[ ]

1
unit of concentration

time1

n1

sec 1

Order of reaction
Zero order

Units
1

mol L time

1st order

time1

2nd order

mol1 Ltime 1

3rd order

mol2 L2 time 1

nth order

mol2 L2 time 1

nth order

L mol

3.9 Common examples of rirst order processes

i) Radioactive decay
ii) Rate of growth of population if there is no change in the birth rate or death rate.
iii) Rate growth of bacterial culture until the nutrients are exhausted.
4. REACTIONS OF VARIOUS ORDERS
4.1 Zero order reactions: A reaction is said to be of zero order if its rate is independent of the concentration of the reactants.

A products be of zero order ,

dx
o
=k [ A ] =k
dt

Some photochemical reactions and a few heterogeneous reactions are zero-order reactions.
Examples:
i) Photchemical reaction between hydrogen and chlorine:

H 2 ( g ) +Cl 2 (g)hv 2 HCl( g)

This photochemical reaction is zero-order reaction. The reaction is studied by placing H2 and Cl2 gases over water.
ii) Decomposition of N2O on hot platinum surface :

N 2 O N 2+1 /2 O2

N2
0

Rate [ N 2 O ] =k [ ]o =k

Or

N
d [ 2 O]
=k
dt

iii) Decomposition of NH3 in presence of molybdenum or tungsten is a zero-order

2 NH 3 [ Mo ] N 2 +3 H 2

4.1.1 Characteristics of zero-order reaction

i) The concentration of reactant decreases linearly with time.

[ A ] t= [ A ]0 kt

ii) The time required for the reaction to complete, i.e., time at which
iii) The units of k are

[A]

is zero.

t completion=

[ A ]0 Initial concentration
k

mol L1 time 1

4.2 First order reactions

A reaction is said to be of first order if its rate is determined by the change of one concentration term only.

Rate constant

dx
=k (ax)
dt
Or

dx
=kdt
(ax)
dx

Upon intergration of above equation

(ax) =k dt

log e ( ax )=kt +c

Or

Where c is integration constant.

When t=0, x=0,

c=log e a

Putting the value of ' c' ,log e ( ax )=ktlog e a

log e alog e ( ax )=kt
log e
k=

a
=kt
(ax )

2.303
a
log 10
t
( ax )

The following two important conclusion are drawn from this equation:
i) A change in concentration unit will not change the numerical value of k.

So ,k =
k=

2.303
na
log 10
t
n (ax)

2.303
a
log 10
t
( ax )

ii) The time taken for the completion of same fraction of change is independent of initial concentration.

x=0.5 at=t t / 2

So,

Or

k=

2.303
log 10
t 1 /2

t 1 /2 =

a
2.303
0.693
=
log 10 2=
0.5 a
t 1 /2
t 1 /2

0.693
k

This time t in which the initial concentration becomes hal is termed as hal life period. Half life period of a first order reaction is
independent of the initial concentration of the reactant.
When the log of the concentration of the reactant at various intervals of time is plotted against the time intervals, a straight line is
obtained.
4.2.1 Examples of first order reactions

4.3 Second-order reactions

Examples of second order reactions
i) Hydrolysis ester by an alkali (saponification) i.e.

CH 3 COOC 2 H 5+ NaOH CH 3 COONa+C 2 H 5 OH

ii)

The decomposition of NO2 into NOO2 i.e.

2 NO 2 2 NO +O 2

4.4 Third-order reactions

Examples of third order reactions.
i)

Reactionbetween nitirc oxideoxygen i. e . 2 NO +O2 2 NO 2

ii)

Reactionbetween nitric oxidechorine i .e .2 NO +Cl2 2 NOCl

4.5 Methods for Determination of order of a reaction

i) Method of integration (Hit and trial method): The most simple method is the one in which the quantities a, x and t are determined
and substituted in the kinetic equations of various orders. The equation, which gives the most constant value for the speciic rate
constant (k) for a series of time intervals is the one corresponding to the order of reaction.

k=

2.303
a
1
1
1
log 10
, for first order reactions ; k =
, for second order reaction ;
t
t
(ax )
(ax) a

k=

1
1
1
2 , for third order reactions .
2
2 t (ax) a

ii) Graphical method: A graphical method basd on the respective rate laws can also be used. If the plot of log (ax) versus t is a
straight line, the reaction follows first order. If the plot of

1
(ax)

versus t is a straight line, the reaction follows second order. If

the

1
plot of (ax)2

versus t is a straight line, the reactions follows third order, in general,

1
for a reaction of nth order, a graph o (ax)n1

versus t must be a straight line.

4.6 Graphical Methods For Determination Of Order

i) Plots of rate vs, concentration for different order reactions [Rate=k (conc.)n]

5. REACTIONS INVOLVING INTERMEDIATES IN EQUILIBRIUM WITH THE REACTANTS

For example, consider the general reaction

The reactants first combine to form an intrmediate X which is in equilibrium with the reactants (as rate constants k 1 and k2 are quite
large). The intermediate X then decomposes slowly to form the products so that equilibrium concentration of X remains almost
undisturbed. The rate of reaction is given by the rat of decomposition of the intermediate. Thus we have

Eqm . const , K =

k
[X]
, K= 1
k2
[ A] [ B ]

Rate of reaction=k 3 [ X ] =k 3 K [ A ][ B ] =

k 3k 1
[ A ] [ B ] =k 0 [ A ] [ B ]
k2

Thus, the reaction is of second order and the rate expression involves all the constants.
6. PARALLEL REACTIONS
When a single reactant gives two or more than two products with different rate constants is known as parallel reaction. This type o
reaction generally occurs in organic chemistry.
Let us consider reactant A breaks into two products B and C with rat constants K1 min1. Let a, b th initial concntration o A, x and y be
the concentration of B and C respectively after time t.

at time t = 0
at time t = t
i) Considering,

a
a (x+y)

A B
Rate of disappearance of A = rate of appearance of B
Or

d [ A]1 d [B ]
=
=K 1 [ A ]
dt
dt

ii) Considering,

A C

Rate of disappearance of A = rate o appearance of C

Or

d [ A ] II d [C]
=
=K 2 [ A ]
dt
dt

K
( 1+ K 2)[ A ]
Net rate of disapparance of
d [ A ]
A=
=K 1 [ A ] + K 2 [ A ] =
dt

Or

K
( 1+ K 2) [ A]
d [ A ]
=
dt

at time t = 0

a( x + y + z)

at time t = t
then we can write as,

K=

2.303
a
log
, K=K 1 + K 2 + K 3
t
a( x + y + z )

7. SEQUENTIAL OR CONSECUTIVE REACTIONS

Let us consider a reaction when there are two successive stages of the first order i.e, A decomposes to B, which further decomposes to
C.

A k1 B k 2C

Rate of disappearanc A ,

Rate of disappearance of B,

d[A]
d [ B]
K 1 [ A ] =rate o formation of B=
dt
dt

d [ B]
d [C]
=K 2 [ B ]=rate o ormationof C=
dt
dt

.(i)

.(ii)

Rate of change of B = rate of formation of B rate of disapparance of B.

d (B)
=K 1 [ A ] K 2 [ B ]
dt

8. COLLISION THEORY OF REACTION RATE (ARRHENIUS THEORY OF REACTION RATE)

i) A chemical reaction takes place due to collision
among reactant molecules. The number of
collisions taking place per second per unit
volume of the reaction mixture is known as
collision frequency (Z). The value of colision
frequency is very high, of the order of 1025 to
1028 in case of binary collisions.
ii) Every collision does not bring a chemical
change. The collisions that actually produce the
products are effective collisions.
8.1 Energy Barrier: The minimum amount energy, which the colliding molecules must possess as to make the chemical reaction to
occur, is known as threshold energy. The minimum amount of energy required by reactant molecules to participate in a reaction is
calle activation energy.
Activation energy = threshold energy average kinetic energy of reacting molecules.
Threshold energy = initial potential energy of reactant molecules + activation energy. A collision between high, energy molecules
overcomes the forces of repulsion and brings theformation of an unstable molecule cluster, called the activated complex. The life
span of an activate complex is very small. Thus, the activated complex breaks either into reactants again or new substances, i.e.,
product. The activation energy (Ea) depends upon the nature of chemical bonds undergoing change and is independent of enthalpies of
reactants and products. The energy changes during exothermic and endothermic reactions versus the progress of the reaction are given
below

Activation energy Ea = E(activated complex) E(ground state)

H = activation energy of forward reaction activation energy of backward reaction
8.2 Orientation Barrier : Energy along not determine the effectiveness of the collision.

Rate of reaction is directly proportional to the number of effectiv collisions.

Rate=

dx
= collision frequency x fraction of effective collisions = z x f
dt

8.3 Factors affecting rate of reaction

8.3.1 Nature of the reactants
i) Physical state of reactants: This has considerable effect over rate of reaction

Gaseus state> Liquid state >Solid state

Decreasing rate of reaction

Simiarly in a heterogeneous system collision is not so effective as in homogeneous system. Thus, reactions in liquid phase or solution
phase will be faster in comparison to heterogeneus conditions when same concentration of the reactants are taken.
ii) Physical size of the reactants : Among the solids, rate increases with decrease in particle size. In powdered state rate of reaction is
maximum because in powdered state, surface area is maximum.
iii) Chemical nature of reactants : Consider the following two reactions:

2 NO ( g )+ O2( g)2 NO2 (g)

.(i)

CH 4 ( g )+ 2O2 ( g ) CO2 ( g ) + H 2 O(l)

.(ii)

The first reaction is faster than the second because in the first reaction only

N O bond is to broken whereas in the second

reaction four (CH) bonds are to be broken.

8.3.2 Concentration of reactants : Let us consider the reaction:

A + B C+ D , Rate=k [ A ] [B ]
Rate of the above reaction decreases with the
Passage of time because the reactants A and B
Will decreases as time passes on
Let us consider the following reversible reaction

A + B C+ D

Rate of forward reaction

Rate of backward reaction

k f [ A ] [ B]
k b [ C ] [ D]

Rate of forward reaction decreases and that of

Backward reaction increases with passes of
Time. At equilibrium both the rates become
equal.
8.3.3 Effect of temperature: The rate of reaction increases considerably with an increase in temperature. The rates of many reactions
are approximatey doubled or tripled for every 100C rise in temperature. The temperature coefficient of a chemical reaction is defind as
the ratio of the specific reaction rates of a reaction at two temperature differing by 100C.

Q10=Temperature coefficient=

k t+ 10
kt

9. ARRHENIUS EQUATION

k =AeE / RT where k =rate constant , A=a constant

a

(frequency factor),
At two temperatures

Ea =energy of activation
T 1 and T 2 , taking log of Arrhenius

Equation, we get

And

log e k 1=log e A

Ea
RT 1

.(i)

log e k 2=log e A

Ea
RT 2

.(ii)

Subtracting Eg. (ii) from Eq. (i) and converting the og to the base 10, we get

[
[

]
]

log10

k1
E a T 2T 1
=

k 2 2.303 R T 1 T 2

log 10

k2
Ea
T 2T 1
=
k 1 2.303 R T 1 T 2

log 10 k=log 10 A

Ea
1
y=m x +c
2.303 R T

[]

It is equation of straight line with negative slope. On

plotting log10 k against [1/T] we get straight line.
In the Arrhenius equation when
When

T , then k= Ae =A .

Ea =0, k= A , then rate of reaction becomes independent of temp.

i) Presence of a positive catalyst: The function of a positive catalyst is to lower down the activation energy. The greater the decrease in
the activation energy caused by the catalyst, higher will be the reaction rate. In the presence of a catalyst, th reaction follows a path of
lower activation energy. Under this condition, a large number of reacting molecules are able to cross over the energy barrier and thus
the rate of reaction increases.
ii) Presence of negative catalyst: A negative catalyst increases the activation energy of reaction by forming a new intermediate of high
energy, i.e., by changing the reaction mechanism.
Due to increases activation energy, some acitve molecules become inactive, therefore, rate of reaction decreases.
10. PHOTOSENSITIZER
It is substance which when added to a reaction mixture helps to initiate the photochemical reaction without undergoing any chamical
change itself. This phenomenon is known as photosensitization e.g., chlorophyll acts as photosensitizer in the photosynthesis.

Some common example of photosensitized reactions are :

Hydrogen molecule does not undergo dissociation when exposed to light. However, it gets dissociated to atomic hydrogen in the
presence of mercury vapours when exposed to light readiatin of some wavelength. The reaction is believed to proceed as :

Hg+ hv Hg

In the above reaction, mercury acts as photosensitizer.

10.1 Importance of Photochemical Reactions : Photochemistry plays an important role in our daily
life. Some common examples are:
i) Photosynthesis is very common example of reaction occuring in plants of the light.
ii) Light is used in the synthesis and manufacture of many organic compounds. This is called photochemical synthesis. For example,
formaldehyde is synthesised from CO and H2 in the presence of Hg using light.
iii) Polymerisation is generally initiated by light.
iv) Photography is based upon photochemistry.
v) Photo etching is used in electronic industry.
vi) Printing technology also makes use of photochemical processes.
vii) Sterilisation of water.
10.2 Quantum yield or quantum efficiency of a photochemical reaction

number of reactantmolecules reactinga giventime

number of photons ( quanta ) of light absorbed the sametime

Different photochemical reactions have different values of quantum efficiency depending upon their mechanisms. For example,
photosynthesis of HBr has low value of

11. FAST REACTIONS The reaction which take place in just a fraction of a second to complete are called fast reactions. The kinetics

10
10
10
of fast reactions are expressed in milli seconds ( 3 s ), micro seconds (6 s) , nano seconds (9 s) and pico

10
seconds (12 s) . The rates of fast reactions can be studied by spectrophotometric techniques based on light absorption and

emission i.e., change in the intensity of the colour of the reaction mixture. Some other techniques based on laser, magnetic properties
and electrical conductances are also being used.
EXAMPLES
EXAMPLE:1 The following data are for the reaction

A + B products

Conc. Of A (M)

Conc. of B (M)

0.1
0.2
0.5
0.5

0.1
0.2
0.1
0.5

mol L
1
(
1 s )
Initial Rate

4.0 104
1.6 103
1.0 102
1.0 102

A. What is th order with respect to A and B for the reaction?

B. Calculate the rate constant.
C. Determine the reaction rate when the concentrations of A and B are 0.2 M and 0.35 M respectively.
EXAMPLE:2 Thermal decmposition of a compound is of first order. If 50% sample of the compound is decomposed in 120
minutes, how long will it take for 90% of the compound to decompose?
EXAMPLE:3 The rate constant for an isomerization reaction
1 M, calculate the rate of the reaction after 1 hour.

A B is 4.5 103 min1 . If the initial concentration of A is

EXAMPLE:4 A substance reacts according to first order kinetics and rate constant for the reaction is

2 1

1 10 s . If its

initial
concentration is 1 M,
A. What is initial rate?
B. What is rate after 1 minute?
EXAMPLE:5 A first order reaction takes 69.3 minutes for 50% completion. How much time will be needed for 80% completion?
EXAMPLE:6 In order to study the kinetics of the reaction
A solution
initially 0.12 in ethylene oxide and 0.007574 M in perchoric acid was prepared and the progress of the reaction was followed
diatometricaly. The following data were obtained at 200C.

T(min.)

30

60

135

300

Dilatometer
18.48
18.05
17.62
16.71
15.22
12.29
Determine the order of the reaction with respect to ethylene oxide and evaluate the specific rate constant.
EXAMPLE:7 The rate constant for the first order decomposition of a certain reaction is given by the equation

1.25 10
(1)=14.34
T
k

Calculate
A. the energy of activation,
B. the rate constant at 500 K.
C. at what temperature will its half life period be 256 minutes?
EXAMPLE:8 Compounds A and B react to form C and D in a reaction that was found to be second-order overall and secondorder in A. The rate constant at 300C is 0.622 L mol1 min1. What is the haf-life of A when

4.10 10

M. of A is mixed

with excess B?
EXAMPLE:9 The rate constant for the decomposition of a certain substanc is

1 1

1.38 10 M s

2.80 103 M 1 s1 at 300 C and

R=8.314 10
0
1 1
50
C
at
. Evaluate the Arrhenius parameters of the reaction ( 3 kJ mol k )

EXAMPLE:10 The rate constant for the first order decomposition of ethylene oxide into CH 4 and CO may be described by

log 10 k ( s1 )=14.34

1.25 10 K
T

A. What is th energy of activation for this reaction?

B. What is the value of k at 670 K?
EXAMPLE:11 The rate of change in concentration of C in the reaction;

2 A+ B 2C +3 D , was reported as 1.0 mole litre

sec1
Caculate the reactin ate as well as rate of change of concentration of A, B and D.
EXAMPLE:12 The reaction;

litre

2 N 2 O 5 4 NO2 +O2 , shos an increases in concentration of NO by 20 103 mol

2

in 5 seconds. Calculate (a) rate of appearance of NO2, (b) rate of reaction and (c) rate of disappearance of N2O5.

EXAMPLE:13 For ;

2 A+ B+ C Products, calculate the;

(excess)
A. rate expression
B. units of rate and rate constant
C. effect on rate if concentration A is doubled and of B is tripled.

4 NH 3 (g) +5 O2 ( g ) 4 NO( g )+ 6 H 2 O(g)

EXAMPLE:14 For the reaction

The rate of reaction in terms of disappearance of

NH
d [ 3]
,
then write the rate expression in terms of concentration of
dt
NH 3 is

O2 . NO and H O
2
EXAMPLE:15 The specific rate constant for the decomposition of formic acid is
specific ratae constant at 458 K if the energy of activation is

5.5 104 sec1 at 413 K. Calculate the

2.37 10 4 calmol1

EXAMPLE:16 Derive the order of reaction for decomposition of H2O2 from the following data.
Time in minutes 10
Volume of

15

O2 given by H 2 O2

15

20

6.30

8.95

25
11.40

13.5

13.75

EXAMPLE:17 In a pseudo first order hydrolysis of ester in water the following results were obtaining t/s
t/s
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.
EXAMPLE:18 A substance undergoes first order decomposition. The decomposition follows two paralel first order reactions as:
The percentage distribution of B an C are:
A. 80% B and 20% C
B. 20% B and 80% C
C. 76.83% B and 23.17% C
D. 23.27% B and 76.83% C
RT

E a /
EXAMPLE 19 For reaction A B , the rate constant k = A e and for the reaction P Q , the rate constant
1
1
1

k 2= A 2 eEa / RT
2

If

8
10
A 1=10 , A2=10 Ea =600, Ea =1200, then the temperature at which k 1=k 2 is
1

A. 600 K
C.

600
K
4.606

B.

300 4.606 K
D.

4.606
K
6 00

EXAMPLE:20 The half life for a zero order reaction equals

A.

C.

1 k
2 a2
2k
a

a2
B. 2 k

D.

a
2k

EXAMPL:21 The rate constants for two parallel reactions were found to be

1.0 102 dm3 mol1 s13.0 102 dm 3 mol1 s1

If the corresponding energies of activation of prallel reactions are 60.0 kJ mol 1 and 70.0 kJ mol1 respectively, the apparent
overall energy of activation is :
A. 130.0 kJ mol1
B. 67.5 KJ mol1

C. 100.0 KJ mol1
EXAMPLE:22

D. 65.0 KJ mol1

2 N 2 O5 4 NO2 +O2

The above reaction is first order and takes 24 min for 75% decomposition of N 2O5. At the end of one hour after the start of the
reaction, the amount of oxide left is
A. nil
C.

B.

D.

EXAMPLE:23 A certain reaction proceeds in a sequence of three elementary steps with the rate constant K 1, K2 and K3. If the
1 /2

[ ]

K1

observed rate constant, Kobs of the reaction is express Kobs

K2

=K 3 . The observed energy of activation of the

reaction is
A.

C.

[ ]
[ ]

1 E1
+E3
2 E2
E
E3 1
E2

B.

1 /2

D.

E3 +

E 3+ E 1
E2

1
[ E +E ]
2 1 2

EXAMPLE:24. the reaction between NO and Br2 takes place into two steps

NO+Br 2

i.

NOBr 2+ NO K 3 2 NOBr

ii)

if

K 1 > K 2 > K 3 , then the rate law of the overal eaction, 2 NO + Br2 2 NOBr can be given by

Br

A.
2
r=K [ NO ]
C.

r=k [ NOBr ] [ NO]

B.

r=k [ NO ] [Br 2 ]

Br 2 2
D. r= [ NO ]

EXAMPLE:25. Reaction A follows first order kinetics and reaction B follows second order kinetics. It their half lives are equal,
the ratio of their reaction rates at the start of reaction is
A.

R1 K1

R2 K2

C.

R1 2 K1
=
R2 K2 a

B.

D.

R1 K1
=
R2 K2 a

R2 K1
=
R1 K2 a

EXAMPLE:26. The slope of the line in the graph of log k versus

1
T

for a reaction is 5841 K. Calculate the energy of

activation for this reaction.

A. 111.84 kJ mol1
B. 115 kJ mol1
1
C. 116.24 kJ mol
D. 114 kJ mol1
EXAMPLE:27. The rate of reaction tripls when temperature changes from 200C to 500C. Calculate the energy of activation for
the reaction. (R=8.31 J K1mol1).
A. 28.82 kJ mol1
B. 2.882 kJ mol1
C. 26.4 kJ mol1
D. 2.64 kJ mol1

EXAMPLE:28. A radioactive substance decays 20% in 10 minutes. If at the start there are

20

5 10

atoms present, after

what time will the number of atoms be reduced to 1018 atoms?

A. 4.65 hour
B. 46.5 hour
C. 4.65 minutes
D. 46.5 minute

N 2 O 4(g ) 2 NO 2 (g ) .

EXAMPLE:29 For the decomposition reaction:

the initial pressure of N2O4 falls from 0.46 atm to 0.28

atm in 30 minutes. What is the rate of appearance of NO2?

A.

1.2 1012 atm min

C.

12 10 atmmin

B.

6 103 atm min1

D.

1.2 10 atm min

EXAMPLE: 30 The values of rate constant for the decomposition of

1
N 2 O5 , N 2 O5 N 2 O 4 + O2 , are 3.46 1054.87 103 at 25 0 C and 650 C respectively.
2

The energy of activation is

A. 24.8 Kcal mol1
C.

31.2 Kcal mol1

B.

2.48 Kcal m ol1

D.

3.12 Kcal mol1

EXAMPLE:31 In a reaction between A and B, the initial rate of reaction was measured for different initial concentrations of A
and B as given below:
A/M
0.20
0.20
0.40
B/M
0.30
0.10
0.05

r 0 / Ms1

5.07 10

5.07 10

7.6 10

What is the order of reaction with respect to A and B?

A.

order w . r . t . A=0.58, order w . r .t . B=0

B.

order w . r . t . A=0, order w . r . t . B=0.58

C.

order w . r . t . A=1,order w . r .t . B=1.5

D.

order w . r . t . A=1.5,order w . r .t . B=1

EXAMPLE:32 How much faster woud a raction proceed at 250C than at 0oC if the activation energy is 65 kJ:
A. 2 times
B. 16 times
C. 11 times
D. 6 times.
III. MULTIPLE CHOICE QUESTIONS (with more than one correct choice)
EXAMPLE:33 Arrhenius equation may be represented as
A.

A Ea
=
K RT

Ea
log
A=log
k
+
C.
2.303 RT

B.

dk Ea
=
dT
RT

( )

Ea
k
log
=
D.
RT
A

EXAMPLE:34 For first reaction

1e
(kt)
A. the degree of dissociation is equal to

B. a plot of reciprocal of conc. of reactant vs time gives a straight line

C.

t 75 =3 t 1 /2

D. The pre-exponential factor in Arrhenius equation has the dimension of time T1.

EXAMPLE:36 The rate law for the reaction

RCl+ NaOH ROH + N aCl

Is given by rate = k[RCI]. The rate of this reaction

A. is doubled by doubling the conc. of NaOH
B. is halved by reducing the conc. of RCI by one half
C. is increased by increasing the temperature of the reaction
D. is unaffected by change in temperature
EXAMPLE:37 Arrhenius equation is

E
( a/ RT 2 )
B.
(d / dt ) K=+

E/ RT
(d
/dt)
K=( 2)
A.

C.

(d /dt )K=( E/ RT )

D.

K= AeE / RT
a

EXAMPLE:39 Which of the following statements are correct?

A. Law of mass action and rate law expressions are some 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 +2 B C is3

EXAMPLE:40 Select the correct statements:

A. for the reaction,

H 2 ( g ) + I 2 ( g ) 2 Hl ;

B. at equilibrium net rate of change

d [ H 2]
=K b [ Hl]2 for backward reaction and
dt

d [ H2]
=K f [ H 2 ] [ I 2 ]
dt

[ H 2 ]=0 for H 2+ I 2 2 Hl

C. a thermodynamically favourable process actually takes place

D. a thermodynamically favourable process will not actualy take place unless it chemical kinetics favourable
EXAMPLE:41 Which statements are correct about the two first order reactions if made with same initial concentrations?

M Product

N Product
A.

t 1 /2 for M is more than t 1 /2 of N

B.

t 1 /2 for M is less than t 1 /2 of N

C. Rate constant for M is more than rate constant for N

D. Rate constant for M is less than rate constant for N

IV. ASSERTION AND REASON
In each of the following questions two statements are given. One is assertion (A) and one is reason (R). Mark the correct answer as
A. If both A and R are true and R is the correct explanation of A
B. If both A and R are true and R is not the correct explanation of A
C. If A is true but R is false
D. If A is false but R is true.

EXAMPLE:42 Assertion (A): For the reaction,

K
2O3 3 O 2 ; therate=

Reason (R): The reaction has ve order for O2.

A. A
B. B
C. C
D. D
EXAMPLE:43Assertion (A): The emission of light during burning of P in O2 is called chemiluminscence.
Reson (R): The chemical energy is converted into light energy.
A. A
B. B
C. C
D. D
EXAMPLE:44 Assertion (A): Phososynthesis in plants involves reaction of CO2 and H2O in presence of light and chlorophyll.
Reason (R): It is chlorophyll which absorbs light and passes this energy to reactant molecules.
A. A
B. B
C. C
D. D
EXAMPLE:45 Assertion (A): The rate of reaction whether exothermic or endothermic. Increases with temperature.
Reason (R): The rate o reaction
A. A
C. C

K [reactant]

and K increases with temperature

B. B
D. D

EXAMPLE:46 Assertion (A): The kinetic of the reaction

mA +nB+ pC m' X + n' Y + p ' Z obeys the rate expression as

B n
dX
=k [ A]m
dt
Reason (R): The rate of the reaction does not depend upon the concentration of C.
A. A
B. B
C. C
D. D
EXAMPLE:47 Assertion (A): According to steady state hyothesis, in a multistep reaction, the change in concentration with time for
reactive intermediates is zero
Reason (R): The intermediates are so reactive that after a brief initia period thir concentrations rise rom zero to a small value and
remains constant for most of the duration of the reaction.
A. A
B. B
C. C
D. D
EXAMPLE:48 Assertion (A): For each ten degree rise of temperature the speciic rate constant is nearly doubled.
Reason (R): Energy-wise distribution of molecules in a gas is an experiment function of temperature.
A. A
B. B
C. C
D. D
V. COLUMN MATCHING
EXAMPLE:49 Match the following
Column I
Column II
Reactions
Experimental Methods
A.

2 N 2 O5 ( g ) 4 NO 2 ( g ) +O2 ( g)

P. Measurement of optical activity

+
H

B.

CH 3 COO H 2 H 5 ( aq ) + H 2 O

Q. Measurment of volume of gas at constant P and T

CH 3 COOH ( aq ) +C 2 H 5 OH (aq)
C.

C6 H 5 N =NCl ( aq ) C 6 H 5 Cl ( l ) + N 2 ( g)

R. Titration of an a liquid of reaction mixture with

alkali

+
H

D.

C12 H 22 O11 ( aq ) + H 2 O

S. Measurmnt of pressure of reaction mixture at constant V

C6 H 12 O6 ( aq ) +C 6 H 12 O6 ( aq)
Glucose
fructose
EXAMPLE:50

and T

C0 = initial concentration of reactant; C = Concentration of reactant at any time t; k = rate constant Match

the following:
Column I
A. C Vs t (abscissa) for zero order
B. log C Vs t (abscissa) for first order
C.

Column II
P. Unity
Q. Zero

Vs C for zero order

( dc
dt )

D. In

R. k

VsC for first order

( dc
dt )

S. k/2.303

TRUE/FALSE
EXAMPLE:51. The rate constant of most of the ionic reactions do not increase with increase in temperature
EXAMPLE:52. The rate of endothermic reaction increases with increasing temperature
EXAMPLE:53. The reaction has rate

1/ 3

K [ A ] [B ]

. It is an elementary process.

EXAMPLE:54. The unit of rate of reaction varies with order of reaction.

EXAMPLE:55. The temperature coefficient of reaction normally lies in between 2 and 3.
EXAMPLE:56. An elementary process involve one step reaction mechanism.
EXAMPLE:57. Time required to complete half of the reactant in a zero order reaction is equal to a/2k.
EXAMPLE:58. The unit of rate constant for a given reaction is

M 1n Ln1 t 1 where n is order of reaction.

EXAMPLE: 59 Decomposition of ozone shows negativ order with respect to oxygen.

FILL IN THE BALANKS
EXAMPLE:60. When

dx /dt =k [ A ][B] 2 , the reaction is said to be of .order in A and of.order in B. The

overal order is.

EXAMPLE:61. The hydrolysis of ethyl acetate in heavy water ..is than in ordinary water.
EXAMPLE:62. For the reaction,

N 2 +3 H 2 2 NH 3 under certain conditions of P and T. The rate of formation of NH 3 is

0.001 kg hr 1 . The rate of conversion of H2 under these conditions is..kg hr1. The rate of conversion of H2 under
these conditions is..kg hr1
EXAMPLE:63. The rate of reaction is.when the activation energy is small.

EXAMPLE: 64. In the Arrhenius equation,

K= A exp(E / RT ) . A may be termed as rate constant at..

a

EXAMPLE:65. The inversion of cane-sugar is a.reaction though its molecularity is..

EXAMPLE:66. Instngtaneous rate and average rate of a reaction are same when..
EXAMPE:67. The unit of rate constant is same as that o rate of..reaction.
EXAMPLE:68. Reaction having molecularity > 2 but order of reaction = 1 are known as..reactions.
EXAMPLE:69. Kinetic studies of reactions involvereactions