Chemical kinetics

1) Chemical kinetics is the branch of chemistry which deals with the study of the velocity of chemical

reactions and their mechanism.

2) Rate of Reaction:

change in concentration of any one of the reactants or products per unit time.
 Unit of rate of a reaction mol L -1 s-1
 For gaseous reactions, the concentration is replaced by partial pressure and so the unit of rate
of reaction is atm/s.
3) Rate of reaction keeps on decreasing with time (except for zero order reaction ) .It is due to
decreases in concentration of reactant
4) Average Rate of Reaction:

change in concentration of any one of the reactants or products in a given time interval
Fora reaction, R → P

5) Instantaneous Rate of Reaction:

the rate of change in concentration of any one of the reactants or products at a particular instant of
time for a given temperature
 Expression of rate of reaction in term of different reactants and products
a) R  P
d [R ]
 Rate of disappearance of R = -
dt
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
 d [P ]
 Rate of appearance of P = -
dt
b) 2A  B+ C
1 d [R ]
 Rate of disappearance of R = -
2 dt
d [B]
 Rate of appearance of P = -
dt
d [C ]
 Rate of appearance of P = -
dt

 rinst = - dx/dt  , what is the significance of -ve sign ?

[Since, Δ[x] is a negative quantity (as concentration of reactants is decreasing), it is multiplied

with –1 to make the rate of the reaction a positive quantity].

 At what condition Average rate equal to instantaneous rate ?

When time interwell is small
 Determination of Instantaneous Rate of a reaction

 Instantaneous Rate of a reaction can be determined

graphically. First conduct the chemical reaction and
find out the concentration of reactants or product at a
regular interval of time. Then plot a graph between
concentration along y-axis and time along x-axis. In
order to determine the Instantaneous Rate at a
particular time, mark the point on the graph at that
time and draw a tangent at the point. The slope of this
tangent gives the instantaneous rate at that time.

 Express the rate of the following reaction in terms of the formation of ammonia:
N2(g) + 3H2(g) → 2NH3(g) (Comptt. All India 2013)
Answer:

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 1.

2.

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 4.

 Factors affecting rate of reaction:

Concentration of reactants, Nature of reactants and products, Temperature, Pressure (for
gaseous reactants), Presence of catalyst, Presence of light (radiation)
 Rate Law
It is the expression relating the rate of a chemical reaction directly proportional to the product
of molar concentration of reactants, in which each concentration term is raised to a power
which may or may not be equal to the stoichiometric coefficients in the balanced chemical
equation.”
- Thus, for a general reaction, aA + bB → cC + dD,
- Rate α [A]x [B]y
- r = k [A]x [B]y
(where x and y may or may not be equal to a and b) and K is rate constant
 Differential rate law expression −d[R]dt = k[A]x [B]v
Rate constant (K)
- the rate of the reaction when the concentration of each of the reactants is unity.
- Units of rate constant k= mol1-nLn-1s-1 or atm1-ns-1( n=order)
 Units of Rate Constant:
 For an nth order reaction, the unit of rate constant is given by the formula, mol1-n Ln-1 s-1 where
n=order of reaction
 For Zero order reaction (n=0) K= mol L-1 S-1
 For First order reaction (n=1) K= S-1
 For Second order reaction (n=3) k= mol-1 L s-1
 order of Reaction:
sum of powers of the concentration of the reactants in the rate law expression.
 Considers general reaction, aA + bB → cC + dD
Rate = k[A]x [B]v
Order = x + y
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
  Order of a reaction is an experimentally determined quantity. It may be zero, whole
number, fractional and even negative.
 BOARD QUESTIONS
1. State the order with respect to each reactant and overall reaction.
Rate = k[A]2 [B]1
2. Identify the order of a reaction from the following rate constant:
L mol-1s-1
3. For a reaction A + B → Product, the rate low is given by r = k[A] 1⁄2 [B]2
What is the order of the reaction?
4. A reaction is of second order with respect to its reactant. How will its reaction rate be
affected if the concentration of the reactant is (i) doubled (ii) reduced to half?
5. What do you understand by the ‘order of a reaction’? Identify the reaction order from each
of the following units of reaction rate constant: (i) L-1 mol s-1 (ii) L mol-1 s-
6. For the reaction: 2A + B → A2B the rate = k[A][B]2 with k = 2.0 × 10–6 mol–2 L2 s–1.
Calculate the initial rate of the reaction when [A] = 0.1 mol L–1, [B] = 0.2 mol L–1. Calculate
the rate of reaction after [A] is reduced to 0.06 mol L–1
7. A reaction is first order in A and second order in B.
(i) Write differential rate equation.
(ii) How is rate affected when concentration of B is tripled?
(iii) How is rate affected when concentration of both A and B is doubled?
8. The rate of a gaseous reaction becomes half when volume of the vessel is
doubled. What is the order of reaction?
9. Find the order and write the rate law
a. Rate becomes 23 times when concentration of A is increased 3 times
b. Rate becomes 4 times when Volume of A is increased 2 times
10. The following results have been obtained during the kinetics studies of the
reaction:C + D
Experiment [A] mol L-1 [B] mol L-1

11. In a reaction between A and B, the initial rate of reaction (r0) was measured
for different initial concentrations of A and B as given below:

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

12. The reaction between A and B is first order with respect to A and zero order with respect to
B. Fill in the blanks in the following table

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
  Elementary reactions – reactions taking place in one step.

 Complex reactions –reactions involving a sequence of elementary reactions. These may be

consecutive reactions, reverse reactions and side reactions.

 Rate exterminating step -slowest step in a chemical reaction

 Molecularity of a Reaction:
number of reacting species (atoms, ions or molecules) taking part in an elementary reaction,
which collide simultaneously in order to bring about a chemical reaction. It is always a whole
number.
 Reactions which involve simultaneous collision between two species are bimolecular.
 When one reacting species is involved in the reaction, it is unimolecular.
Example:
NH4NO2 → N2 +2H2O
O3 → O2 + O
 Reactions which involve simultaneous collision between two species are bimolecular.
Example:
2 Hl → H2 + l2
 Reactions which involve simultaneous collision between three species are trimolecular or
termolecular.
Example :
2 NO + O2 → 2 NO2
 The probability that more than 3 molecules can collide and react simultaneously is very small.
Hence, molecularity greater than 3 is not observed.
In a complex reaction, the slowest step in a reaction determine the rate of reaction, i.e., slowest
step is the rate determining step.
 For the following reaction

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
  difference between order and molecularity

Order Molecularity

1. It is sum of the powers of the concentration 1. It is the number of reacting species undergoing
terms in the rate law expression. simultaneous collision in the reaction.

2. It is determined experimentally. 2. It is a theoretical concept.

3. It can be a whole number, zero or even

3. It always a whole number.
fraction.

4. It gives some idea about reaction machanism. 4. It does not tell us the reaction mechanism.

 Difference between Rate of reaction and rate constant

Rate of reaction rate constant

1. change in concentration of
any one of the reactants or
products per unit time
2 Unit of rate of a reaction
mol L-1 s-1
It is proportionality constant in the rate law
equation and its equal to rate of reaction when
molar concentrations each reactant is unity
Units of rate constant is given by the formula,
mol1-n Ln-1 s-1

 Examples of zero order and First order

Zero order reaction First order reaction

Decomposition of ammonia on Pt surface All naturally and artificial Radioactive decay

Decomposition of N2O5

F 061, Rev 0, dtd 18th June 2017

Decomposition of HI on Gold surface Hydrogenation of ethene
MOHMMED.ILIAS
  Pseudo First Order Reaction :
Reaction which appear to be of higher order but actually follow lower order kinetics.

Example:
Acid hydrolysis of ethylacetate.

Rate = k[CH3-COOC2H5]

 Since the concentration of H2O is quite large and does not change appreciably, it does not
appear in the rate law.

Another example: In version of cane sugar

in presence of dilute acids.
 State a condition under which a bimolecular reaction is kinetically first order reaction.

Ans. A bimolecular reaction becomes first order reaction when one of the reactants is in excess.

 Why canít molecularity of any reaction be equal to zero ?

Ans. Molecularity of a reaction means the number of molecules of the reactants taking

place in an elementary reaction. Since at least one molecule must be present, so

that molecularity will be at least one.

Integrated Rate Equation :

Integrated rate equation gives a relation between concentrations at different times and rate constant.

Zero Order Reaction:

The rate of reaction is independent of the concentration of the reactants.

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 GRAPH

SLIOPE =-k

First Order Reaction

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 First Order Reaction
Fora reaction, R → P

Derivation:
For a first order reaction R → P, the rate
constant is given by the equation,

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
BOARD QUESTIONS;

1) Rate constant of first order reaction is 200 s -1. Calculate the half life
2) A first order reaction has a rate constant of 0.0051 min-1. If we begin with 0.10 M concentration of
the reactant, what concentration of reactant will remain in solution after 3 hours?
3) The rate law for a reaction is Rate = K [A] [B] 3/2. Can the reaction be an elementary process ?
Explain.
4) Determine the order of reaction

5) What is the order of reaction whose rate constant has the same units as the rate of reaction ?
6) Give an example of a reaction having fractional order.
7) The rate constant for a reaction of zero order A is 0.0030 mol L-1s-1 How long will it take for the
initial conc. of A to fall from 0.10M to 0.075M ?
8) For a first order reaction time taken for half of the reaction to complete is t1 and ¾ of the reaction
to complete is t2 How are t1and t2 related ?
9) For reaction

(a) What is the order of the reaction ?

(b) What is the slope of the curve ?

10) Show that in case of first order reaction, the time required for 99.9% of the reaction to take place is
about ten times than that required for half the reaction.
11) For a first order reaction, show that time required for 99% completion is twice the time required for
completion of 90% reaction
12) The rate constant for first order reaction is 60/s. How much time will it take to reduce the
concentration of the reaction to 1/10 of its initial value ?
13) For a chemical reaction R → P, variation in ln[R] vs time (f) plot is given below:
For this reaction:
(i) Predict the order of reaction

14) A first order reaction takes 30 minutes for 50% completion. Calculate the time required for
90% completion of this reaction
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
15) The rate constant for a first order reaction is 60 s–1. How much time will it take to reduce the initial
concentration of the reactant to its 1/16th value?
16) During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1μg of 90Sr was
absorbed in the bones of a newly born baby instead of calcium, how much of it will remain after 10
years and 60 years if it is not lost metabolically
17) is twice the time required for the completion of 90% of reaction. 4.19 A first order reaction takes 40
min for 30% decomposition. Calculate t1/2.
18) Sucrose decomposes in acid solution into glucose and fructose according to the first order rate law,
with t1/2 = 3.00 hours. What fraction of sample of sucrose remains after 8 hours?
19) For a reaction: H2 + Cl2 ⟶hv 2HCl
Rate = k
(i) Write the order and molecularity of this reaction.
(ii) Write the unit of k.
20) For the hydrolysis of methyl acetate in aqueous solution, the following results were obtained:

t/s 0 10 20
[CH3COOCH3]/mol L-1 0.10 0.05 0.025
i) Show that it follows pseudo first order reaction, as the concentration of water remains constant.
(ii) Calculate the average rate of reaction between the time interval 10 to 20 seconds. (Given : log 2
= 0.3010, log 4 = 0.6021) (
1) For a first order reaction, show that time required for 99% completion is twice the time
required for the completion of 90% of reaction.
2) A first order reaction takes 40 minutes for 30% decomposition. Calculate t1/2 for this reaction.
(Given log 1.428 = 0.1548) 
3) ollowing equation:
4) 4 PH3 (g) → P4 (g) + 6 H2 (g)
5) It is found that the reaction follows the following rate equation :
6) Rate = K [PH3].
7) The half-life of PH3 is 37.9 s at 120° C.
8) (i) How much time is required for 3/4th of PH3 to decompose?
9) (it) What fraction of the original sample of PH3 remains behind after 1 minute? (All India 2010)
10) Answer:
11)

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 1

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 For a reaction R → P, half-life (t1/2) is observed to be independent of the initial
concentration of reactants. What is the order of reaction? 
First order

Pseudo First Order Reaction :

Reaction which appear to be of higher order but actually follow lower order kinetics.
Example:
Acid hydrolysis of ethylacetate.

Rate = k[CH3-COOC2H5]
Since the concentration of H2O is quite large and does not change appreciably, it does
not appear in the rate law.

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 Another example: In version of
cane sugar in presence of dilute acids.

For the reaction ; 2A + B → A2B, the reaction rate = k [A][B]2 with k = 2·0 x

10-6 mol-2 L2 s-1. Calculate the initial rate of the reaction when [A] = 0·1 mol
L-1; [B] = 0·2 mol L-1. Also calculate the reaction rate when [A] is reduced
to 0·06 mol L-1.
The decomposition of NH3 on platinum surface is zero order reaction.
What are the rates of production of N2 and H2 if K=2.5 x 10-4 mol-1 Ls-1.
A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three
times?
(iii) How is the rate affected when the concentrations of both A and B is
doubled?
During nuclear explosion, one of the products is 90Sr with half-life of 28.1
years. If 1 µg of 90Sr was absorbed in the bones of a newly born baby
instead of calcium, how much of it will remain after 10 years and 60
years if it is not lost metabolically ?
Consider a certain reaction A → Products with k = 2.0 × 10-2 s-1.
Calculate the concentration of A remaining after 100 s if the initial
concentration of A is 1.0 mol L-1.

Sucrose decomposes in acid solution into glucose and fructose according to the first
order rate law, with t1/2 = 3.00 hours. What fraction of sample of sucrose remains
after 8 hours?

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 The reaction between A and B is first order with respect to A and zero order with
respect to B. Fill in the blanks in the table:

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
  Elementary reactions – reactions taking place in one step.

 Complex reactions –reactions involving a sequence of elementary reactions. These may be

consecutive reactions, reverse reactions and side reactions.

 Rate exterminating step -slowest step in a chemical reaction

 Molecularity of a Reaction:
number of reacting species (atoms, ions or molecules) taking part in an elementary reaction,
which collide simultaneously in order to bring about a chemical reaction. It is always a whole
number.
 Reactions which involve simultaneous collision between two species are bimolecular.
 When one reacting species is involved in the reaction, it is unimolecular.
Example:
NH4NO2 → N2 +2H2O
O3 → O2 + O
 Reactions which involve simultaneous collision between two species are bimolecular.
Example:
2 Hl → H2 + l2
 Reactions which involve simultaneous collision between three species are trimolecular or
termolecular.
Example :
2 NO + O2 → 2 NO2
 The probability that more than 3 molecules can collide and react simultaneously is very small.
Hence, molecularity greater than 3 is not observed.
In a complex reaction, the slowest step in a reaction determine the rate of reaction, i.e., slowest
step is the rate determining step.
 For the following reaction

difference between order and molecularity

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 Order Molecularity

1. It is sum of the powers of the concentration 1. It is the number of reacting species undergoing
terms in the rate law expression. simultaneous collision in the reaction.

2. It is determined experimentally. 2. It is a theoretical concept.

3. It can be a whole number, zero or even

3. It always a whole number.
fraction.

4. It gives some idea about reaction machanism. 4. It does not tell us the reaction mechanism.

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
 The thermal decomposition of HCO2H is a first order reaction with a rate constant of 2.4 ×
10-3 s-1 at a certain temperature. Calculate how long will it take for three-fourths of initial
quantity of HCO2 H to decompose. (log 0.25 = -0.6021) (All India 2011)

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
F 061, Rev 0, dtd 18th June 2017
MOHMMED.ILIAS
 Pt
For a reaction: 2NH2(g) ⟶ N2(g) + 3H2(g)
Rate = k
(i) Write the order and molecularity of this reaction.
(ii) Write the unit of k. (Delhi 2016)
Answer:
2NH2(g) ⟶Pt N2(g) + 3H2(g)
(i) It is a zero order reaction and its molecularity is two.
(ii) Unit of k is mol L-1 s-1.
itrogen pentoxide decomposes according to equation :
2N2O5(g) → 4 NO2(g) + O2(g).
This first order reaction was allowed to proceed at 40°C and the data below were
collected :
[N2OJ (M) Time (min)
0.400 0.00
0.289 20.0
0.209 40.0
0.151 60.0
0.109 80.0
(a) Calculate the rate constant. Include units with your answer.
(b) What will be the concentration of N2O5 after 100 minutes?
(c) Calculate the initial rate of reaction. (Delhi 2009)

The rate constant for a first order reaction is 60 s-1. How much time will it take to reduce
the initial concentration of the reactant to its l/10th value? (Comptt. All India 2015)

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 For the first order thermal decomposition reaction, the following data were obtained:
C2H5Cl(g) → C2H4(g) + HCl(g)
Time/sec               Total pressure/atm
0                                        0.30
300                                   0.50
Calculate the rate constant (Given: log 2 = 0.301, log 3 = 0.4771, log 4 = 0.6021) (All
India 2016)

For the hydrolysis of methyl acetate in aqueous solution, the following results were
obtained :
t/s 0 30 60
0.3 0.1
[CH3COOCH3]/mol L-1 0.60
0 5
(i) Show that it follows pseudo first order reaction, as the concentration of water remains
constant.
(ii) Calculate the average rate of reaction between the time interval 30 to 60 seconds.
(Given log 2 = 0.3010, log 4 = 0.6021) (Delhi 2015)

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS
 As k is constant in both the readings, hence it is a pseudo first order reaction.
(ii) Rate = – Δ[R] /Δt, Average rate between 30 to 60 seconds
= −(0.15−0.30)60−30=0.1530
= 0.5 × 10-2 mol L-1 sec-1

F 061, Rev 0, dtd 18th June 2017

MOHMMED.ILIAS