ENJOY CHEMISTRY

Unit: 4:- CHEMICAL KINETICS

Rate of Reaction Average rate of reaction, Instantaneous rate of reaction Rate law, rate
constant, order of reaction, Molecularity & units of rate constants
1. Rate of Reaction: The rate of a reaction can be defined as the change in concentration of a
reactant or product in unit time. To be more specific, it can be expressed in terms of: (i) the
rate of decrease in concentration of any one of the reactants, or (ii) the rate of increase in
concentration of any one of the products.
1. Average Rate of reaction Consider a reaction: aA + bB  cC + dD
1 [ A] 1 [ B ] 1 [C ] 1 [ D]
Rav = - =- =+ =
a t b t c t d t
2. Instantaneous Rate of reaction Consider a reaction: aA + bB  cC + dD
1 d [ A] 1 d [ B] 1 d [C ] 1 d [ D ]
RIns = - =- =+ =
a dt b dt c dt d dt
e.g. 5Br   BrO3  6H   3Br3  3H 2O
1 d ( Br  ) d ( BrO3 ) 1 d ( H  ) 1 d ( Br2 )
RIns. =    
5 dt dt 6 dt 3 dt
3. Units of rate of a reaction:The units of rate are concentration time–1. For example, if
concentration is in mol L–1 and time is in seconds then the units will be mol L-1s–1. However, in
gaseous reactions, when the concentration of gases is expressed in terms of their partial
pressures, then the units of the rate equation will be atms–1
4. Rate Law : Consider a reaction: aA + bB  cC + dD
Rate  [A]x[B]y  Rate = K[A]x[B]y (Note: The value of x & y may and may not be equal to a &
 dR
b)  = K[A]x[B]y, This form of equation is known as differential rate equation, where k
dt
is a proportionality constant called rate constant.
5. Rate law is the expression in which reaction rate is given in terms of molar concentration of
reactants with each term raised to some power, which may or may not be same as the
stoichiometric coefficient of the reacting species in a balanced chemical equation.
6. Rate constant may be defined as the rate of reaction when the concentration of each reactant
in the reaction is unity.
7. Rate law for any reaction cannot be predicted by merely looking at the balanced chemical
equation, i.e., theoretically but must be determined experimentally.

8. Order of Reaction: The sum of powers of the concentration of the reactants in the rate law
expression is called the order of that chemical reaction.
Consider a reaction: aA + bB  cC + dD , Rate = K[A]x[B]y
Order of Reaction= x + y
Order of a reaction can be 0, 1, 2, 3 and even a fraction
9. Elementary & Complex reactions: A balanced chemical equation never gives us a true picture
of how a reaction takes place since rarely a reaction gets completed in one step. The reactions
taking place in one step are called elementary reactions. When a sequence of elementary
reactions (called mechanism) gives us the products, the reactions are called complex
reactions.
10. Units of rate constant(K)= (Conc )1-n Time-1 where n is order of reaction ,Taking SI units of
concentration, mol L–1 and time, s, the units of k = (mol L-1 )1-n s-1 where n is order of reaction

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 For example
Reaction Order Unit
Zero order of reaction 0 K =molL-1s-1
First order of reaction 1 K=Sec-1
Second order of reaction 2 K= mol- 1L Sec-1
11. Molecularity of a Reaction: The number of reacting species (atoms, ions or molecules) taking
part in an elementary reaction, which must collide simultaneously in order to bring about a
chemical reaction is called molecularity of a reaction.
Unimolecular Reaction: When one reacting species is involved, for example, decomposition of
ammonium nitrite. NH4NO2  N2 + 2H2O
Bimolecular Reactions :When two reacting species involve simultaneous collision, for example,
dissociation of hydrogen iodide. 2HI H2 + I2
Trimolecular Reactions involve simultaneous collision between three reacting species, for example,
2NO + O2  2NO2
Note: The molecularity greater than three is not observed. Because the probability that more than
three molecules can collide and react simultaneously is very small.
Molecularity cannot be zero or a non integer.
12. Rate determining step.:The overall rate of the reaction is controlled by the slowest step in a
reaction called the rate determining step.
Consider the decomposition of hydrogen peroxide which is catalysed by iodide ion in an
alkaline medium
 d[ H 2 O2 ]
2H2O2 I  2H2O + O2 ,Rate = = K [ H 2O2 ] [I-]
-
, Alkaline
dt
Mechanism: Evidences suggest that this reaction takes place in two steps
(i) H2O2 + I–  H2O + IO– (slow) (ii) H2O2 + IO– H2O + I– + O2
Question based on Rate of Reaction Average rate of reaction, Instantaneous rate of reaction
Rate law, rate constant, order of reaction, Molecularity & units of rate constants
1. Explain the term rate of reaction,average rate & Instantaneous rate of reaction
2. For the reaction R P, the concentration of a reactant changes from 0.03M to 0.02M in 25
minutes. Calculate the average rate of reaction using units of time both in minutes and seconds.
3. In a reaction2AProducts, the concentration of A decreases from 0.5mol L -1 to 0.4 mol L-1 in
10 minutes. Calculate the rate during this interval?
4. The decomposition of N2O5 in CCl4 at 318K has been studied by monitoring the concentration
of N2O5 in the solution. Initially the concentration of N2O5 is 2.33 mol L–1 and after 184 minutes,
it is reduced to 2.08 mol L–1. The reaction takes place according to the equation 2 N2O5 (g)  4
NO2 (g) + O2 (g). Calculate the average rate of this reaction in terms of hours, minutes and
seconds. What is the rate of production of NO2 during this period?
5. Explain the term rate law.Also Define rate constant.
6. Write a short note on Order of reaction.
7. Give the units of rate constant for zero, first & second order reaction.
8. For a reaction, A + B  product, the rate law is given by r = K [A]1/2 [B]2 what is the order of
the reaction?
9. The conversion of molecules x to y follows second order kinetics. If the concentration of x is
increased to three lines, how will it affect the rate of formation of y?
10. Calculate the overall order of a reaction whichhas the rate expression (a) Rate = k [A] 1/2 [B] 3/2
(b) Rate = k [A] 3/2 [B] -1
11. Identify the reaction order from of the following rate constants. (i) k = 2.3 x 10-5 L mol-1s-1
(ii) k = 3 x10-4 s-1
12. From the rate expression for the following reactions determine their order of reaction and
dimensions of the rate constants.
a) H2O2 (aq) + 3 I - (aq) + 2H+  2H2O (l) + 3I-1 Rate = k [H2O] [I-]
b) CH3 CHO (g) CH4(g) + CO(g) Rate = k [CH3 CHO]3/2
c)3NON2O (g) Rate = k [NO]2
d)C2H5ClC2H4 + HCl Rate = k[C2H5 Cl]

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 13. The decomposition reaction of ammonia gas on platinum surface has a rate constant = 2.5 x
10-4 mol L-1 S-1. What is the order of the reaction?
14. 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.
15. A reaction is first order in A and second order in B. Write differential rate equation.
ii) How is the rate affected when concentration of B is tripled?
iii) How is the rate affected when the concentration of both A and B is doubled?
16. A reaction is second order with respect to a reactant. How is the rate of reaction affected if the
concentration of the reactant is(i) doubled (ii) reduced to half ?
17. For the reaction A B the rate becomes 27 times when the concentration of A is increased 3
times. What is the order of reaction?
18. 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 L-1 S-1?
19. The decomposition of dimethyl ether leads to the formation of CH 4, H2 and CO and the
reaction rate is given by Rate = k [CH3 CHO]3/2 The rate of reaction is followed by increase in
pressure in a closed vessel, so the rate can also be expressed in terms of the partial pressure of
dimethyl ether, i.e., Rate = k (pCH3 CHO)3/2 If the pressure is measured in bar and time in
minutes, then what are the units of rate and rate constants?
20. Explain the tem Molecularity with example.
21. Define Rate determining step, Elementary & Complex reactions
22. Distinguish between order of reaction & Molecularity.
Integrated rate law equations:- Zero Order Reactions & First Order Reactions
1. Zero Order Reaction: In this the rate of the reaction is proportional to zero power of the
concentration of reactants.
Consider the reaction, R P
 d [ R]
Rate = …………………………(i) Rate =K[R]0…………………………….(ii)
dt
 d [ R]
From (i) & (ii) = K[R]0
dt
 d [ R]
 =K
dt
 d [R] = - K dt
Integrating both sides
 ∫ d [R] = - K ∫ dt
 [R] = - K t + C…..(iii) where, C is the constant of integration.
At t = 0, the concentration of the reactant R = [R] 0, where [R]0 is initial concentration of the reactant.
[R]0= - K x 0 + C  [R]0= C, Substituting the value of C in equation (iii)
 [R] = - K t + [R]0
[R] 0  [ R]
 K=
t
Variation in the concentration vs time plot for a zero order reaction:-

Half life period for a zero order reaction

[R] 0  [ R]
t=
k
[R] 0
At t1/ 2 , [R] =
2
[R] 0  [ R]0 / 2
 t1/ 2 =
k
[ R]
 t1 / 2 
If we plot [R] against t, we get a straight line 2K
with slope = –k and intercept equal to [R]0.
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Examples of zero order reaction (a)The decomposition of gaseous ammonia on a hot platinum surface
is a zero order reaction at high pressure (b)The thermal decomposition of HI on gold surface.
2. First Order Reactions: The rate of the reaction is proportional to the first power of the
concentration of the reactant R.
Consider the reaction, R P
 d [ R]
Rate = …………………………(i)
dt
Rate =K[R]1…………………………….(ii)
 d [ R]
From (i) & (ii) = K[R]1
dt
 d [ R]
 = K dt
[ R]
Integrating both sides
 d [ R]
∫ = K∫ dt
[ R]

-ln[R]=kt + C ………(iii )where, C is the constant of integration

At t = 0, the concentration of the reactant R = [R] 0, where [R]0 is initial concentration of the
reactant.
-ln[R]0=kx0 + C  C=-ln[R]0, Substituting the value of C in equation (iii)
 -ln[R]=kt -ln[R]0
1
K = { ln[R]0 - ln[R]}
t
1 [ R ]0 2.303 [R ] 0
K= ln  k= log
t [ R] t [ R]

 If we plot ln [R] against t (Fig. 4.4) we get a straight line with slope = –k and intercept equal to ln [R]0
 If we plot a graph between log [R]0/[R] vs t, (Fig. 4.5), the slope = k/2.303

Half life period for a First order reaction

2.303 [R ] 0 2.303
t= log  t1/ 2 = x0.3010
k [ R] k
0.693
At t1/ 2 , [R] =
[R] 0  t1 / 2 
2 K
[R ] 0 It can be seen that for a first order reaction,
2.303
 t1/ 2 = log half-life period is constant, i.e., it is
k [ R]0 / 2 independent of initial concentration of the
2.303 reacting species
 t1/ 2 = log 2
k
 Examples : All natural and artificial  Decomposition of N2O5 and N2O are some
radioactive decay of unstable nuclei take more examples of first order reactions
place by first order kinetics.

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 2.303 [ P] i
Integrated rate equation for a gaseous system: k = log
t [2 Pi  Pt ]
Question on Integrated rate law equations: - Zero Order Reactions & First Order Reactions
1. Derive the Integrated rate equation for Zero order reaction. Find half life period and plot the
graph associated to it.
2. The rate constant for a reaction of zero order reaction in A is 0.0030molL-1s-1.How long will it
take for the intial concentration of A to fall from 0.10 M to 0.075M?
3. Derive the Integrated rate equation for first order reaction. Find half life period and plot the graph
associated to it.
4. For a first order chemical reaction: (i) Plot variation in the concentration in [R] vs. time (s) (ii)
what are the units of rate constant k? (iii) give the relationship between k and t ½ (half life
period) (iv) Give the slope (v) Draw the plot log [R]0 / [R] vs. time t(s)
5. A first order reaction has a rate constant 1.15 x 10 -3 s-1. How long will 5 g of this reactant take to
reduce to 3 g?
6. Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If the
decomposition is a first order reaction, calculate the rate constant of the reaction.
7. The initial concentration of N2O5 in the following first order reaction N2O5 2(g) +
1/2O2 (g) was 1.24 × 10 mol L at 318 K. The concentration of N2O5 after 60 minutes was 0.20 ×
–2 –1

10–2 mol L–1.Calculate the rate constant of the reaction at 318 K.

8. A first order reaction is found to have a rate constant. k = 5.5 x 10-4 s-1 . Find the half-life of the
reaction.
9. Show that in a first order reaction, time required for completion of 99.9% is 10 times of half-life
(t1/2) of the reaction.
10. For a first order reaction, show that time required for 99% completion is twice the time required
for the completion of 90% of reaction.
11. Calculate the half-life of a first order reaction from their rate constants given :(i) 200 s–1 (ii) 2
min–1 (iii) 4 years–1.
12. The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood
had only 80% of the 14C found in a living tree.Estimate the age of the sample
13. 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 1/16 th value?
14. .During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1  g 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.
15. A first order reaction takes 40 min for 30% decomposition. Calculate t 1/2.
16. k = 2.0 × 10–2s–1. Calculate the concentration of A
remaining after 100 s if the initial concentration of A is 1.0 mol L–1..
17. 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?
18. A first order reaction has a rate constant 0.0051min-1 .If we begin with 0.10 M concentration of
the reactant ,what concentration of the reactant will be left after 3 hours.
19. The decomposition of phosphine PH3 proceeds according to the following equation: 4PH3→P4 +
6H2 ,It is found that the reaction follows rate reaction rate=K[PH 3] The half life of PH 3 is
37.9seconds at 120oC. (i)How much time is required for 3/4 th of PH3 to decompose? (ii)What
fraction of the original sample of PH3 remains behind after 1 minute?
20. For the decomposition of azoisopropane to hexane and nitrogen at 543k, the following data were
obtained. Calculate the rate constant.
t (sec) P(mm of Hg)
0 35.0
360 54.0
720 63.0

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1. Factors affecting the rate of Chemical Reaction
 Nature of reactants  Temperature
 Concentration of reactants  Catalyst
 Surface area of reactants  Radiation
2. Pseudo First Order Reaction : The reaction which is bimolecular but order is one is known as
Pseudo first order reaction. In this type of reaction one of the reactant is present in large
excess i.e. the concentration does not get altered much during the course of the reaction e.g.

Hydrolysis of ester
H
CH3COOC2H5 + H2O  CH3COOH + C2H5OH ,Rate = K[CH3COOC2H5]
Inversion of cane sugar is another pseudo first order reaction
H
C12H22O11 + H2O  C6H12O6 + C6H12O6 Rate = K[C12H22O11]
3. Temperature Dependence of the Rate of a Reaction(Arrhenius equation): It has been
found that for a chemical reaction with rise in temperature by 10°, the rate constant is nearly
doubled. The temperature dependence of the rate of a chemical reaction can be accurately
Ea
explained by Arrhenius equation. k  Ae RT , where A is the Arrhenius factor or the
frequency factor. It is also called pre-exponential factor. It is a constant specific to a particular
reaction. R is gas constant and Ea is activation energy measured in joules/mole (J mol –1).
E
Taking natural logarithm of both sides of Arrhenius equation ln k=lnA- a  log k = log A -
RT
Ea
2.303RT

K  Ea  1 1 
log 2      where T is temperature in K.
 K1  2.303R  T1 T2 
K K K
Note- If rate of reaction doubles 2 = 2, If it triples 2 =3, If quadruples 2 = 4.
K1 K1 K1

Ea
In Fig. 4.10, slope = - and intercept = ln
R
A

4. Threshold Energy : Minimum amount of energy required for reacting species to form
activated complex.
5. Activated Complex : Transition state of Reactant and product Or Unstable intermediate
formed between reacting molecule which in highly unstable and readily changes into
product. It can be understood clearly using the following simple reaction.
H2(g) + I2(g)2HI(g)

6. Activation Energy: It is extra energy which must be supplied to the reactants from
outside so that the colliding particles must produce effective collision i.e.have total
energy equal to the threshold energy.

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 (C), is known as activation energy (Ea).
Fig. 4.7 is obtained by plotting potential
energy vs reaction coordinate. Reaction
coordinate represents the profile of energy
change when reactants change into
products. Some energy is released when the
complex decomposes to form products. So,
the final heat of the reaction depends upon
the nature of reactants and products

The energy required to form this

intermediate, called activated complex
7. Effect of Catalyst: Catalyst are specific which reduces the activation energy barrier by forming
an intermediate product It is believed that the catalyst provides an alternate pathway or
reaction mechanism by reducing the activation energy between reactants and products and
hence lowering the potential energy barrier as shown in Fig. 4.11.

It is clear from Arrhenius equation (4.18)

that lower the value of activation energy
faster will be the rate of a reaction.

8. Collision Theory of Chemical Reactions: It is based on kinetic theory of gases. According to this:
 The reactant molecules are assumed to be hard spheres and reaction is postulated to occur
when molecules collide with each other.
 The number of collisions per second per unit volume of the reaction mixture is known as
collision frequency (Z).
 The collisions in which molecules collide with sufficient kinetic energy (called threshold
energy*) and proper orientation, so as to facilitate breaking of bonds between reacting
species and formation of new bonds to form products are called as effective collisions
 Another factor which affects the rate of chemical reactions is activation energy.
 The Proper orientation of reactant molecules lead to bond formation whereas improper
orientation makes them simply bounce back and no products are formed.
  Thus, in collision theory activation energy and proper orientation of the molecules
together determine the criteria for an effective collision and hence the rate of a
chemical reaction

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  Collision theory also has certain drawbacks as it considers atoms/molecules to be hard
spheres and ignores their structural aspect
Exercise…..
1. Mention the factors that affect the rate of a chemical reaction.
2. Define Pseudounimolecular reaction with an example.
3. What is the effect of temperature on the rate constant of a reaction? How can this temperature
effect on rate constant be represented quantitatively?
4. Write Arrhenius Equation. Give its Logarithmic form and Plot graph
5. The rate of a reaction quadruples when the temperature changes from 293 K to 313 K. Calculate the
energy of activation of the reaction assuming that it does not change with temperature.
6. The rate of reaction increases four times when the temperature changes from 300 K to 320 K.
Calculate the energy of activation of the reaction assuming that it does not change with
temperature.(R=8.314JK-1mol-1)
7. The rate of chemical reaction doubles for an increase of 10 K in absolute temperature from 298K.
Calculate Ea.
8. The rate constants of a reaction at 500K and 700K are 0.02s–1 and 0.07s–1 respectively. Calculate the
values of Ea and A.
9. The first order rate constant for the decomposition of ethyl iodide by the reaction C 2H5I(g) →
C2H4 (g) + HI (g) at 600K is 1.60 × 10–5 s–1. Its energy of activation is 209 kJ/mol. Calculate the rate
constant of the reaction at 700K.
10. The activation energy for the reaction 2 HI(g)  H2(g) + I2(g) is 209.5 KJ mol-1 at 581K. Calculate the
fraction of molecules of reactants having energy equal to or greater than activation energy.
11. The rate constant for the decomposition of hydrocarbons is 2.418 × 10 –5s–1 at 546 K. If the energy of
activation is 179.9 kJ/mol, what will be the value of pre-exponential factor.
12. The decomposition of A into product has value of k as 4.5 x 103 s–1 at 10
60 kJ mol–1. At what temperature would k be 1.5 × 104s–1?
13. The time required for 10% completion of a first order reaction at 298K is equal to that required for
its 25% completion at 308K. If the value of A is 4 × 1010s–1. Calculate k at 318K and Ea.
14. Define the terms : (i) Threshold Energy (ii) Activated Complex (iii) Activation energy
15. Explain the Effect of Catalyst on activation energy.
16. Write a note on Collision Theory of Chemical Reactions.
17. For a certain chemical reaction A + 2B  2C + D.The experimentally obtained information is
tabulated below.
Experiment [A]0 [B]0 Initial rate

1 0.30 0.30 0.096

2 0.60 0.30 0.384
3 0.30 0.60 0.192
4 0.60 0.60 0.768
(i) Derive the order of reaction w.r.t. both the reactants A and B. (ii) write the rate law.(iii) calculate the
value of rate constant k (iv) Write the expression for the rate of reaction in terms of A and C.
18. For a certain chemical reaction 2A + B - C+D The following result has been obtained :
Experiment [A] mol L-1 [B] mol L-1 Initial rate mol L-1min-1
I 0.1 0.1 6.0 x 10-3
II 0.3 0.2 7.2 x 10-2
III 0.3 0.4 2.88 x 10-1
IV 0.4 0.1 2.40 x 10-2
Determine the rate law and rate constant for the reaction
19. 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:

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 Experiment [A] mol L-1 [B] mol L-1 Initial rate mol L-1min-1
I 0.1 0.1 2.0 × 10–2
II – 0.2 4.0 × 10–2
III 0.4 0.4 –
IV – 0.2 2.0 × 10–2
20. 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:
A/ mol L–1 0.20 0.20 0.40
B/ mol L –1 0.30 0.10 0.05
r0/mol L–1s–1 5.07 × 10–5 5.07 × 10–5 1.43 × 10–4
What is the order of the reaction with respect to A and B?

Some Solved Numericals:

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