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Unit: 4:- CHEMICAL KINETICS
TOPIC : RATE OF REACTION AVERAGE RATE OF REACTION, INSTANTANEOUS RATE OF REACTION RATE LAW,
RATE CONSTANT, ORDER OF REACTION, MOLECULARITY & UNITS OF RATE CONSTANTS
1. CHEMICAL KINETICS : The branch of chemistry, which deals with the study of reaction rates and their
mechanisms, called chemical kinetics. The word kinetics is derived from the Greek word ‘kinesis’
meaning movement.chemical kinetics tells about the rate of a reaction
2. 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.
3. AVERAGE RATE OF REACTION :It is the appearance of products or disappearance of reactants over a
long time interval : Consider a reaction: aA + bB → cC + dD
1 [ A] 1 [ B] 1 [C ] 1 [ D]
Rav = - =- =+ =
a t b t c t d t
• Negative sign indicates that the concentration of reactant is decreasing & positive sign indicates that the
concentration of product is increasing
4. INSTANTANEOUS RATE OF REACTION :It is defined as the change in concentration of any one of the
reactants or products at that particular instant of time.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
5. 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
6. FACTORS INFLUENCING RATE OF A REACTION: (a)concentration of reactants (pressure in case of gases)
(b) Surface area of reactants (c) temperature (d) catalyst
7. 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 & b) ➔
− dR
= K[A]x[B]y, This form of equation is known as differential rate equation, where k is a
dt
proportionality constant called rate constant.
Statement: 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..
8. RATE CONSTANT may be defined as the rate of reaction when the concentration of each reactant in the
reaction is unity.
9. Rate law for any reaction cannot be predicted by merely looking at the balanced chemical equation, i.e.,
theoretically but must be determined experimentally.

10. 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. Order of a reaction is an experimental quantity.
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
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11. 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.
12. 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
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
13. 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.
14. RATE DETERMINING STEP.:The overall rate of the reaction is controlled by the slowest step in a reaction
called the rate determining step.like for example, chances to win the relay race competition by a team
depend upon the slowest person in the team.
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-] Mechanism: Evidences suggest that this
-
, Alkaline
dt
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. Define the term rate of reaction.
2. Explain the difference between average rate & Instantaneous rate of reaction
3. 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.[ Ans: 4 ×10−4
M min−1 6.67 × 10−6 M sec-1 ]
4. 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? .[Ans: 5 × 103 Mmin−1]
5. For the reaction 2N2O5(g)→4NO2 (g)+ O2 (g) the rate of formation of NO2(g) is 2.8 x 10-3Ms-1.Calcualte
the rate of disappearance of N2O5(g) [Ans:1.4×10−3Ms−1]
6. For the reaction H2 + Cl2 → 2 HCl , Rate = k ,Write the order,Molecularity & unit of k.
7. For the reaction 2NH3 → N2+ 3H2 Rate = k ,Write the order,Molecularity & unit of k.
8. 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?
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9. Explain the term rate law.
10. Define rate constant.
11. Write a short note on Order of reaction.
12. Give the units of rate constant for zero, first & second order reaction.
13. Express the rate of the following reaction in terms of disappearance of hydrogen & formation of
ammonia in the reaction : 3H2 + N2→2NH3
14. 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?
15. Write the rate equation for the reaction 2A + B →C if the order of the reaction is zero.
16. The conversion of molecules x to y follows second order kinetics. If the concentration of x is increased
to three times, how will it affect the rate of formation of y?
17. Calculate the overall order of a reaction which has the rate expression (a) Rate = k [A] 1/2 [B] 3/2
(b) Rate = k [A] 3/2 [B] -1
18. 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
19. 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]
20. 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?
21. 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.
22. 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?
23. 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 ?
24. 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?
25. For the reaction A → B , the rate of reaction becomes three times when the concentration of A is
increased nine times. What is the order of the reaction ?
26. The conversion of molecules x to y follows second order kinetics. If the concentration of x is increased to
three times, how will it affect the rate of formation of y?
27. For the reaction 2X → X2, the rate of reaction becomes three times when the concentration of X is
increased 27 times. What is the order of the reaction ?
28. For the reaction A → B , the rate of reaction becomes three times when the concentration of A is
increased nine times. What is the order of the reaction ?
29. 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?
30. The decomposition of dimethyl ether leads to the formation of CH4, 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?
31. Explain the tem Molecularity with example.
32. Define Rate determining step, Elementary & Complex reactions
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33. Distinguish between order of reaction & Molecularity.
34. For which type of reactions, order and molecularity have the same value?
35. For a reaction A + B → Products, the rate law is — Rate = k [A][B]3/2
36. Can the reaction be an elementary reaction? Explain
37. For a zero order reaction will the molecularity be equal to zero? Explain.
38. Why can’t molecularity of any reaction be equal to zero?
39. Why molecularity is applicable only for elementary reactions and order is applicable for elementary as
well as complex reactions?
40. Why can we not determine the order of a reaction by taking into consideration the balanced chemical
equation?
41. Mention the factors that affect the rate of a chemical reaction.
42. The possible mechanism for the reaction : 2NO (g) + O2 (g) → 2NO2 (g) is
(i) NO + O2 K NO3 (fast) (II) NO3 + NO ⎯K⎯→ 2
NO2 + NO2 (g) (slow).
Write the rate law for the reaction
43. .For a reaction 2H2O2 ⎯I⎯ ⎯⎯→ 2H2O + O2 the proposed mechanism is as follows
-
, Alkaline

(i) H2O2 + I → H2O + IO (slow) (ii) H2O2 + IO–→ H2O + I– + O2 (fast)

– –

(a)Write the rate law for the reaction. (b) Write the overall order of reaction. (iii)Out of steps (i) & (ii)
which one is rate determining step.
44. For a chemical reaction A + 2B → 2C + D.The experimentally obtained information is given 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.
45. 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:
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
–1
B/ mol L 0.30 0.10 0.05
–1 –1 –5 –5
r0/mol L s 5.07 × 10 5.07 × 10 1.43 × 10–4
What is the order of the reaction with respect to A and B?

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TOPIC : 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] − d [ R]
From (i) & (ii) = K[R]0  =K  d [R] = - K dt
dt 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]
At t1/ 2 , [R ] = 0
2
[R] 0 − [ R]0 / 2
 t1/ 2 =
k
[ R]
 t1 / 2 =
2K
If we plot [R] against t, we get a straight line
with slope = –k and intercept equal to [R]0.

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) Rate =K[R]1…………………………….(ii)
dt
− d [ R] − d [ R]
From (i) & (ii) = K[R]1  = K dt
dt [ R]
− d [ R]
Integrating both sides ∫ = 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, Su bstituting the value of C in equation (iii)  -ln[R]=kt -ln[R]0
1
K = { ln[R]0 - ln[R]}
t

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1 [ R] 2.303 [R ] 0
K= ln 0  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
[R] 0  t1 / 2 =
At t1/ 2 , [R ] = K
2
[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.
first order gas phase reaction
3. INTEGRATED RATE EQUATION FOR FIRST ORDER GAS PHASE REACTION A(g) → B(g) + C(g)
2.303 [ P] i
: k= log
t [2 Pi − Pt ]
4. 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
+
CH3COOC2H5 + H2O ⎯⎯→ H
CH3COOH + C2H5OH ,Rate = K[CH3COOC2H5]
Inversion of cane sugar is another pseudo first order reaction
+
C12H22O11 + H2O ⎯⎯→ H
C6H12O6 + C6H12O6 Rate = K[C12H22O11]
QUESTION ON INTEGRATED RATE LAW EQUATIONS: - ZERO ORDER REACTIONS & FIRST ORDER
REACTIONS, PSEUDO FIRST ORDER REACTION
1. Derive the Integrated rate equation for Zero order reaction. Find half life period and plot the graph
associated to it.
2. For a zero order chemical reaction: (a) Plot variation in the concentration in [R] vs. time .(b) what are
the units of rate constant k? (c) give the relationship between k and t ½ (half life period) (d) Give the
slope
3. A substance with initial concentration ‘a’ follow zero order kinetics with rate constant ‘k’ mol L-1 s-1. In
how much time will the reaction go to completion?

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-1 -1
4. The rate constant for a reaction of zero order reaction in A is 0.0030molL s .How long will it take for
the intial concentration of A to fall from 0.10 M to 0.075M?
5. The decomposition of NH3 on platinum surface is zero order reaction. If rate constant is 4 x 10-3Ms-
1
,how long will it take to reduce the intial concentration of NH3 from 0.1M to 0.064M.
6. Derive the Integrated rate equation for first order reaction. Find half life period and plot the graph
associated to it.
7. For a first order chemical reaction: (i) Plot variation in the concentration in ln[R] vs. time & Give the
slope (s) (ii) Draw the plot log [R]0 / [R] vs. time t(s) & Give the slope (iii) what are the units of rate
constant k? (iii) give the relationship between k and t ½ (half life period) (iv) Give the slope
8. For a reaction R→P half-life period is is independent of initial concentration of the reacting
species.What is the order of reaction.
9. (a) Define half life period of a reaction .(b)Write the expressions of half life for (i) first order chemical
reaction (ii) zero order chemical reaction
10. What are pseudo first order reactions? Give one example of such reaction.
11. 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?
12. 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.
13. The initial concentration of N2O5 in the following first order reaction N2O5(g) → NO2(g) + 1/2O2 (g) was
1.24 × 10–2 mol L–1 at 318 K. The concentration of N2O5 after 60 minutes was 0.20 × 10–2 mol L–
1
.Calculate the rate constant of the reaction at 318 K.
14. 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.
15. 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.
16. For a first order reaction, show that time required for 99% completion is twice the time required for
the completion of 90% of reaction.
17. 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.
18. 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
19. 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?
20. .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.
21. H2O2 decomposes to H2O and O2 in a reaction that is first order and has rate constant k = 1.06 x 10-3
min-1.How long will it take 15% of a sample of H2O2 to decompose.
22. A first order reaction takes 30 minutes for 50% decomposition. Calculate the time required for 90%
completion for this reaction
23. A first order reaction takes 100 minutes for 60% decomposition. Calculate the time required for 90%
completion for this reaction
24. A first order reaction takes 20 minutes for 25% decomposition. Calculate the time required for 75%
completion for this reaction
25. A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
26. Consider a certain reaction A→ Products with 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..
27. 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?
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28. 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. The
29. A reactant has a half life of 10 min.(i)Calculate the rate constant for the first order reaction (ii) what
fraction of the reactant will be left after an hour of the reaction has occurred.
30. 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[PH3] The half life of PH3 is 37.9 second at
120oC. (i)How much time is required for 3/4th of PH3 to decompose? (ii)What fraction of the original
sample of PH3 remains behind after 1 minute?
th
31. For a first order reaction, time taken for half of the reaction to complete is t1 , whereas that for 3
4
of the reaction to complete is t 2 . How are t1 and t 2 related ?
32. 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
33. For the first order thermal decomposition C2H5Cl(g)→ C2H4(g) + HCl (g). Calculate the rate constant.
Experiment Time Pressure (atm)
1 0 0.30
2 300 0.50
34. The Following data were obtained during the first order thermal decomposition of SO2Cl2 at a constant
volume: SO2Cl2(g)→ SO2(g) + Cl2(g). Calculate the rate constant.
Experiment Time Pressure (atm)
1 0 0.4
2 100 0.7
35. The following data were obtained during the first order thermal decomposition of N 2O5 (g) at constant
volume: 2N2O5(g)→2N2O4(g) + O2(g). Calculate the rate constant.
S.No Time Pressure (atm)
1 0 0.5
2 100 0.512
36. Following data were obtained for the reaction : N2O5(g)→2NO2(g) +1/2 O2(g).
Time (s) 0 300 600
-2 -2
[N2O5(g)] 1.6 x 10 0.8 x 10 0.4 x 10-2
(mol/l)
(i) Show that it follows first order reaction (ii)Calculate the half life
37. In a pseudo first order hydrolysis of ester in water, the following results were obtained:
Time (s) 0 30 60 90
[Ester] 0.55 0.31 0.17 0.85
(mol/l)
(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.

TOPIC : TEMPERATURE DEPENDENCE OF THE RATE OF A REACTION(ARRHENIUS EQUATION)

1. TEMPERATURE COEFFICIENT : It is the ratio of rate constant at temperature 308 (298 + 10)K to the
rate constant at 298K. It has been found that for a chemical reaction with rise in temperature by 10°,
the rate constant is nearly doubled.

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2. ARRHENIUS EQUATION. : The temperature dependence of the rate of a chemical reaction can be
−Ea
accurately 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).
• In the Arrhenius equation the factor e -Ea /RT corresponds to the fraction of molecules that have
kinetic energy greater than Ea.
E
• Taking natural logarithm of both sides of Arrhenius equation ln k=lnA- a & log k = log A -
RT
Ea
2.303RT
• The plot of lnk vs 1/T gives a straight line according to the equation
Slope : -Ea/R & Intercept = lnA

3. Thus, it has been found from Arrhenius equation that increasing

the temperature or decreasing the activation energy will result in an
increase in the rate of the reaction and an exponential increase in
the rate constant.

At Temperature T1 &

At Temperature T2 

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

3. THRESHOLD ENERGY : It is the minimum energy which the colliding molecules must have for effective
collisions. i.e. those collisions which lead to the formation of product molecules.
4. ARRHENIUS THEORY :It states that product are formed through the 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)

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According to Arrhenius, this reaction can take place only when a molecule of hydrogen and a molecule of
iodine collide to form an unstable intermediate . It exists for a very short time and then breaks up to form two
molecules of hydrogen iodide. The energy required to form this intermediate, called activated complex , is
known as activation energy (Ea).
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. Or It is the energy needed to form the intermediate, called activated complex
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 (C),
is known as activation energy (Ea). Fig. 4.7
7. EFFECT OF CATALYST: Catalyst are It is clear from Arrhenius equation
specific which reduces the activation that lower the value of activation energy
energy barrier by forming an faster will be the rate of a reaction.
intermediate product It is believed A small amount of the catalyst can catalyse
that the catalyst provides an a large amount of reactants. A catalyst does
alternate pathway or reaction not alter Gibbs energy, ΔG of a reaction. It
mechanism by reducing the catalyses the spontaneous reactions but
activation energy between reactants does not catalyse non-spontaneous
and products and hence lowering the reactions. It is also found that a catalyst
potential energy barrier as shown in does not change the equilibrium constant of
Fig. 4.11. a reaction rather, it helps
in attaining the equilibrium faster, that is, it
catalyses the forward as
well as the backward reactions to the same
extent so that the equilibrium
state remains same but is reached earlier.

8. Collision Theory of Chemical Reactions:

(a) According to the collision theory rate of reaction depends on the collision frequency and effective
collisions.
(b) The number of collisions per second per unit volume of the reaction mixture is known as collision
frequency (Z).
(c) 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.

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(d) For a bimolecular elementary reaction A + B → Products rate of reaction can be expressed as
Rate = Z AB e−Ea/ RT where ZAB represents the collision frequency of reactants, A and B and e−Ea/ RT
represents the fraction of molecules with energies equal to or greater than Ea.
(e) 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.
(f) To account for effective collisions, another factor P, called the probability or steric factor is
introduced. It takes into account the fact that in a collision, molecules must be properly oriented i.e.,
Rate = PZ AB e−Ea/ RT
(g) Another factor which affects the rate of chemical reactions is activation energy.
(h) 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

• Collision theory also has certain drawbacks as it considers atoms/molecules to be hard

spheres and ignores their structural aspect
Exercise…..
1. What is the effect of temperature on the rate constant of a reaction? How can this temperature
effect on rate constant be represented quantitatively?
2. Why does the rate of a reaction increase with rise in temperature?
3. Write Arrhenius Equation. Give its Logarithmic form and Plot graph.
4. Draw a plot of lnk vs 1/T for a chemical reaction .What does the intercept represent.What is the
relation between slope and Ea?
5. With a help of diagram explain the role of activated complex in a reaction.
6. 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.
7. 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)
8. The rate of chemical reaction doubles for an increase of 10 K in absolute temperature from 298K.
Calculate Ea.
9. 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.
10. The rate constants of a reaction at 650K and 700K are 2.15 x 10-8Lmol-1s–1 and 2.39 x 10-7Lmol-1s–1
respectively. Calculate the values of Activation energy.
11. A first order reaction is 50% completed in 40 minutes at 300K and in 20 minutes at 320 K. Calculate
the value of Activation energy

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12. 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.

13. The Rate constant for the first order reaction is given by following equation
Calculate Ea for this reaction and rate constant k if its half period be 200 min.
14. The rate constant for the first order decomposition of H2O2 is given by the following equation:
log k = 14.34 – 1.25 × 104 K/T Calculate Ea for this reaction and at what temperature will its half
period be 256 minutes?
15. The decomposition of hydrocarbon follows the equation k = (4.5 × 1011s–1) e-28000K/T Calculate Ea.
16. 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.
17. 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.
18. The decomposition of A into product has value of k as 4.5 x 103 s–1 at 100C and energy of activation
60 kJ mol–1. At what temperature would k be 1.5 × 104s–1?
19. 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.
20. Define the terms : (i) Threshold Energy (ii) Activated Complex (iii) Activation energy
21. Explain the Effect of Catalyst on activation energy.
22. What is the effect of adding a catalyst on (i)Activation energy (ii)Gibbs Energy
23. Write a note on Collision Theory of Chemical Reactions.
24. In some cases, it is found that a large number of colliding molecules have energy more than threshold
value, yet the reaction is slow. Why ?
25. The reaction between H2(g) and O2(g) is highly feasible yet allowing the gases to stand at room
temperature in the same vessel does not lead to the formation of water. Explain.
26. Oxygen is available in plenty in air yet fuels do not burn by themselves at room temperature. Explain.
27. Thermodynamic feasibility of the reaction alone cannot decide the rate of the reaction. Explain with
the help of one example.
28. Why in the redox titration of KMnO4 vs oxalic acid, we heat oxalic acid solution before starting the
titration?

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