CLASS – 12TH

CBSE 2024

CHEMICAL KINETICS
APNI KAKSHA NOTES

APNI KAKSHA 1
APNI KAKSHA 2
 CHEMICAL KINETICS
For a chemical reaction 𝐑 → 𝐩: Three questions are important.
(i) Reaction will happen or not? : Thermodynamics: Reaction is feasible only if ΔG < 0.
(ii) To which extent reaction will happen? : Chemical Equilibrium
(iii) What is the speed of chemical reaction? : Chemical kinetics: concept of rate of a reaction.

Rate of reaction -: [Velocity of reaction]

The rate of change of concentration of any species taking part in a chemical reaction with time
is known as rate of reaction.
Change in Concentration ΔC
→ For a reaction R → P rate = =
time Δt
(mol/𝐿) (𝑎𝑡𝑚)
→ Unit: 𝑠
or 𝑠
→ for gaseous reactant or product.

Types of rate: -
Total change in conc cn
(i) Average Rate: - R av = Total time taken
−Δ[ Reactant ] Δ[ Product ] c2−c1 Δc
Rate = = = = Δt
Δt Δt t2−t1
→R⟶P
at time t1 : c1 [Concentration of product after time t1 ]
at time t 2 : c2
(ii) Instantaneous Rate -: Rate at a given time
Δc dc
R inst = limit Δt→0 R ar = limit Δt→0 Δt = dt
= Slope of concentration and time graph.
# Rate of appearance and rate of disappearance: -
Let us consider a reaction R → P
At time t1 : R1 P1 ΔR = R 2 − R1
t2: R 2 P2 ΔP = P2 − P1
Δt = t 2 − t1
Decrease in [R] Δ[R]
→ Rate of disappearance of R = =−
Time taken Δt
Increase in [P] Δ[P]
→ Rate of appearance of P = =
Time taken Δt

APNI KAKSHA 3
Example: - Hg(l) + Cl2 (g) ⟶ HgCl2 (s)
→ Rate of reaction = Rate of dis appearance of Hg g ∣ U2 = Rate of appearance of HgCl2
Δ[Hg] Δ[Cl2 ] Δ[HgC2 ]
=− =− =
Δt Δt Δt

Note: If stoichiometric coefficients of reactants or products are hat equal to one, then rate of
disappearance of any of the reactants or rate of appearance of products is divided by their
respective stoichiometric coefficients.
→ aA + bB ⟶ cC + dD
−1 Δ[A] 1 Δ[B] 1 Δ[C] 1 Δ[D]
Rate of reaction = = −b =c =d
a Δt Δt Δt Δt
Example -: (i) 2HI(g) → H2 (g) + I2 (g)
→ Rate of disappearance of HI = 2 × Rate of appearance of H2 ∣ I2
1
→ Rate of reaction = Rate of appearance of H2 ∣ I2 = 2 Rate of disappearance
Δ[H2 ] Δ[I2] 1 Δ[HI]
= = = −2
Δt Δt Δt
(ii) 5Br − (aq.) + BrO−
3 (aq.) + 6H(aq.) ⟶ 3Br2 (aq.) +3H2 O (l)
+

1 Δ[Br− ] Δ[BrO−
3] 1 Δ[H+ ]
Rate of reaction = − 5 =− = −6
Δt Δt Δt

Question: For the reaction 2 N2 O5 (g) ⟶ 4NO2 (g) + O2 (g), the rate of formation of NO2 (g) is
2.8 × 10−3 MS −1 . Calculate the rate of dis appearance of N2 O5 (g)?
Answer: 2 N2 O5 (g) ⟶ 4NO2 (g) + O2 (g)
−1 Δ[N2 O5 ] 1 Δ[NO2 ]
Rate of Reaction = =4
2 Δt Δt
−Δ[N2 O5 ] 1 Δ[NO2 ]
→ Rate of disappearance of N2 O5 = =2×
Δt 4 Δt
−3 −1 Δ[NO2 ]
Given that rate of formation of NO2 = 2. d × 10 𝑀𝑠 = Δ𝑡
1 −3 −1
= 2 × 2.8 × 10 Ms
= 1.4 × 10−3 Ms −1

Question: The decomposition of N2 O5 in CCl4 at 318 K has been studied by monitoring the
concentration of N2 O5 in the solution. Initially the concentration of N2 O5 is 2.33 mol L−1 and
after 184 minutes, it is reduced to 2.08 mol L−1 . Calculate the average rate of this reaction and
what is the rate of production of NO2 during this period?
2 N2 O5 ( g)4NO2 ( g) + O2 ( g)
1 Δ[N2 O5 ] −1 (2.08−2.33)
Answer: Average Rate = − 2 = [ mol L−1 ]
Δt 2 184 min
6.79×10−4
= 6.79 × 10−4 molL−1 /min = mol L−1
60 s
= 1.13 × 10−5 mol L−1 S −1
1 Δ[NO2 ] molL−1
→ Rate = 4 [ ] = 6.79 × 10−4
Δt min
Δ[NO2 ]
→ = 4 × 6.79 × 10 −4
= 2.79 × 10−3 molL−1 min−1 = Rate of production of NO2
Δt

APNI KAKSHA 4
Factors influencing rate of a reaction:
(i) Concentration: - Rate of reaction increases with concentration of reactant.
→ In case of gases, pressure ↑⇒ Rate ↑
(ii) Temperature: - Rate of a reaction increases with increase of temperature.
(iii) Nature of reactants: - Different reactant require different amount of energies for
breaking of old bonds and for formation of new bonds.
(iv) Catalyst: - It changes the rate of reaction. Without being used (consumed) in the reaction.

Rate Law | Rate Equation | Rate Expression: - [Dependence of rate on 𝐜𝐨𝐧𝐜 𝐧 ]

→ Rate law is expression in which reaction rate is given in terms of molar conc n of reactants
with each term raised to some power.
→ The power raised on concentration terms in rate expression may or may nat be same as
stoichiometric coefficient of the reacting species in a balanced chemical equation.
→ Consider a general reaction: aA + bB ⟶ cC + dD
Rate equation: Rate α[A]x [B]y
Rate = K[A]x [B]y → Rate constant
→ Exponent x and y may or may not be equal to stoichiometric coefficient (and b).
→ The equation which relate, rate of a reaction to concentration of the reactants is called rate
equation or rate expression.

Order of a reaction: - The sum of powers of the concentration of the reactants in rate law
expression is called order of that chemical reaction.
For a reaction: aA + bB ⟶ cC + dD
Rate = k[A]x [B]y then order of reaction = x + y
→ Order of a reaction can be determined only be experiment. We can not predict theoretically.
→ order of a reaction can be 0,1,2 and even a fraction.
Reaction Experimental rate expression order of reaction
1
→ CHCl3 + Cl2 → CCl4 + HCl Rate = K[CHC3 ]1 [Cl2 ]1/2 1 + = 1.5 2

O
||
→ CH3 − C − O C2 H5 + H2 O Rate = 𝐾[CH3 COOC2 H5 ]1 [H2 O]0 1+0 =1
↓
CH3 COOH + C2 H5 OH

Units of rate constant: - From above: Rate = K[A]x [B]y

Rate conc n 1 time Conc n 1
Then k = [A]x [B]y ; unit of k = (concn)x(concn)y = ⋅ [concn]x+y
time
(mol L−1 ) 1
→ Unit of k = × (mol L L−1 )n n = order of reaction = x + y.
s
→ For zero order reaction: n = 0 then unit of k = mol L−1 S −1
→ For first order reaction: n = 1 : unit of k = s−1
→ For second order reaction: n = 2 : unit of k = m0. l−1 LS −1

APNI KAKSHA 5
Question: Identify order of following reaction:
(i) k = 2.3 × 10−5 Lmal−1 S −1 (ii) 3 × 10−4 S −1
Answer: (i) Lmol−1 S −1 : unit of second order
So, this represent second order reaction.
(ii) S −1 : unit of first order reaction.

Question: Write the rate equation for reaction 2NO(γ) + O2 (r) → NO2 (g) by 4 sing following
experimental data table?
Solution: Let us write rate expression for reaction: Rate = k[NOx ][O2 ]y … … (i)
put the data of experiment (i) in equation (i):
→ 0.096 mol L−1 S −1 = K[0.30]x [0.30]y … … (ii)

Initial Initial Initial rate of formation

Experiment
[NO]/molL−1 [NO]/molL−1 of NO2 /molL−1 s−1

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

Similarity, experiment (ii) and equation (i) −: 0.384mal L−1 S −1 = k[0.60]x [0.30]y … … (iii)
→ Experiment (iii) and equation (i) −: 0.192 mol L−1 S −1 = k[0.30]x [0.60]y … … (iv)
0.096 0.30 x 0.30 y
Divide equation (ii) by (iii) −: 0.384 = [0.60] [0.30]
1 1
⇒ 4 = 2x then x = 2
0.192 0.30 x 0.60 y
Divide (iv) by (ii): 0.096 = [0.30] [0.30] ⇒ 2 = 2y then y = 1
put the value of x and y in equation (i): -
Rate = k[NO2 [O2 ]1 … … (v)
# Order of reaction = 2 + 1 = 3
# value of rate constant -: Put the value of rate, [NO], [O2 ] in equation (v) from any experiment.

Question: for the reaction 2NO(8) + Cl2(8) → 2NOCl(8), the following data were collected. All
the measurements were taken at 263k.
(i) Write the expression for rate law.
(ii) Calculate the value of rate constant and specify its unit.
(iii) What is the initial rate of disappearance of Cl2 in experiment 4?

APNI KAKSHA 6
 Initial rate of
Exp. No. Initial [No] (M) Initial [𝐂𝐥𝟐 ] (M) disappearance of
𝐂𝐥𝟐 (M/min)
1. 0.15 0.15 0.60
2. 0.15 0.30 1.20
3. 0.30 0.15 2.40
4. 0.25 0.25 ?

Answer: Rate law: Rate = K[NOx [U2 ]Y

→ Initial rate becomes (Rate) = k[NOx ][Cl2 ]y
→ Comparing experiment 1 and 2: (Rate) 1 = k[0.15]x [0.15]y = 0.60 … … (i)
(Rate )2 = K[0.15]x [0.30]y = 1.20 … … (ii)
→ Dividing equation (ii) by equation (i) →
( Rate )2 1.20 k[0.15]x [0.30]y
= = Then, 2y = 21
( Rate )1 0.60 k[0.15]x [0.15]y
→ Comparing experiments 1 and 3:( Rate )1 = K[0.15]x [0.15]y = 0.60 … … (iii)
( Rate )3 = K[0.30]x [0.15]y = 2.40 … … (iv)
Dividing equation (iv) by equation (iii): -
( Rate )3 k[0.30]x [0.15]y 2.40
= =
( Rate )1 k[0.15]x [0.15]y 0.60
⇒ 2x = 4 then x = 2

# Rate haw: Rate = K[NO2 [Cl2 ]

Rate 0.60
# Rate constant K = [NO2 [Cl ] = (0.15)2 (0.15) = 177.51 mol−2 L2 min−1
2
# Initial rate of disappearance of a2 in experiment 4 is γ4 .
r4 = k[NO2 [U2 ] = 177.51 × (0.25)2 (0.25)
M
r4 = 2.77
min

Molecularity of a reaction: -
→ The no. of reacting species [ atoms, ions or molecules] taking part in a one step reaction [ an
elementary reaction], which must collide simultaneously in order to bring about a chemical
reaction is called molecularity of a reaction.
Molecularity → Unimolecular Reaction → When one reacting species is involved.
→ Bimolecular Reaction → Reaction via simultaneous collision between two species.

Δ
Example: (i) NH4 NO2 ⟶ N2 + 2H2 O : Unimoleculer.
(ii) 2HI ⟶ H2 + I2 : Bimolecular.
Note: Generally, molecularity greater than 3 is not observed, because simultaneous collisions
of more than 3 molecules are not possible.

APNI KAKSHA 7
 Difference between order and molecularity
Molecularity Order
(i) It is defined as the no. of molecules of (i) It is defined as the sum of the power of
reactant taking part in a reaction. concentration terms that appear in rate law.
Δ Δ
(ii) Example: NH4 NO2 ⟶ N2 + 2H2 O (ii) NH4 NO2 ⟶ N2 + 2H2 O
molecularity = 1 Rate = K[NH4 NO2 ], order = 1
(iii) It is a theoretical value. (iii) It is an experimental value.
(iv) It is always a whole no. It can neither (iv) It may be zero, fractional or integer
be zero nor fractional.
(v) It is derived from rate determining (v) It is derived from rate expression
step in the mechanism of a reaction.

I−
Note: Let us consider a reaction 2H2 O2 → 2H2 O + O2
Alkaline Medium
Evidences suggest that this reaction takes place in two step.
(i) H2 O2 + I ⊖ ⟶ H2 O + IO⊖ [slow]
(ii) H2 O2 + IO⊖ ⟶ H2 O + I ⊖ + O2 [fast]

→ Slow step [first step] is the rate determining step [RDS].

→ Rate equation for reaction can be written on the basis of RDS.
d[H2 O2 ]
Rate = − = k[H2 O2 ]1 [I − ]1
dt
→ overall order of reaction = 1 + 1 = 2

Integrated Rate Equations

Zero order Reaction: - Let us consider a zero-order reaction R → P
d[R]
Then rate = − = k[R]0 = k Differential rate Equation.
dt
⇒ d[R] = −kdt ⟹ on integrating both side: ∫ d[R] = −k ∫ dt + I constant of integration.
⇒ [R] = −kt + I − i
At t = 0, the concentration of reactant R = [R].
By equation (i) ⇒ [R]0 = −k × 0 + I then I = [R]0
→ put the value of I in equation (i) −: [R] = −k t + [R]0 Integrated rate Equation.
y = mx +c

→ Straight line graph between [R] and f

→ slope = −k

APNI KAKSHA 8
Example of zero order reaction: - (i) Enzyme catalysed reactions.
(ii) Decomposition of NH3 on a hot platinum surface at high pressure.
1130 K
2NH3 (g) → N2 (g) + 3H2 (g)
Pt catalyst
→ Rate = K[NH3 ]∘
Explanation: - At high pressure the metal surface gets saturated with gas molecules. So, a
further change in reaction condition is unable to change the amount of ammonia on the surface
of the catalyst, making rate of reaction independent of its concentration.
Au
(iii) 2HI(g) ⟶ H2(g) + I2 (q)

Integrated rate equation of first order reactions: -

d[R] d[R]
consider a first order reaction: R → P Rate = − = k[R] ⇒ = −kdt
dt [R]
d[R]
on integration ⇒ ∫ = −k ∫ dt + I
[R]
→ When t = 0 then [R] = [R]0
→ Put this value in equation (i) −: ln[R]0 = −k × 0 + I ln[R] = −k + +I … … (i)
I = ln[R]0 … … (ii) constant of
integration.
→ By equation (i) and (ii): - ln[R] = −k ⋅ t + ln[R]0 … … (iii)
↓ ↓ ↓ ↓
y = m x + c
[R]0
→ 2 ⋅ 303log = kt
[R]
[R]0 k
→ log = t
[R] 2.303
↓ ↓ ↓
y = m∙x
k
slope =
2.303

1 [R]0
⟶ k = ln
On rearranging equation (iii): ln[R] − ln[R]0 = −kt t [R]
[R]
→ ln = −kt
[R 0 ]
[R]
→ [R] = e−kt then [R] = [R]0 e−kt
0

APNI KAKSHA 9
Graph between [R] and time t →
At t1 , [R]1 Then By equation (iii) →
At t 2 , [R]2 ln[R]1 = −k±1 + ln[R]0
ln[R]2 = −kt 2 + ln[R]0
1 [R]
K = (t ln [R]1
2−t1 ) 2

Example -: (i) All natural and artificial radioactive decay of unstable nuchi take place by 1st
order kinetics. 226 4 222
88 Ra ⟶ 2 He + 86 Rn
pt
(ii) Hydrogenation of ethene C2 H4 (g) + H2 (g) ⟶ C2 H6 (g): Rate = k[C2 H4 ]

Question: The initial concentration of N2 O5 in the following 1st order reaction

1
N2 O5 ( g) ⟶ 2NO2 ( g) + 2 O2 (g) was 1.24 × 10−2 mol L − 1 at 318 K. The concentric of N2 O5
after 60 minutes was 0.20 × 10−2 mol L-1. Calculate the rate constant of the reaction at 318K ?
2.303 [R]
Answer: For 1st order reaction: K = (t log [R]1
2−t1) 2
2.303 1.24×10−2malL−1 2.303
→ K = (60 min−0 min) log 0.20×10−2 mol L−1 = log 6.2 min−1
60
→ K = 0.0304 min−1

First order gas phase reaction: -

Let us consider a 1st order reaction: A(g) → B(g) + C(g)
Pi : Initial pressure of A. At t = 0: Pi atm 0 0
Pt: Total pressure at time t. At time t: ( Pi − x) x x
PA , PB , PC : Partial pressure of A, B, C respectively.
x: Decrease in pressure after time t.
Total pressure at time t
Pt = PA + PB + PC
Pt = (Pi − x) + x + x
2.303 P
→ Rate Constant K = log (P i ) then x = Pt − Pi
t A
2.303 P
K= i
log 2P −P # Partial pressure of A at time t
t i t

PA = Pi − x = pi − (pt − Pl )
PA = 2Pi − pt

Question: Experimental data for the first order thermal decomposition of SO2 Cl2 at constant
volume.
Δ
SO2 Cl2 ⟶ SO2 + Cl2

Exp. Time Total pressure

1. 0s Pi = 0.4
2. 100 s Pt = 0.7

APNI KAKSHA 10
 2.303 p
Answer: k = i
log 2p −p
t i t
2.303 0.4 2.303
= 100 s log 2×0.4−0.7 = (2log 2) = 1.387 × 10−2 s
100

Half life of a reaction: - "The time in which the concentration of a react is reduced to one half
of its initial concentration."
→ For reaction R → P
At t = 0 [R]0
[R]0
At t = t y2 2

→ Half life for zero order Reaction → Half life (t1/2 ) is independent of initial concentration.
[R]0−[R] 2.303 [R]0
↪ Rate constant k = ↪ Rate constant k = log
t t [R]
[R]0 2.303 [R]0
At t = t1/2 (Half life) [R] = ↪k= log [R]
2 t1/2 0/2
[R]
[R]0− 0 2.303
2
k= ↪k= log 2
t1/2 t1/2
[R]0 [R]0 0.693 0.693
k = 2t t1/2 = ↪k= t1/2 =
1/2 2k t1/2 k

→ Half life of zero order reaction → Half life (t1/2 ) is independent of initial concentration.
depends on initial concentration
of reactant.
1
(a) t1/2 ∝ [R]0 (b) dy2 ∝ k → Half life [t1/2 ] for 1th order reaction

A → Products

APNI KAKSHA 11
APNI KAKSHA 12
Ques: A first order reaction is found to have a rate constant k = 5.5 × 10−14 s.
Find the half life of the reaction.
Ans: For first order, Half life
0.693 0.693
t1/2 = =
k 5.5 × 10−14
t1/2 = 1.26 × 1014 s

Ques: A first order reaction takes place in 30 min for 50% completion. Calculate the time
required for 90% completion of this reaction. Given log 2 = 0.3010
Ans: 50 % Completion time = t y/2 = 30 min
0.693 0.693
k= = = 0.023 min−1
t y/2 30 min
⇒ for the same reaction, time required for 90% completion: -
k = 0.023 min−1 ; [R]0 = 100 [R] = 100 − 90 = 10
2.303 [R]0 2.303 100
⇒ t= log = −1
log = 100.13 min.
k [R] 0.023 min 10
Pseudo first order reaction: - A chemical reaction between two substances when
one reactant is present in exes quantity.
(i) Hydrolysis of ethyl acetate: -
O O
|| ||
H
CH3  C  OC2H5  H2O   CH3  C  OH  C2H5OH
If At time t = 0: 0.01 mol 10 mol 0 mol 0 mol
and, at time t: 0 mol 9.99 mol 0.01 0.01
⇒ [H2 O]t=0 ≃ [H2 O]+ mean that concentration of H2 O does not change. So it can not
change the rate.
[H2 O] = constant
k H2 O] = constant
′[

=k
⇒ Rate of reaction = K ′ [H2 O][CH3 COOC2 H5 ]
Rate of reaction = K[CH3 COOC2 H3 ] ⇒ I ≠ indicates 1st order kinetics.

(ii) Hydrolysis of Cane sugar: -


C12H22O11  H2O 
H
 C6H12O6  C6H12O6
Glucose Fructose

Rate = K [e12 H22 O11 ]

APNI KAKSHA 13
Ques: For the hydrolysis of methyl a alate in aqueous solution, the following results were
obtained.
(i) If concentration of water remains constant then show that it follows pseudo first order
reaction.
Time (Second) 0 10 20
O
||
[CH3  C  OCH3 ] [mol L1 ] 0.10 0.05 0.025

(ii) Calculate average rate of reaction between time interval 10 to 20 second.

Ans: (i) [H2 O] = Constant (During reaction)
O O
|| ||
H2O
So, rate  K [Methylocetate] CH3  C  OCH3  CH3  C  OH  CH3  OH
__________ O
| ||

2.303 [CH3  C  OCH3 ]O
First order, then K  log
t O
||
[CH3  C  OCH3 ]

At time t1 = 10 second
2.303 0.10
⇒ K1 = log = 6.93 × 10−2 s−1
10 0.05
At time t 2 = 20 second
2.303 0.10
⇒ k2 = log = 6.93 × 10−2 s−1
20 0.025
# Rate constant for the reaction has a constant value under any given time interval. Hence
the given reaction follows pseudo firth order kinetics.
O
||
(ii)
 [CH3  C  OCH3 ] [0.025  0.05]
Average rate    0.0025 mol L1 S1
t 20  10

APNI KAKSHA 14
 Important Previous Year Questions
(1) For a first order reaction H2 O2 (99) ⟶ H2 O(l) + O2 (g),
rate constant k = 1.06 × 10−3 min−1 .
(a) How long will it take for 15% of a sample of H2 O2 to decompose?
Ans: Let us consider [H2 O2 ]0 = 100 mall h, then [H2 O2 ]z = 100
2.303 [H2 O2 ]0 2.303 100
k= log ⇒t= −3
log = 153.3 min.
t [H2 O2 ] 1.06 × 10 85
(b) How long time it will take for 05% of the sample to decompose?
⇒ Now: [H2 O2 ]0 = 100 mol/h [H2 O2 ]t = 100 − 05 = 15mal/L
2.303 [H2 O2 ]0 2.303
t= log = log 6.667 = 1790.05 min
k [H2 O2 ]t 1.06 × 10−3

(2) The rate constant for a zero order reaction is 0.0030 mol L−1 S −1 . How long will it take
for the initial concentration to fall from 0.10M to 0.075 m
Ans: For zero order reaction ⇒ K = [R]0 − [R]
[R]0 = 0.10 M
[R 0 ]0 − [R] 0.10 − 0.075
[R] = 0.075 M Time t = =
k 0.0030
K = 0.0030 mol L−1 S −1 t = 0.33 second

1
(3) For a reaction N2 O5 → 2NO2 + 2 O2

(i) Show that it follows first order reaction?

(ii) Calculate the half life?

time (s) 0 300 600

mol
[N2 O5 ] ( ) 1.6 × 10−2 0.8 × 10−2 0.4 × 10−2
2s

2.303 [N O5]0
Ans: (i) for first order reaction K = log [ N2
t 2 O5 ]

(a) At t = 300 second, [N2 Os ]0 = 1.6 × 10−2 mol h−1 δ−1 and [N2 O5 ] = 0.01 × 10−2
2.303 1.6 × 10−2
K= log = 2.31 × 10−3 s −1
300 0.8 × 10−2
(b) At t = 600, [ N2 O5 ] = 0.4 × 10−2

APNI KAKSHA 15
 2.303 1.6 × 10−2
k= log = 2.31 × 10−3 s−1
600 0.4 × 10−2
⇒ Rate constant remains lame in both condition (a & b). So we can say above reaction is
first order.
0.693 0.63
(𝐢𝐢) k = 2.31 × 10−3 s − 1 then t y2 = = = 300 s.
k 2.31 × 10−3

(4) First order reaction 2 N2 O5 (g) ⟶ 4NO2 (g) + O2 (g) at 40∘ c, data is given below –

[𝐍𝟐 𝐎𝐬 ]( mot /L) Time (min)

0.400 0.00

0.289 20.0

0.209 40.0

0.151 60.0

0.109 80.0

(i) Calculate the rate constant (with its unit).

mal
At time t = 20 min, [ N2 O5 ] = 0.289
L
md
& [N2 O5 ]0 = 0.4
L
2.303 0.4 2.303
k= log = log 1.304
20 0.289 20
k = 0.01625 min−1 = 1.62 × 10−2 min−1
(ii) What will be concentration of N2 O5 of ter 100 min ?
2.303 0.4 0.4 1.62
k= log = 1.62 × 10−2 thin log = = 070
100 [N2 O5 ] [N2 05] 2.303
0.4 0.4 mol
⇒ = antilog 0.705 = 5.07 then [N2 O5 ] = = 0.078
[ N2 O5 ] 5.07 L
(iii) Initial rate of reaction?
mol
Initial rate = k[ N2 O5 ] = 0.4 × 1.62 × 10−2 = 6.4 × 10−3
L min

(5) For a reaction A + B → P the rate is given by Rate = k[A][B]2

APNI KAKSHA 16
(a) How is the rate affected if [B] is doubled?
Rate of reaction = k[A] [2B]2 = 4[A] [B]2 = 4 × original rate
(b) What is overall order of reaction if A is present in large exes?
⇒ If A is present in large excess, then the reaction will be independent of the concentration
of A.

Thin order of reaction = 2

Temperature dependence of the rate

⇒ The rate of the reaction is dependent on temperature. This is expressed in terms of
temperature coefficient. Rate of reaction increases with temperature
Temperature Coefficient:-
It is the ratio of rate constant at temperature 300 K[298 + 10] to the rate constant at
temperature 298 K.
⇒ It is observed that for a chemical reaction with rise in temperature by 10∘ , the rate
constant is nearly doubled.
Arrhenius Theory:-
Arrhenius theory state that products are formed through intermediates or activated
complex.
H2 (g) + I2 (g) ⟶ 2HI(g)
⇒ When a molecule of H2 and a molecule of I2 collide to form an unstable intermidiate.
unstable intermidiate [ activated complex] exist for a very short time and then breaks up
to form 2 molecules of HI.

APNI KAKSHA 17
Activation Energy [𝐄𝐚 ] :-
Minimum energy required to convert a reactant into activated complex is known as
activation energy.
Ea = Energy difference between activated complex and reactant molecules.
Arrhenius Equation:-
The temperature dependence of rate of a chemical reaction is expressed by Arrhenius
equation.
Ea
K = A ⋅ e−RT
𝐀 − ∶ Frequency factor
𝐄𝐪 − ∶ Activation Energy
𝐓 − ∶ Temperature
𝐑 − ∶ Gas Constant
⇒ Taking log of both side of Arrhenius Equation :-
Ea
log k = log A −
2.303 RT
1 −Ea
𝐆𝐫𝐚𝐩𝐡: log K vs gives slope =
T 2.303R
Intercept = log A

APNI KAKSHA 18
 Ea
# If k1 is the rate constant at log K1 = log A −
2.303 R T1

temperature T1 at temperature T1
E9
⇒ At T2 ⇒ rate constant k 2 log K 2 = log A −
2.303RT2
K2 E9 T2 − T1
log = [ ]
K1 2.303R T1 ⋅ T2

Ques: The rate of most reactions become double when their temperature is raised from 290 K
to 300 K. Calculate their activation energy.
[Given, R = 8.314 J mol−1 K −1 ]
k
Ans: T1 = 290 K, T2 = 308 K, k2 = 2
1

K2 E9 T2 − T1
log = [ ]
k1 2.303R T1 ⋅ T2
Ea 300 − 290
⇒ log 2 = [ ]
2.303 × 8.314 298 × 300
Eq = 52903.05 J mol−1

Ques: The rate constant for the first order decomposition of H2 O2 is given by the following
1×104
equation log K = 14.2 − K.
T
Calculate E9 for this reaction and rate constant K, if its half life period be 200 min.
[Given R = 8.314 J K −1 mal−1 ]
1 × 104
𝐀𝐧𝐬: log k = 14.2 − k … (i)
T
Arrhenius Equation:

APNI KAKSHA 19
 E9
log k = log A − … (ii)
2 ⋅ 303RT
on comparing equation (i) / (ii) :
Ea
= 1 × 104 K
2.303R
⇒ Eq = 2.303 × 8.314 × 104 = 191.4 kJmal−1
Calculation of rate constant 𝐊 :-
Given t1/2 = 200 min = 200 × 60 s
0.693 0.693
k= = = 5.77 × 10−5 s −1
t1/2 200 × 60 s

Ques: For a decomposition reaction, the values of k at two different temperatures are given
below : K1 = 2.15 × 10−8 L/ (mol s) at 650 K
K 2 = 2.39 × 10−7 L (mol s) at 700 K
Calculate the value of E9 for the reaction.
[Given log 11.11 = 1.046, R = 0.314Jk −1 mol−1 ]
K2 E9 T2 −T1
Ans: log = [ ]
K1 2.303R T1 ⋅T2

2.39 × 10−7 Ea 700 − 650

⇒ log = [ ]
2.15 × 10−8 2.303 × 0.314 700 × 650
E9 50
⇒ log 11.11 = 1.046 = [ ]
2.303 × 0.314 4.55 × 105
Eq = 182.25 kJ/mol

Ques: The decomposition of A into products has a value of k as 4.5 × 103 5−1 at 10∘ C and energy
of activation 60 kJ mol−1 . At what temperature would K be 1.5 × 104 5−1 ?
Ans: T1 = 10 + 273 = 283 K, K1 = 4.5 × 103 s−1 , Eq = 60KJ mol−1
At T2 =? ⇒ K 2 = 1.5 × 104 s−1
K2 E9 T2 − T2
⇒ log = [ ]
K1 2.303R T1 ⋅ T2
1.5 × 104 60 T2 − 283
⇒ log 3
= [ ]
4.5 × 10 2.303 × 8.314 283T2
T2 − 283
⇒ 0.523 = 3133.63 [ ]
203T2
⇒ 0.953T2 = 283 T2 = 297 K.

APNI KAKSHA 20
Maxwell Boltzmann Distribution curve:-
According to Maxwell and Boltzmann. The distribution of Kinetic Energy may be
described by plotting the fraction of molecules with a given kinetic energy.
⇒ The peak of the carve corresponds to the most probable kinetic energy. The most
probable kinetic energy is the kinetic energy of maximum fraction of molecules.
⇒ When the temperature is raised, the maximum of the curve moves to the higher energy
value and curve broadens out and proportion of molecules with higher energy increases.
⇒ Increasing the temperature of the substance increases the fraction of molecules, which
collide with energy greater than Ea.

Effect of catalyst :
⇒ The rate of a chemical reaction changes by the presence of catalyst. It alters the rate by
providing alternative path of lower / greater activation energy to the reactants.
⇒ The catalyst [which increases rate of a reaction] reduces the activation energy.
⇒ A catalyst does not change the enthalpy [ΔH] , Gibbs energy of reaction [ΔG] and
equilibrium constant [K] of a reaction.

Collision Theory : This theory is based on Kinetic theory of gases.

APNI KAKSHA 21
 According to this theory - the reactant molecules are assumed to be hard spheres and
reaction is postulated to occur when molecules collide with each other perfectly.
Collision Frequency :
The no. of collisions per second per unit volume of reaction mixture is known as collision
frequency.
⇒ For a biomolecular elementary reaction A + B → Products

rate of this reaction = ZAB e−Ea/RT

ZAB : Collision frequency of reactants A and B.

e−Ea/RT : Represents the fraction of molecules with energies equal to or greater than Ea.
⇒ The proper orientation of reactant molecules lead to bond formation whereas improper
orientation makes them simply bounce back and no products are formed.
̅ H ⟶ CH3 OH + ̅̅̅
CH3 Br + O Br

⇒ 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.

Rate = PZAB e−Ea/RT

⇒ 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.

APNI KAKSHA 22
APNI KAKSHA 23