CHEMICAL KINETICS

Rate of the Reaction

Rate → speed

change in position
S=
change in time

change in concentration
R=
change in time

Unit of rate of reaction is concentration time−1 or mol l−1 s−1 .

If expressed in terms of partial Pressure unit will be atm s−1 .
 Rate of the Reaction

Reactant Product

Rate of disappearance of R [P]2

decrease in concentration of R ∆[R] [P]1

= =−
Time taken ∆t
[R]1

Conc.
Rate of appearance of P
[R]2
increase in concentration of P ∆[P]
= =+
time taken ∆t t1 t2
Time
 Rate of the Reaction

Types of reaction

Moderate reaction Slow reaction

Fast reaction E.g Inversion of cane sugar, Conversion of graphite to
Hydrolysis of starch diamond, Rusting of iron
Eg: Acid-Base reactions
 Average Rate of Reaction
Rate of reaction measured in certain interval of time.

Consider a reaction:
R→P [P]2

Total change in concentration [P]1

ravg = Conc.
Total time taken
[R]1
∆R [R]2 −[R]1
ravg = − =− [R]2
∆t t 2 − t1

∆[P] [P]2 − [P]1 t1 t2

ravg = + =+
∆t t 2 − t1 Time
 Instantaneous Rate of
Reaction
The rate at particular moment of time.

∆R ∆[P]
ravg =− ravg =
∆t ∆t
50
As ∆t → 0 40

∆R 30
rinst = lim −
∆t →0 ∆t 20
dR d[P] 10
rinst =− rinst =
dt dt 0 20 40 60 80 100 120
𝐭𝟏
It is determined graphically by drawing a tangent at time t on either of curves for
concentration of R and P versus t and calculating it’ s slope.
Q. For a reaction concentration of product is given as C = 2.5t 2 − 4 mol l−1 .
Find average rate of reaction between time interval t1 = 10 sec and t 2 =
20 sec. Also find instantaneous rate of reaction at t = 12 sec.
Sol. Concentration of P at t1 = 10 sec.
C1 = 2.5t 2 − 4 = 2.5 10 2 − 4 = 246 mol l−1
Concentration of P at t 2 = 20 sec.
C2 = 2.5(20)2 − 4 = 996 mol l−1
Average rate of reaction:
ΔC 996 − 246 750
= = = = 75 mol l−1 s−1
Δt 20 − 10 10

Instantaneous rate of reaction:

dC d(2.5t 2 − 4)
= = = 5t
dt dt
At t = 12 sec.
rate = 5 × 12 = 60 mol l−1 s−1
 Expression for Rate for Reaction
Stoichiometric coefficients of reactant or products are not equal

N2 + 3H2 → 2NH3

1 mol consumed 3 mol consumed 2 mol produced

d[N2 ] 1 d H2 3 d NH3 2
− = mol min−1 − = mol min−1 = mol min−1
dt 1 dt 1 dt 1
𝟏 𝟏
𝐑𝐚𝐭𝐞 𝐨𝐟 𝐝𝐢𝐬𝐚𝐩𝐩𝐞𝐚𝐫𝐚𝐧𝐜𝐞 𝐨𝐟 𝐍𝟐 = 𝐑𝐚𝐭𝐞 𝐨𝐟 𝐝𝐢𝐬𝐚𝐩𝐩𝐞𝐚𝐫𝐚𝐧𝐜𝐞 𝐨𝐟 𝐇𝟐 = 𝐑𝐚𝐭𝐞 𝐨𝐟 𝐚𝐩𝐩𝐞𝐚𝐫𝐚𝐧𝐜𝐞 𝐨𝐟 𝐍𝐇𝟑
𝟑 𝟐

d[N2 ] 1 d H2 1 d NH3
− =− = Rate of Reaction
dt 3 dt 2 dt
 aA + bB → cC + dD

rate of disappearance of A 1d A
rate of reaction with respect to A = =−
stiochiometric coefficient a dt

rate of diappearance of B 1d B
rate of reaction with respect to B = =−
stiochiometric coefficient b dt

rate of appearance of C 1 d[C]

rate of reaction with respect to C = =+
stiochiometric coefficient c dt

rate of appearance of D 1 d[D]

rate of reaction with respect to D = =+
stiochiometric coefficient d dt

−1 d[A] −1 d[B] +1 d[C] +1 d[D]

R= = = =
a dt b dt c dt d dt
Example 1:
Hg l + Cl2 g → HgCl2 s

Rate of reaction:
d Hg d Cl2 d HgCl2
=− =− =
dt dt dt

Example 2:

2HI → H2 + I2

Rate of reaction:
1 d[HI] d[H2 ] d[I2 ]
=− = =
2 dt dt dt
Q. In a reaction 2A → Products. The concentration of A decreases from
0.5 mol l−1 to 0.4 mol l−1 in 10 mins. Calculate the rate of reaction during
this interval?
Q. In a reaction 2A → Products. The concentration of A decreases from
0.5 mol l−1 to 0.4 mol l−1 in 10 mins. Calculate the rate of reaction during
this interval?

Sol. As we know,
Rate of reaction with respect to A,

rate of disappearance of A 1d A
= =−
stiochiometric coefficient of A 2 dt

1 0.4 − 0.5 0.1

=− =
2 10 20

= 5 × 10−3 mol l−1 s −1

Q. For the reaction
N2 g + 3H2 (g) → 2NH3 (g)
If rate of appearance of ammonia is 34 kg hr −1 . Calculate the rate of
disappearance of nitrogen and hydrogen in kmol hr −1 .

Sol. −
d[N2 ]
=−
1 d[H2 ] 1 d[NH3 ] 1
= = ×2
Rate of reaction: dt 3 dt 2 dt 2
d[N2 ] 1 d[H2 ] 1 d[NH3 ]
− =− = Rate of disappearance of N2
dt 3 dt 2 dt

d[NH3 ] d[N2 ] 1
= 34 kg hr −1 =− = × 2 = 1 kmol hr −1
dt dt 2

Convert kg hr −1 into kmol hr −1 Rate of disappearance of H2

d[NH3 ] 34 d H2 1
= = 2 kmol hr −1 =− = 3 × × 2 = 3kmol hr −1
dt 17 dt 2
 Rate Law
Rate of Reaction ∝ (concentration of reactants)n

aA + bB → cC + dD

Rate ∝ [A]x [B]y

Rate = k [A]x [B]y

Reaction

Rate
Constant
Temperature
 Order of Reaction

aA + bB → cC + dD

Rate ∝ [A]x [B]y

Rate = k [A]x [B]y

x→order of reaction w.r.t ‘A’

y→order of reaction w.r.t ‘B’

n = (x+y)→overall order of reaction

 Order of Reaction

Order can be determined experimentally not by balanced equation

Balanced equation

2NO g + O2 (g) → 2NO2 (g)

Q. The conversion of molecules X to Y follows second order kinetics. If
concentration of X is increased to three times how will it affect the
rate of formation of Y ?
Q. The conversion of molecules X to Y follows second order kinetics. If
concentration of X is increased to three times how will it affect the
rate of formation of Y ?
Sol. X→Y

rate = k[X]2

Let initial concentration of X be X1 , So,

rate = k[X1 ]2

Let final concentration of X be 3X1 , So,

rate = k[3X1 ]2 = 9k[X1 ]2

Rate is increased by 9 times.

Q. 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 0.2 0.2 0.4

B mol l−1 0.3 0.1 0.05

r0 (mol l−1 s −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?

Sol. From rate law, rate = k[A]x [B]y 5.07 × 10−5 = [0.2]x [0.3]0 ⋯ 3

5.07 × 10−5 = [0.2]x [0.3]y ⋯ 1 1.43 × 10−4 = [0.4]x [0.05]0 ⋯ 4

Divide (3) by (4)
5.07 × 10−5 = [0.2]x [0.1]y ⋯ 2 5 1x 3
Divide (1) by (2) = →x=
14.3 2 2
5.07 × 10−5 [0.2]x [0.3]y
−5 = x y ⟹ 1 = [3]y 3
5.07 × 10 [0.2] [0.1] Order with respect to A is & B is 0
[3]0 = [3]y → y = 0 2
 Unit of Rate Constant
aA + bB → cC + dD

Rate = k[A]x [B]y

Rate
k=
[A]x [B]y

rate of reaction mol l−1 s −1

Unit of k = =
(concentration of reactant)x+y (mol l−1 )x+y

n = x + y = overall order of the reaction

Unit of k = mol l−1 (1−n) s −1

Unit of Rate Constant
Unit of k = mol l−1 1−n −1
s

Order Unit of 𝐤

0
mol l−1 s−1

1 s−1

2
l mol−1 s−1
Q. Identify the reaction order from each of the following rate constant.
1 −1 −1 1
−1
i . k = mol l2 2 s ii . k = mol 2 l s −1
2

Sol.
(i) We know that, (ii)

Unit of k = mol l−1 1−order s −1 Comparing power of mole,

1
− = 1 − order
Unit of k = mol1−order lorder−1 s −1 2
3
order of reaction =
Comparing power of mole, 2
1
= 1 − order
2
1
order of reaction =
2
 Elementary Reaction

Reaction which takes place in single step.

2H2 + O2 → 2H2 O

For elementary reaction,

Order of reaction = Sum of stoichiometric coefficients of reactants.

 Complex Reaction

The reaction which takes place in more than one step.

4HBr + O2 → 2H2 O + 2Br2

Step 1: HBr + O2 → HO2 Br

Step 2: HO2 Br + HBr → 2HOBr Each step is called

elementary reaction
Step 3: 2HOBr + 2HBr → 2H2 O + 2Br2

Overall rate of complex reaction is determined by slowest step

 Molecularity of Reaction
Molecularity is the number of reactant molecules, atoms and ions taking
part in a elementary reaction which collide simultaneously to form
product.

Elementary reaction:
xA + yB → C

Molecularity = x + y
Unimolecular

Reaction in which only one molecule takes part

Example:
PCl5 PCl3 Cl2
 Molecularity of Reaction
Bimolecular

Reaction in which 2 molecules take part in reaction

Example: CH4
Cl2 HCl CH3 Cl

Trimolecular

Reaction in which 3 molecules take part in the reaction

Molecularity of three is
very rare because the
Example: 2NO O2 2NO2 probability of more than
three molecules
colliding simultaneously
with the correct
orientation and
sufficient energy is
extremely low.
 Integrated Rate Equation
For reaction,
R→P

Rate law:
rate ∝ [R]n

rate = k[R]n

n = order of reaction, k = rate constant

Instantaneous rate:
d[R]
rinst = −
dt
dR
− = k[R]n
dt
 Integrated Rate Equation
dR
− = k[R]n
dt

dR
= −k × dt
Rn

dR
න = න −k × dt
Rn
Initial time: t 0 = 0 ⟹ R = R 0

Any time: t ⟹ R = R

R t
dR
න n = න −k × dt
[R0 ] R t0
 Zero Order Reaction
For reaction, R→P • Enzyme catalysed reactions
d[R]
− = k[R]n • Reactions occurring on
dt metal surfaces:
For zero order, n = 0
dR Pt, 1130 K
− =k 2NH3 N2 + 3H2
dt

d R = −kdt
Integrate both sides,
R t
න d R = න −kdt
R0 0

R t
R R0 = −k × t 0 ⟹ R = R0 − k × t
 Graphical representation of Zero Order Reaction
R→P

R = R 0 − kt

y = mx + c ⋯ straight line
Completion time t100% :
[R 0 ]
R = R 0 − kt
Slope = −k

[R] →
t = t100% ⟹ [R] = 0

0 = R 0 − k × t100%

R0
t100% = time → t100%
k
Q. A zero order reaction having concentration of reactant 0.4 M
completes in 80 minutes . Find the value of rate constant for the
reaction.
Q. A zero order reaction having concentration of reactant 0.4 M
completes in 80 minutes . Find the value of rate constant for the
reaction.
Sol.
For the zero order reaction,

R0
t100% =
k
R0
k=
t100%

R 0 = 0.4 M; t100% = 80 minutes

0.4
k= = 0.005 mol l−1 min−1
80
 First Order Reaction
For reaction, R→P
• Radioactive Decays:
dR
− = k[R]n 226
→ 42He + 222
dt 88Ra 86Rn
For first order, n = 1
dR • Decomposition of N2 O5
− = k[R]
dt
1
d[R] N2 O5 → 2NO2 + O2
= −kdt 2
[R]
Integrate both sides, R
R
d[R] t 2.303 × log = −kt
න = න −kdt R0
R0 [R] 0

R
ln R − ln R 0 = −kt ⟹ ln = −kt
R0
 Graphical representation of First Order Reaction
R→P

R
ln = −kt ⟹ R = R 0 e−kt
R0

[R] kt
2.303 log = −kt ⟹ log R = log R 0 −
[R 0 ] 2.303

log[R 0 ]
[R 0 ]
R →

log[R] →
Slope = −
2.303
Takes infinite time to complete
t100% = ∞

time → time →
First Order Reaction for Gaseous Phase Reactions
A g → B g + C g

ti = 0 pi 0 0

tf = t pi − x x x
pf
ln = −kt
pi
pi − x
ln = −kt
pi

PT = pi − x + x + x = pi + x

x = PT − pi ⟹ pf = pi − x = 2pi − PT
2pi − PT
ln = −kt
pi
Q. A first order reaction has a rate constant 1.15 × 10−3 s−1. How long
will 5 g of this reactant take to reduce to 3 g ?

Sol. As we know, for first order reaction:

[R]
2.303 log = −kt
[R 0 ]

2.303 R0
log =t
k R

2.303 5
t= log
1.15 × 10−3 3

2.303
t= log 5 − log 3 = 799.2 s
1.15 × 10−3
 Half Life
The half life of a reaction is the time in which the concentration of a
reactant is reduced to one half of its initial concentration.
Half Life is
238 214
U→ Pb + radiation equal to 3.1
minutes
Radioactivity Time(min)
8 0
4 3.1
2 6.2
1 9.3 Half life → t 1
2
0.5 12.4
 Half Life for Zero Order Reaction
R→P

R = R0 − k × t

R0
at t = t 1 ; R =
2 2

t1 →
R0

2
= R0 − k × t1
2 2

R0 R0
k × t1 = ⟹ t1 =
2 2 2 2k
R0 →
 Half Life for First Order Reaction

R→P 2.303 × log 2 0.693

t1 = =
[R] 2 k k
2.303 × log = −k × t
R0

R0
At t = t 1 ; R =
2 2

R0

t1 →
2.303 × log 2 = −k × t 1

2
R0 2

1
2.303 × log = −k × t 1 ⟹ 2.303 × log2 = k × t 1
2 2 2
R0 →
Q. For following first order reaction:
1
H2 O2 → H2 O + O2
2
Case 1:[H2 O2 ]i = 4M, [H2 O2 ]f = 2M
Case2:[H2 O2 ]i = 5M, [H2 O2 ]f = 2.5M
In which case we require more time for conversion??
Q. For following first order reaction:
1
H2 O2 → H2 O + O2
2
Case 1:[H2 O2 ]i = 4M, [H2 O2 ]f = 2M
Case2:[H2 O2 ]i = 5M, [H2 O2 ]f = 2.5M
In which case we require more time for conversion??

Sol. For first order reaction:

0.693
t1 =
2 k

Half life is independent of initial concentration, so in each case same

amount of time is require for conversion.
 Q. A first order reaction takes 40 minutes for 30% completion. Calculate the
half life t 1 .
2

Sol. For first order reaction 1 100

k= × 2.303 log
40 70
R
2.303 log = −k × t k = 8.918 × 10−3 min−1
R0

R0 For first order reaction

2.303 log
R
k= 0.693
t t1 =
2 k
R = 100 − 30 % ⟹ R = 70% R 0
0.693
t1 =
1 R0 2 8.918 × 10−3 min−1
k= × 2.303 log
40 70
R
100 0 t 1 = 77.7 min
2
 Pseudo First Order Reaction
The type of reaction which obey first order rate law although it has higher
molecularity for the reaction.

CH3 COOCH3 + H2 O → CH3 COOH + CH3 OH

At t = 0 0.1 mol 50 mol 0 mol 0 mol

At t = t 0 mol 49.9 mol 0.1 mol 0.1 mol

Rate = k H2 O [CH3 COOCH3 ]

k ′ = k[H2 O]

Rate = k ′ [CH3 COOCH3 ]

Example: Acidic hydrolysis of sugar

 Observation of Van’t Hoff
At every 10℃ rise in temperature T → T + 10 the value of rate of reation
gets doubled or tripled.

In case of constant concentration:

rate ∝ k

298 K ⟹ k T

298 + 10 = 308 K ⟹ k T+10

k T+10
= 2 to 3
kT

Temperature coefficient
 Arrhenius Equation
A mathematical relation between rate constant and temperature.

Ea
−RT
k=A×e

Rate Constant Arrhenius Gas Temperature Activation

Factor Constant Energy
or
Pre-exponential
Factor
 Activation Energy

H2 (g) I2 (g) HI(g) HI(g)

H I H I H I

H I H I
H I

Reactant Activated complex Product

 Activation Energy

Activated Complex

Ea

Energy

H2 + I2
2HI

Reaction coordinate
Minimum energy which must be provided to a chemical system with
potential reactants to undergo reaction and form products.
EReactant > Ea
 Maxwell- Boltzmann Distribution

Fraction of molecules
T More number of
Ea molecules

T + 10

Kinetic Energy

Area under the graph gives the total number of molecules

Fraction of molecules having energy greater than activation energy =
a E
−RT
e
Q. The rate constant for the decomposition of some hydrocarbon is
2.418 × 10−5 s−1 at 546 K . If the energy of activation is 179.9 KJ mol−1 ,
what will be the value of pre-exponential factor ?

Sol. Ea
We know that, log A = log k +
Ea 2.303 × RT
−RT
k=A× e
179.9 × 103
= log 2.418 × 10−5 +
Taking logarithm of both sides, 2.303 × 8.314 × 546
E
− a log A = 12.583
ln k = ln A × e RT

Ea Taking antilog,
ln k = ln A −
RT
A = 3.82 × 1012
Ea
2.303 × log k = 2.303 × log A −
RT
 Mathematical Interpretation of Arrhenius Equation
Arrhenius equation: Ea 1
log k = − + log A
−Ea 2.303 × R T
k= Ae RT
y = mx + c ⋯ Straight line
taking logarithm both sides
−Ea log A
ln k = ln Ae RT
Ea
−Ea slope = −

log k →
ln k = ln A + ln e RT 2.303 × R

Ea
ln k = ln A −
RT
Ea 1
ln k = − + ln A 1
R T →
T
 Mathematical Interpretation of Arrhenius Equation
Ea
log k = log A −
2.303 × RT
T1 ⟹ k1
Ea
log k1 = log A − ⋯1
2.303 × RT1
T2 ⟹ k 2 k2 Ea 1 1
Ea log = −
log k 2 = log A − ⋯2 k1 2.303 × R T1 T2
2.303 × RT2

Subtracting eq. 1 from eq. 2

k2 Ea T2 − T1
log =
Ea Ea k1 2.303 × R T1 T2
log k 2 − log k1 = −
2.303 × RT1 2.303 × RT2
Q. For a reaction, the values of rate constants at 300 K and 400 K are found
to be 1.2 × 10−3 and 2.4 × 10−2 s −1 . Find the activation energy for the
reaction.

Sol. T1 = 300 K ⇒ k1 = 1.2 × 10−3 s−1

T2 = 400 K ⇒ k 2 = 2.4 × 10−2 s−1

k2 Ea T2 − T1
log =
k1 2.303 × R T1 T2

k2 T1 T2
Ea = 2.303 × R × log ×
k1 T2 − T1

2.4 × 10−2 300 × 400 Ea = 29869.5 J mol−1

Ea = 2.303 × 8.314 × log ×
1.2 × 10−3 400 − 300 = 29.869 KJ mol−1
 Collision Theory for Rate of Reaction

Collision Theory

Molecules Hard Spheres Effective Collision

EReactant ≥ Ea Proper orientation

 Collision Theory for Rate of Reaction
NO + O3 → NO2 + O2

ON O3 ON O3
ON O3

NO O3 NO O3 NO O3

NO O3 NO2 O2
 Collision Theory for Rate of Reaction

Rate ∝ no. of collision collision frequency = ZAB

Rate ∝ probability of effective collison P

−Ea
Rate ∝ fraction of molecules with energy greater than or equal toEa e RT

−Ea
Rate ∝ P × ZAB × e RT

−Ea
Rate = P × ZAB × e RT
Rate = k [R]n
−Ea P × ZAB = A × [R]n
k= Ae RT
 Effect of Catalyst
Activation Energy Ea
R Activated complex → P

Activated complex

New activated complex

Ea UC
Ea C
Energy

P
Reaction Coordinate
 Effect of Catalyst
For uncatalysed reaction:
Ea UC
log k UC = log A − ⋯1
2.303 × RT

For catalysed reaction:

Ea C
log k C = log A − ⋯2
2.303 × RT

Subtracting eq. 1 from eq. 2

Ea C Ea UC
log k C − log k UC = − − −
2.303 × RT 2.303 × RT

kC Ea UC − Ea C
log =
k UC 2.303 × RT
Q. The activation energy for the reaction:
2NH3 (g) → N2 g + H2 (g)
are 20 KJ mol−1 at 1000 K. If Pt is added as the catalyst at same
temperature, the rate constant becomes 100 times of uncatalysed
reaction. Find the activation energy for the catalysed reaction.
Q. The activation energy for the reaction:
2NH3 (g) → N2 g + H2 (g)
are 20 KJ mol−1 at 1000 K. If Pt is added as the catalyst at same
temperature, the rate constant becomes 100 times of uncatalysed
reaction. Find the activation energy for the catalysed reaction.

Sol.
kC
Ea UC = 20 KJ mol−1 = 20000 J mol−1 ; = 100
k UC

kC Ea UC − Ea C
log =
k UC 2.303 × RT

20000 − Ea C = log 100 × 2.303 × 1000

Ea C = 20000 − 4606 = 15396 J mol−1 = 15.396 KJ mol−1

Q. The time required for 10% completion of a first order reaction at 298 K
is equal to that required for its 25% completion at 308 K. If the value of
A is 4 × 1010 s−1 . Calculate k at 318 K and Ea .

Sol. k2 Ea T2 − T1
log =
For 1st order, k1 2.303R T1 T2
R
ln = −kt Ea 308 − 298
R0 log 2.729 =
At 298 K 2.303 × 8.314 308 × 298
1 100 0.1054
t1 = ln = Ea = 76.64KJmol−1
k1 90 k1
At 308 K To calculate k at 318 K,
1 100 2.2877
t2 = ln = Ea −76.64×103
k 2 75 k2 −RT
k=A× e = 4 × 1010 × e 8.314×318
as t1 = t 2 k 2 = 2.729 × k1
k = 1.034 × 10−2 s −1
Q. The activation energy for the reaction 2 HI(g) → H2 + I2 (g) is
209.5 kJ mol−1 at 581 K. Calculate the fraction of molecules of reactants
having energy equal to or greater than activation energy?
Q. The activation energy for the reaction 2 HI(g) → H2 + I2 (g) is
209.5 kJ mol−1 at 581 K. Calculate the fraction of molecules of reactants
having energy equal to or greater than activation energy?

Sol.

As we know, fraction of molecules having energy equal to or greater than

activation energy
−Ea
e RT
So,

209.5×103
e−8.314×581 = 1.46 × 10−19