CHEMICAL KINETICS

Chemical kinetics is concerned with the speed, or rates of

chemical reaction and mechanisms by which they occur.

Rate of reaction describes how fast reactants are used up

and products are formed
The factors that affect reaction rates
1. The nature of the reactants and products
2.The concentration of the reacting species
3. The effect of temperature
4. The influence of Catalysts
• Reaction Rates and their Measurements
The rate (or speed) of any chemical reaction can
be expressed as the ratio of the change in
concentration of a reactant ( or product) to a
change of time.
• Rate of Chemical reaction = Change in
concentration / Time

= mol.L-1 S-1
Consider the typical reaction
aA+ bB→ cC+ dD

Rate of reaction= Rate of disappearance A =Rate of

disappearance B
=Rate of appearance C =Rate of
appearance D
Rate of Reaction = - 1/a ( ∆ [A] / ∆ t)
= - 1/b ( ∆ [B] / ∆ t)
= 1/c ( ∆ [C] / ∆ t)
= 1/d ( ∆ [D] / ∆ t)
Example
For the oxidation of ammonia
4NH3+3O2→2N2+6H2O
it was found that the rate of formation of N2 was 0.27 mol L-1 S-1
At what rate was water being formed?
At what rate was ammonia being consumed?
SOLUTION
a) From the equation, Δ[H2O] = 6/2 Δ[N2], so the rate of formation of
H2O is
3 × (0.27 mol L-1 S-1) = 0.81 mol L-1 S-1
b) 4 moles of NH3 are consumed for every 2 moles of N2 formed, so
the rate of disappearance of ammonia is
2 × (0.27 mol L-1 S-1) = 0.54 mol L-1 S-1
Rate Laws:-
The rate is directly proportional to the concentration of the reactants
raised to some power.
A→B
Rate α [ A]x
Rate = K [ A]x
K is the rate constant
Where, x is called the order of reaction, when
X=1 → First order of the reaction,
X=2 → Second order reaction,
X=3 → Third order reaction,
X=0 → Zero-order reaction
The value of X can only be determined from experiment.
• Example :-
2 NO(g) + Br2(g) → 2 NOBr(g) At 273 °C
Determine the rate law for the reaction and
compute the value of the rate constant
Experiment Initial concentration mol/L Initial Rate
NO Br2 (mol.L-1S-1
1 0.1 0.1 12
2 0.1 0.2 24
3 0.1 0.3 36
4 0.2 0.1 48
5 0.3 0.1 108
• Solution:-
Rate = r =K [NO ]x [Br2 ]y
For Br2 r2 / r1 == ( 0.2 / 0.1)y 24/12 =2y
2y = 21
y for Br2 = 1 first order respect to Br2
For NO r4 / r1 = 48/12= ( 0.2 / 0.1)x
4 = 2x 22 = 2x
X for NO =2 second order with respect to NO
Therefor Rate = K [NO ]2 [Br2 ]
12 mol/L.S = K ( 0.1 mol/L)2 ( 0.1 mol/L)
12 mol/L.S = K ( 0.001 mol3/L3)
K = 12 mol/L.S / 0.001 mol3/L3
K =1.2 104 L2 / mol2. S
Half-lives ( t1/2 ):-
The length of time required for the
concentration of the reactant to be deceased
to half of its initial value.
At this point t1/2 [A]t = 1/2[A]0
 Zero order Reaction
• zero-order reaction is a chemical reaction where the rate
does not vary with the increase or decrease in the
concentration of the reactants. Therefore, the rate of
these reactions is always equal to the rate constant of
the specific reactions
• Reaction rate is independent of reactant concentration
Rate = - d [A] / dt =K [A]0
d [A] = -K t
Integration
[A] = [A]ο - Kt
t1/2 = [Aο] / 2K
 First Order Reaction
A reaction is said to be first order if its rate is
determined by the change of one concentration
term only
-The rate increase as number of times the
concentration of reactant is increased.
-Consider reaction
A→ Products
[Aο] =initial concentration of A
[At]=concentration of A after time t
Rate = - d [A]/ dt =K [A]
By integration
Ln [Aο] / [A] = kt

Log [Aο] / [A] = kt /2.303

t = 0.693/k
1/2
 Second order Reaction
• The rate is proportional to the square of molar concentration only one.
• A reaction is called a second order reaction when the overall order is two
-suppose if the reaction is as
2 A → Product
Rate =- d [A] / dt = k [A]2
By integration
1/ [A] = 1/ [Aο] + Kt
-If both the reactant are different
A +B →product
x y
Rate = - d[A] /dt = - d[B] /dt = K[A] [B]
Where x+ y = 2

t1/2 = 1/ K [Aο]
t1/2 = 1/ K [A]ο
• Relation of concentration and time for various orders of
reactions, their half-lives and K units.

Order of Rate law Relation of t1/2 K units

reaction concentration and time

Zero-order r=K CB° - CB =Kt CB° / 2K Mol/L.S

First-order r=K[B] log CB° / CB = Kt /2.303 0.693 /K S-1

Second- r = K[B]2 1/ CB =1/ CB° + Kt 1/ K CB° L/mol.S

order

Third-order r = k[B]3 1/ (CB°)2 -1/ (CB)2= -2Kt 3/ 2 K CB° 2 L2 / mol .S

Example
In an investigation of the decomposition of N2 O5 (g) at 35 °C
2 N2 O5 (g) → 4 NO2(g) + O2(g)
An initial concentration of [N2 O5]0 of 0.03 mol/L was used.
The rate constant was found to be 1.35 x 10-4 S-1
a)What will the concentration of N2 O5 (g) be after 30.0
minutes?
b) How many minutes will it take for the concentration of N2
O5 (g) to drop to 0.02 mol/L.
C) How many minutes will it take for 90% of N2 O5 (g) to
decompose?
d)What is the half-life for the reaction?
Solution :-
Since units of K in S-1 The reaction is first order reaction
Since the question are asked in terms of minutes, it is convenient to
convert the value of K into units of min-1 from S-1
K = 1.35 x 10-4 / 1S x 60 S/ 1 min = 8.10 x 10-3 min-1
a) log CB° / CB = Kt /2.303
log [N2 O5]0 / [N2 O5] = kt/2.303
log 0.03 mol/L / [N2 O5] = 8.10 x 10-3 min-1 x 30 min /2.303 = 0.1055
0.03 mol/L / [N2 O5] = antilog 0.1055 = 1.275
[N2 O5] =0.03 mol/L / 1.275 = 0.0253 mol / L
b) log 0.03( mol/L) / 0.02 (mol/L) = (8.10 x 10-3 min-1) x t / 2.303
2.303 log 1.5 = (8.10 x 10-3 min-1) t
t = 2.303 x 0.176 / 8.10 x 10-3 min-1 = 50 min
C)Since 90% of N2 O5 (g) has decomposed, [N2 O5] is
equal to 10.0 % of the original concentration [N2
O5]0
[N2 O5] = 0.100 [N2 O5] 0
[N2 O5] =0.1 x 0.03 mol/L = 0.003 mol / L
log [N2 O5]0 / [N2 O5] = kt/2.303
log 10 = 8.10 x 10-3 min-1 x t / 2.303
t = 284
d) t1/2 = 0.693 /K
t1/2 =0.693 / 8.10 x 10-3 min-1 = 85.6 min
 Molecularity
The term molecularity indicates the number of
reactant particles in the rate determining step.
Unimolecular : a rate determining step that
involves a single reactant particle
A → Product
Rate = K [ A]
Bimolecular : a rate determining step that
involves two reactants particles
A + B → Product
Rate = K [ A] [ B]

Termolecular : a rate determining step that involves three

reactants particles
A + B + C → Product
Rate = K [ A] [ B] [ C]
Example: The experimental data for the reaction is
as follows Exp. No. [A] [B2] Rate
2 A +B → 2 AB
2 Mol/L Mol/L Mol
/L/S
1 0.5 0.5 1.6 x10
-4
2 0.5 1 3.2 x 10
-4
3 1 1 3.2 x
10-4

Determine the order of overall of reaction &

Molecularity & Rate constant& rate law
 Theories of reaction rate

1-Collision Theory
Collision theory states that the rate of a chemical
reaction is proportional to the number of collisions
between reactant molecules.
To summarize, the requirements for an effective
collision (for a chemical reaction to occur):
1-The reactants must collide with each other.
2- The molecules must have sufficient energy to
initiate the reaction (called activation energy).
3- The molecules must have the proper orientation.
Effect of Temperature on reaction rate
All molecules having kinetic energy equal or
higher than Ea are capable of reacting. An
increase in temperature increase the rate of the
reaction increases.
• Arrhenius equation
K = A e-Ea /RT
Where
K is The rate constant,
A ( frequency factor is constant),
e is the base of natural logarithms,
Ea is the energy of activation for the reaction ( J/
mol),
R is the molar gas constant ( 8.314 J/K mol),
T is the absolute temperature.
If we take the logarithms of the Arrhenius
equation
Log K = log A – Ea / 2.303 RT
The values of Ea and A for a reaction can be
found from the rate constant at T1 is K1 and at T2
is K2 ,then
Log (K2 / K1 ) = Ea / 2.303 R(1/T1 -1/ T2 )
Ea = 2.303 R (T1 T2 / T2 – T1 ) log ( K2 / K1)
Example
For the reaction
2NOCl→ 2 NO(g) + Cl2
The rate equation is rate of production of Cl2 = k
[NoCl]2
The rate constant, K is 2.6 x 10-8 L/mol.S at 300 °K
and 4.9 x10-4 L/mol.S at 400 ºK
a)What is the energy of activation, Ea for the
reaction?
b)Find the value of K at 500 ºK.
Solution:
T1 = 300 ºK K1 = 2.6 x 10-8 L/mol.S
T2 = 400 ºK K1 = 4.9 x 10-4 L/mol.S
R is 8.31 J/ ºK.mol
Ea = 2.303 R (T1 T2 / T2 – T1 ) log ( K2 / K1)

= 2.303 x 8.31 (300 x400 / 400-300 ) log (4.9 x10-4 / 2.6 x 10-8 )
=19.1 x 1200 log 1.88 x 10 4 = 22.9 x 4.28
= 98000 J/mol = 98.0 KJ/mol = 9.8 x 104 J/mol.
b)Let T1 = 400 ºK K 1 = 4.9 x 10-4
L/mol.S
T2 = 500 ºK K 2 = unknown
Ea= 9.8 x 104 J/mol.
log ( K2 / K1) =Ea / 2.303 R (T2 – T1 / T1 T2)
=9.8 x104 / 2.303 x 8.31 ( 500-400 / 500 x 400
) =2.57
K2 / K1 =antilog 2.57 = 3.7 x 102

K2 = 3.7 102 x 4.9 10-4 = 0.18 L / mol.S

 2)Transition state theory
The transition stat or activated complex theory assumes that
-During a chemical reaction, reactant do not suddenly convert to
products.
-The formation of products is a continuous process of bonding
breaking and forming.
-At some point, a transition species is formed containing partial bonds.
-This species is called the transition state or activated complex
-The activation energy is therefore the energy needed to reach the
transition state.
-Note also that the transition state can go on to form product or break
apart to reform the reactants.
The catalyzed path has a lower overall energy of activation than the uncatalyzed
path does
Two additional points can be derived from
figure
1)The enthalpy change, ∆ H, for the catalyzed
reaction is the same as the ∆ H for the un-
catalyzed reaction.
2) The energy of activation for catalyzed
reaction is lower than the energy of activation
for un-catalyed reaction
 Catalysts:
A catalysts is a substance that increase the rate
of a reaction without being consumed; after the
reaction has ceased, it can be recovered from
the reaction mixture chemically unchanged.
Problem (1)
The following data were collected for the reaction of t-butyl bromide,
(CH3)3 C Br, with hydroxide ion at 55 ºC.
(CH3)3 C Br +OH- → (CH3)3 COH + Br-
Experiment Initial concentration (mol/L) Initial Rate
formation of
(CH3)3 COH
(CH3)3 C Br OH- (mol.L-1S-1
1 0.1 0.1 0.001
2 0.2 0.1 0.002
3 0.3 0.1 0.003
4 0.1 0.2 0.001
5 0.1 0.3 0.001

What is the rate law and rate constant for this reaction?
Solution:- we expect a rate law of the form
Rate = K [(CH3)3 CBr ]x [ OH- ]y
For (CH3)3 C Br
r2 / r1 == ( 0.2 / 0.1)x = 0.002/0.001
x=1
So the reaction is first order with respect to (CH3)3 CBr
In experiment 1,4,5, the [(CH3)3 CBr ] concentration is the same.
Changing the [ OH- ] has no effect on the rate . This means that the reaction is Zero-
order with respect to OH-.
Therefore
Rate = K [(CH3)3 CBr ]1 [ OH- ]0
Rate = K [(CH3)3 CBr ]
0.001 mol/L.s = K (0.1 mol/L)
K=0.001 mol/L.s/ 0.1 mol/L = 0.01 S-1
Problem (2)
Given the following experimental data, find the rate law and the
rate constant for the reaction:
NO (g) + NO2 (g) + O2 (g)  N2O5 (g)

Run [NO]o , M [NO2]o , M [O2]o , M Initial Rate, Ms-1

1 0.10 0.10 0.10 2.1 x 10-2

2 0.20 0.10 0.10 4.2 x 10-2

3 0.20 0.30 0.20 1.26 x 10-1

4 0.10 0.10 0.20 2.1 x 10-2

Solution
Rate = K [NO ]x [NO2 ]y [O2 ]z
For NO
r2 / r1 = ( 0.2 /0.1)x = ( 4.2 x 10-2 /2.1 x 10-2)
X=1
So the reaction is first order with respect to NO
For NO2
r3 / r1 = ( 0.3 /0.1)y = (1.26 x 10-1 /2.1 x 10-2)
y= 1
So the reaction is first order with respect to NO2
For O2
In experiment 1,4 the [NO ] and [NO2 ] concentration is the same.
Changing the [ O2 ] has no effect on the rate . This means that the reaction is
Zero-order with respect to O2
Rate = k[NO] [NO2]
2.1 x 10-2 = K x 0.1 x 0.1
k = 2.1 M-1s-1
Problem (3)
Given reaction rate data for:
F2(g) + 2ClO2(g) → 2FClO2(g)
Experimental [F2](M) [ClO2](M) Initial rate

1 0.10 0.010 1.2 x 10-3

2 0.10 0.040 4.8 x 10-3
3 0.20 0.010 2.4 x 10-3

Determine the order of each reactant and the

overall reaction order.
Solution
For F2
r3 / r1 = ( 0.20 /0.10)x = 2.4 x 10-3 / 1.2 x 10-3
x=1
So the reaction is first order with respect to F2
For ClO2
r2 / r1 = (0.04 / 0.01 )y = (4.8 x 10-3 / 1.2 x 10-3 )
y=1
So the reaction is first order with respect to ClO2
Rate = K F2 ClO2
the overall reaction order is x + y = 2