Effect of T on K:

-rA = f1(T). f2(CA) = k(T).f2(CA)

(1) Arrhenius Equation:

k = k0 exp(-Ea/RT)

ln k = ln ko – (Ea/RT)

k0 = Frequency Factor, (same unit as k)

Ea = Activation Energy, (J/mol)

R = Universal Gas Constant, (8.314 J/mol K)

T = Absolute Temperature, (K)

 k is calculated estimated experimentally at different

 Experimental Data (ln k) vs (1/T) is plotted
 Ea is calculated from the slope. k0 is estimated from the intercept.

(2) Collision Theory:

1
k =k 0 T exp (-Ea/RT)
' 2

(3) Transition-state Theory:

k =k } ¿ exp (-Ea/RT)

● High Ea: The reaction is highly temperature – sensitive. A small change in

temperature will impact k and the rate of reaction significantly.

1
PROBLEM#2:

At 500K, the rate of a bimolecular reaction is 10 times the rate at 400 K. Calculate
the energy of activation.

SOLUTION: k = koexp(-E/RT)

lnk1 = lnk0-E/RT1;

lnk2 = lnk0-E/RT2;

ln(k1/k2) = -E/R(1/T1-1/T2)

k1/k2 = 10;

T1 = 500K, T2 = 400K

ln(10) = E/8.314(1/400-1/500)

E = 38,249 J/mol

2
Kinetic models for non-elementary reactions:
Non-elementary reactions assumed to consist of a number of elementary reactions.
Minute immeasurable quantity of unstable intermediate formed.
1. Non chain reaction
Reactant  (intermediate)*  (products)
2. Chain reactions
Reactants  (Intermediate)* [Initiation]
(Intermediate)* + Reactants  (Intermediate)* + Product [Propagation]
(Intermediate)*  Product [Termination]
The intermediate catalyses the reaction
(i) Free radical, chain mechanism:
Free radicals (molecules with unpaired electrons)
H₂ + Br₂  2HBr
Br2 ❑ Br .+Br . [Initiation & Propagation]
⇔

Br .+ H 2 ❑ HBr+ H . [Propagation]
⇔

H .+Br 2 ❑ HBr+ Br . [Propagation]

⇔

(ii) Molecular intermediate, non-chain:

e.g. Enzyme-catalyzed fermentation reaction. A E
⇔
R

A+ E ❑( A . E)¿
⇔

( A . E)¿ → R+ E
(iii) Transition Complex non-chain:
Energised, unstable transition complex formed.
A+A  A* + A (Formation of energized molecule)
A* + A  A+A (Return to stable form by collision)
A*  R+S (Spontaneous decomposition to products)
e.g: Decomposition of azomethane (CH₃)2N₂→ C₂H₆ + N₂

3
Search for Reaction Mechanism:

Pseudo Steady State Assumption: - (PSSA)

 Concentration of Intermediate is very small
 d[X]/dt ≈ 0

Prob. The irreversible reaction A + B  AB is found to be following a rate eqn r AB =

k[B]2 The chemistry suggests that the intermediate consists of an association of
reactant molecules and the chain reaction does not occur. Search for a suitable
reaction mechanism.

Soln. Expt. Observed rAB = k[B]2

Model 1: Let’s try a simple 2-stage model.
k1
2A A2*
k2

k3
A2*+B A + AB
k4

rAB = k3[A2*][B] - k4[A][AB]

rA2* = 1/2 k1[A]2 - k2[A2*] - k3[A2*][B] + k4[A][AB]
rA2* = 0 (PSSA)
[A2*] = 1/2 k1[A]2 + k4[A][AB]
k2+k3[B]
rAB = 1/2k1 k3[A]2[B] – k2 k4[A][AB]
k2+k3[B]
If k2 is very small, rAB = 1/2k1[A]2
If k4 is very small, rAB = k1 k3/(2k2)[A]2[B]
1+k3/k2[B]
None of these fits the observed rate equation.

4
Model 2: Interchanging A & B 1

B + B  B2 *
3
*
A + B ⇌ AB + B
2
4
∴ We get rAB = k[B] when k2 = 0. So this is the desired reaction scheme.
2

Prob. Show that the following scheme proposed by Ogg is consistent with and
explain the first order decomposition of N2O5.

K1

N2O5 ⇌ NO2+NO3∗
K2

k3
NO3 → NO∗+O2
∗

k4
NO∗+NO3∗ → 2NO2

Soln :

r NO3* = k1[N205] – k2[NO2][ NO3∗] – k3[NO3∗] – k4[NO∗][NO3∗] = 0

[NO3∗] =

rNO* = k3[NO3*] – k4[NO*][NO3*] = 0

[NO*] = k3/k4

[NO3∗] = =

-rN2O5 = k1[N2O5] –k2[NO2][NO3*] =

If - rN2O5 = k1[N2O5]