3.

From Reaction Mechanism

Reaction mechanism shows all the elementary steps involved

in a particular chemical change.

The assumption about the elementary steps in a reaction

mechanism is that one of the steps is far slower than the other
steps the rate-determining step.

The following terms are used to describe a reaction mechanism:

Terms

Meaning / Definition
Chemical equations showing the

Elementary steps

colliding molecules in a reaction

mechanism.
Number of reactant molecules
in each elementary step.

Molecularity

Molecularity 1 = Unimolecular
Molecularity 2 = Bimolecular
Molecularity 3 = Termolecular
Species which are produced and

Intermediate in a mechanism

subsequently consumed in a
reaction mechanism.
Species which are involved in a

Catalyst in a mechanism

reaction

mechanism

and

regenerate after the reaction.

The slowest step of the reaction
mechanism the one with the
Rate determining step

highest
and

the

activation
smallest

energy
rate

constant.
Relationship between reaction mechanism and rate
expression

Number of respective species involved in the ratedetermining step of the reaction mechanism refers
to the order of reaction with respect to the
reactants.

Rate expression never shows the intermediate, but only the

catalysts and the reactants.

Example 1 Deducing rate expression from reaction mechanism
The following overall equation for the reaction between NO and H2 is
shown as follows:
2NO(g) + 2H2(g) N2(g) + 2H2O(g)
Mechanism of the reaction:
Step 1: NO + NO N2O2
Step 2: N2O2 + H2 N2(OH)2
Step 3: N2(OH)2 + Rh N2(OH)2-Rh
Step 4: N2(OH)2-Rh + H2 N2 + 2H2O + Rh
(a) Deduce the rate expression of the above reaction when
(i)

Step 2

(ii)

Step 3

Is the rate-determining step. Outline reasons for each of your

answer.

(b)Identify the intermediates and catalysts (if there are any) in the
above mechanism. Justify your answers.

Constructing reaction mechanism from a reaction

A reaction mechanism is constructed based on the following:

1. The sum of all species in the elementary steps equals that shown
in the overall chemical equation.
2. The reaction mechanism is consistent with the rate-determining
step.
Example 2 Constructing a reaction mechanism from rate expression
NO and CO reacts according to the following equation.
2NO + CO N2 + CO2
The rate expression of the reaction is found to be rate =
k[NO]1[CO]1. Construct a two-step mechanism for the reaction.

Example 3 Incorporating catalyst in a reaction mechanism

The reaction A + B AB is found to be catalyst by enzyme E.
Outline a two-step reaction mechanism for each of the following
proposed rate expression:
(a) Rate = k[E][B]
(b)Rate = k[E][A][B]

16.3 Activation Energy

Activation Energy can be described quantitatively using

Arrhenius Equation which is shown as follow:
Ea

k =A e RT , where
k = rate constant
A = Arrhenius constant
tells the collision geometry and frequency in a reaction, i.e. a
measure of the proportion of molecules that collide with enough
energy and correct orientation
Ea = activation energy (unit: J/mol or kJ/mol)
R = universal gas constant (J/mol-K)
T = temperature in Kelvin

Taking Ln on both sides of the equation gives the following:

lnk = lnA +

E a 1
)
R T

Plotting ln k vs 1/T gives the Arrhenius plot where

ln A = y-intercept, and
(

E a
)
R

= slope.

A = ey-intercept and Ea = -R x slope

Example Determining activation energy from Arrhenius plot

Given the following Arrhenius plot for a reaction:

(a) Calculate the activation energy and Arrhenius constant for the
reaction.

(b)Sketch on the above graph when

(i)

a catalyst is added to the reaction

(ii)

surface area of solid reactant is increased.

Explain each of your sketch.