Consecutive Reactions

The reactions which proceed from reactants (R) to products (P)

in two or more steps, one after the other through one or more
intermediate steps, involving intermediate (I) are called
consecutive reactions.
Consider a simple consecutive first order reactions :

The rate of consumption of reactant

-------Eqn.(1)
 Consecutive Reactions
Separating the variables of equation (1) and integrating between
the limits

-------Eqn.(2)

Reactant R decreases exponentially with time

 Consecutive Reactions
The rate of formation of Intermediate

-------Eqn.(3)

Substituting the value of x from equation (2) in equation (3), we

get

-------Eqn.(4)

Equation (4) is a linear first order differential equation whose

solution is

-------Eqn.(5)
 Consecutive Reactions
As per the condition of conservation of mass we have
a=x+y+z
The concentration of product P( =z) may be calculated as
z=a-x-y

Substituting the values of x andy from equations (2) and (5), we

get
Consecutive Reactions

-------Eqn.(6)
 Consecutive Reactions
Case I. When k1 > > k2

Then
hence e-k1.t can be neglected in equation (6).

As

-------Eqn.(7)
The formation of product P therefore involves only k2 , which
therefore is the rate determining step.
 Consecutive Reactions
Case II. When k1 < < k2 , then e-k1.t > > e-k2.t

Then equation (18) reduces to

-------Eqn.(8)

The concentrations of x, y and z are plotted as functions of time

in the consequent figure
 Consecutive Reactions

From the figure , it can be concluded that the concentration of

reactant (R) decreases exponentially with time, while equations
(7) or (8) suggest the concentration of product (P) increases
gradually to the value of a when all reactant has changed into
product. The concentration of the intermediate (I) rises to a
maximum value and then falls asymptotically to zero.
 Complex Reactions

Intermediate is formed in the first fast equilibrium step which

subsequently slowly reacts in the second rate determining step.
 Complex Reactions

Mechanism of the reaction is

As the product NOCI is being formed in second step, so we can

consider the rate of formation of product as the overall rate of
the reaction.

-------Eqn.(1)
 Complex Reactions

For the calculation of concentration of intermediate, [NOCl2], we

can apply the steady state approximation.
Rate of formation of Intermediate, NOCI2 = Rate of consumption
of intermediate, NOCl2

-------Eqn.(2)
 Complex Reactions

Substituting the value of [NOCl 2 ] from equation (2) into

equation (1), we get

-------Eqn.(3)
 Complex Reactions

Assuming k2 [NO] << k-1 and neglecting the former, we get

The overall rate of the reaction

 Complex Reactions

k
2

Such reactions involve more than two elementary steps with

atleast one slow step
 Complex Reactions

The reaction for the formation of phosgene

For this reaction, the following mechanism has been

proposed :

k2

k-2
 Complex Reactions

From step (iii), the rate of formation of phosgene is

-------Eqn.(1)

From step (ii)

- ------Eqn.(2)

From step (i)

-------Eqn.(3)
 Complex Reactions

Substituting the value of [Cl] from equation (3) in equation

(2), we get

-------Eqn.(4)

Substituting this value of [COCl] from equation (4) in equation

(1), we get
Complex Reactions
 Lindemann Unimolecular Reactions
An elementary reaction is unimolecular if the rearrangement of
a single molecule or ion produces one or more molecules of
product.

In unimolecular reactions, only one reactant molecule takes

part in the reaction like
-------Eqn.(1)
According to this theory, the reactant molecules (R) are first
activated by collisions with other reactant molecules.
 Lindemann Unimolecular Reactions

The activated reactant molecule do not decompose immediately

but it remains in the activated state for a finite time. There is a
time lag before decomposition of the activated reactant
molecules. During this time lag, the activated molecules may
get deactivated to ordinary molecules in second biomolecular
collisions.

If in the time lag, activated reactant molecules are not

deactivated, they will undergo a decomposition reaction
leading to the formation of products.
 Lindemann Unimolecular Reactions
In this mechanism, according to Lindemann, the activated
reactant molecules are produced as reactive intermediate. So,
we can apply steady-state-approximation to find out the
concentration of this short-lived species.
 Lindemann Unimolecular Reactions
As the products are being formed in the last step.