Chemical Kinetics

Complex Reaction

Opposing or Reversible Reaction

Certain reactions in which product of a chemical change react to form the original reactants are
known as reversible or opposing reactions. In opposing reaction, the net rate of the reaction
will be influenced by both forward and backward rates and that causes serious disturbance in
the measurement of reaction.
Ex: 1. Muta rotation of -D glucose into -D glucose
2. Conversion of ammonium cyanate into urea

There are several types of opposing reaction

1) Both forward and backward reactions are of first order
2) First order reaction is opposed by second order
3) Both forward and backward reactions are of second order
Let us consider the case when the both forward and backward reactions are of first order
k1
A B
k2

Where k1 and k2 represents first order rate constants for the forward and backward reactions
respectively.
Suppose a is initial concentration of A, then after time t, x mole of A decomposed to form B.
Thus the concentration of A after a time t is a-x and that of B is x. Therefore, the rate of forward
and backward reactions equals to k1(a-x) and k2x.
Thus, the net rate of formation of B is

= 1 ( ) 2 -------(1)


At equilibrium, the net rate is zero, =0

1 ( ) 2 = 0--------(2)
1 ( )
2 = -------------(3)

is the equilibrium concentration.

Substituting the value of k2 in equation 1, we get
1 ( )
= 1 ( )

 1 ( )
= -----------(4)

1
On rearranging eqn. 4 we get,
( )
= ------------(5)

1
On integrating we get, ln( ) = + ----------(6)

When t=0, x=0, then = ln --------------------(7)

Substituting eq.7 in eq.6 we get 1 = -----------(8)

Thus value of k1 can be calculated by using eqn. 8. If xe, x and t are known, by substituting
the value of k1 in eq.3 k2 can be calculated.