104 Chemical reaction engineering

�P

0.0 0.1 0.2 0.3 0.4 0.5

�P

Figure E6.6 According to Equation 6.61.

6.4.3 Series–parallel reactions

A + B → P1

where k are the rate constants.

P1 + B → P2 k1
...........................

Pn−1 + B → Pn kn−1

This is the scheme of a polymerization reaction by addition of radicals. Although

this system is complex and usually solved by numerical methods, the general solution
using the integral method will be shown here. This is the easiest way to identify the
kinetic parameters involved and indicate a general solving method for complex reac-
tions of this type, although the numerical solution is more appropriate. We should start
from a batch system (constant volume), whose equations for the rates of reactants and
products are described as follows:

dCA
− = k 0 CA CB (6.62)
dt
dCP1
= k0 CA CB − k1 CP1 CB (6.63)
dt
...........................
 Kinetics of multiple reactions 105

dCPn−1
= kn−2 CPn−1 CB − kn−1 CPn−1 CB (6.64)
dt

dCPn
= kn−1 CPn−1 CB (6.65)
dt

Considering that:

CA + CP1 + CP2 + · · · + CPn−1 + CPn = CA0 (6.66)

Since for each molecule of P1 a molecule of B is consumed and for each molecule
of P2 two molecules are consumed and so on, the global balance for B will be:

CB + CP1 + 2CP2 + · · · + (n − 1)CPn−1 + nCPn = CB0 (6.67)

Using the same dimensionless variables defined previously, ie, ϕA = CCA0

A
, ϕB = CCB0
B
,
etc.
A generic parameter is also defined for the relation between the rate constants, i.e.:

ki
κi =
k0

where i = 1, 2, . . . , n − 1.
Equations 6.62–6.66 are transformed and after solving them, we have:

dϕP1 ϕP
= κ1 1 − 1 (6.68)
dϕA ϕA

By using the integration factor, we obtain the solution with the boundary condition
that ϕA = ϕP1 = 0:

1
ϕP1 = (ϕA − ϕAκ1 ) (6.69)
(κ − 1)

By relating ϕP1 and ϕP2 with ϕA , we analogously obtain:

dϕP2 ϕP ϕP
= κ1 1 − κ2 2 (6.70)
dϕA ϕA ϕA

Substituting from Equation 6.69, we have:

dϕP2 ϕP2 κ1  (κ −1)


− κ2 =− 1 − ϕA 1 (6.71)
dϕA ϕA 1 − κ1

Using the integral factors with the boundary conditions = 0, ϕA = 1, we obtain the
generic solution:
κ1  
ϕP2 = (κ1 − κ2 )ϕA − (1 − κ2 )ϕAκ1 + (1 − κ1 )ϕAκ2 (6.72)
(1 − κ1 )(1 − κ2 )(κ1 − κ2 )
106 Chemical reaction engineering

Knowing the concentration ϕPi as a function of the concentration of the component

ϕA , we can determine the concentration of Pi by integrating Equation 6.71, which is
generically given by:

κ 1 κi+1
ϕPi+1 = −κi ϕAi+1 κi+1 f (ϕA )dϕA + CϕA (6.73)
ϕA

where C is a constant. Therefore, to determine the reaction rate constants, we proceed

as in the case for reactions in series, in which the concentration of Pi increases, reaches
a maximum and afterward decreases. From the condition of maximum concentration,
ϕPi+1 is differentiated and equaled to zero.
For P1 , the maximum concentration will be:


κ1
ϕP max = κ1 1−κ1
(6.74)

We observe that ϕPi max depends on the relation between the reaction rate constants
κ1 . Analogously, ϕPi+1 max will be determined only as a function of the relations κi .
Knowing the experimental values of CA , CPi as a function of the time tmax , we
can separately calculate ϕP max and consequently the rate constants. To determine the
reaction time t, we should start from Equation 6.68 and substitute ϑB as a function of
ϕPi . We finally obtain:
 1
1
τ= dϕA
A f (ϕA )

In this expression, we only have the distribution of the reactant A as a function of

the other components.