Lecture 8

Multiple Reactions Part 2

Series Reactions

Irreversible:
A P
A+AP
A+BP

Reversible:
A

Parallel:
A R
AS

Series:
ARS

Eg 1

reaction of ethylene oxide (EO) with ammonia to form mono-, diand triethanolamine

CH2-CH2 + NH3 HOCH2CH2NH2

O

EO

EO

(HOCH2CH2)2NH (HOCH2CH2)3N

E.g. 2
C6H6 +Cl2 C6H5Cl +Cl2 C6Cl6

k1

dC A

= k1C A
dt

k2

eqn 1

dC R
= k1C A - k 2 C R
dt
dC S
= k 2C R
dt

eqn 2
eqn 3

Initial conditions: CA0, CR0 = CS0 = 0

Integrating Eqn 1 gives

CA
ln
= k1t
C A0
CA = CA0 exp(-k1t)

Eqn 4

Substituting into Eqn 2 gives

dC R
+ k 2 C R = k1C A0 exp(k1t )
dt

Eqn 5

This equation is a first order differential equation of the form:

dy
+ Py = Q
dx

with y = CR and Q = f(x)

Use an integrating factor

exp( Pdx)

here : exp(k 2 t )

Boundary conditions: t=0, CR0 = 0

The solution is:

CR =

k1
C A0 e k1t e k2t
k 2 k1

Eqn 6

Since CA0 = CA + CR + CS by stoichiometry

Then CS = CA0 CA - CR

k2
k1
CS = C A0 1 +
e k1t +
e k2t
k 2 k1

k1 k 2

Eqn 7

If k2 is much larger than k1 then Eqn 7 reduces to:

CS = C A0 1 e k1t ,

k 2 >> k1

The rate is determined by k1 i.e. the 1st step

If k1 is much larger than k2 then Eqn 7 reduces to:

C S = C A 0 1 e k 2t ,

k1 >> k 2

The rate is determined by k2 i.e. the 2nd step

In general, for any number of reactions in series it is the slowest step that
has the greatest influence on the overall reaction rate:

Rate Determining Step

CS
CA
Ci
CR

To find CRmax differentiate and set dCR/dt = 0

t max =

ln(k 2 / k1 )
k 2 k1

Eqn 8

The maximum concentration of R is found by inserting Eqn into the

expression for CR (Eqn 6)

C R ,max
C A0

k
= 1
k2

k 2 /( k 2 k1 )

Eqn 9

k1

k2

S
CS Eqn 7

CA Eqn 4
Ci
CR Eqn 6

CRmax
Eqn 9

tmax
Eqn 8