CL605: Advanced Reaction Engineering

Activation energy for complex reactions



* Overall rate constant is made up of many individual rate constants

* let

rA

k1 k2 k3
k4

1 2

CA



1 2

k1 k2 k3
* then the overall rate constant is k
k4
* if the temperature dependence of this rate constant is found, then we can write the pre-exponential and the activation
energy k1 k2 k3
E1 E2 E3 E4
E
1
ln k
ln k0
RT
2 ln
k4
RT

 

 
 

     


* or the overall pre-exponential is k


* the overall activation energy is E
1 2
E  E  E
0

k10 k20 k30

k40

1 2

E4
* note that this activation energy may turn out to be negative.
1

First-order reaction networks

* Wei and Prater analysis of first-order reaction networks
* Consider all possible single reactant, single product reactions between the three species A 1 , A2 , and A3 .
* The reactions can be written down as:
A2
A1 k12
A1 k13
A3
k
21
A1
A2
A2 k23
A3
A3 k31
A1
k
32
A3
A2
* there are six reactions in all. No assumptions such as partial equilibrium and pseudo-steady-state can be applied. all
reactions are elementary.
* we can write the mole balance for constant volume batch reactor as:
dy1
k12 k13 y1 k21 y2 k31 y3
dt
dy2
k12 y1
k21 k23 y2 k32 y3
dt
dy3
k13 y1 k23 y2
k31 k32 y3
dt
* this can be written in matrix notation as
dY
KY
dt
where K is the matrix of rate constants and Y is the vector of concentrations.
* Note that these equations cannot be solved analytically in a straightforward manner
* However, from matrix algebra it can be shown that:
X 1 KX where X is the matrix of eigenvectors of K, and is a diagonal matrix with the eigenvalues of K on the
diagonal.
* Then, if we define new fictitious compositions vector Z such that Z X 1 Y, it can be shown that:
z1 z10 exp 1 t
z2 z20 exp 2 t
z3 z30 exp 3 t
where zi is the ith component of vector Z and i are the eigenvalues of K.
* In other words the balance equations in z i are:
dz1
1 z1
dt
dz2
2 z2
dt
dz3
3 z3
dt










 


 


 







(decoupled from each other)

* Thus, once the matrix K of rate constants is made, then its eigenvalues and eigenvectors are to be determined. The
time-dependence of the fictitious concentrations z are to be found, and finally the real concentrations found from multiplication of the eigenvector matrix and Z.
Generalised approach to solving multiple reaction problems
* In general if there are several reactions and species occurring simultaneously in a reactor, we have to solve the following
equations simultaneously:
(i) Mass balance for each of the species:
N
dCi
1 2 Nspecies )
j rxns
1 i j R j (i
dt
Here Ci is the concentration of species i, R j is the rate of reaction j, i j is the stoichiometric coefficient of species i in
reaction j (negative if i is a reactant, positive if i is a product, and zero if i does not participate in reaction j), N rxns is the total
number of reactions and Nspecies is the total number of species.
(ii) Overall energy balance for reactor:
Nspecies
V Nj rxns
H j R j qAk
i 1 MiCiC pi dT
1
dt
where Mi is the molecular weight, Ci is the concentration, and C pi is the heat capacity of species i; V is the volume of
reactor, H j is the enthalpy change associated with reaction j (at temperature T), and qA k represents the heat loss term due to
cooling coils..