Chapter 6

Multiple Reactions
 Overview
Multiple reactions types
Define Selectivity. How it can be used in the
design?
Solve engineering problems with multiple
reactions
 6.1 Definitions
6.1.1 Types of reactions
There are four types of multiple reactions
1. Parallel reactions (competing reactions) where the reactant
is consumed by two different reaction pathways to form
different products A k1
B
A k2
C
e.g oxidation of ethylene to ethylene oxide
2. Series reactions (consecutive reactions) where the reactant
forms an intermediate product, which reacts further to form
another product
e.g EO with NH3 to form mono, di and triethanolamine

A
k1
B
k2
C
3. Complex reactions are reactions that involve a
combination of both series and parallel
reactions
e.g formation of butadiene from ethanol
A B C D
AC E

4. Independent reactions are reactions that

occur at the same time independently
e.g cracking of crude oil to form gasoline
A BC
DEF
 We want to minimize the formation of
undesired products and maximize the
formation of desired products to reduce the
cost of separating undesired from desired
products

A
kD
Desired
A
kU
Undesired
or A
kD
Desired
kU
Undesired
 Selectivity
Selectivity quantifies the formation of desired wrt
undesired products
Instantaneous selectivity
rate of formation of desired r
S D /U D
rate of formation of undesired rU
Overall selectivity
Exit molar rate of desired FD
S D /U
Exit molar rate of undesired FU
ND
For a batch reactor S D /U
NU
For CSTR S D /U S D /U
 Yield
Yield is defined as the ratio of the reaction rate of a
given product to that of the key reactant
Instantaneous yield Y
rD
rA
D

FD
YD
Overall yield FA0 FA

ND
YD
For a batch reactor N A0 N A

For CSTR YD YD
 6.2Parallel Reactions
We examine ways to maximize SD/U for parallel
reactions
A
kD
D
A
kU
U
1
rD k D C A
2
rU kU C A
1 2
rA rD rU k D C A kU C A
rD k D 1 2
S D /U CA
rU kU
 rD k D a
Case 1: 1>2 let 1 2 a S D /U
CA
rU kU
Keep the conc of reactant A as high as possible
If gas phase no inerts and high pressure are used
If liquid phase use of diluents is minimized
Batch or PFR is used because conc drops progressively
while in CSTR the conc is always at the lowest exit
value rD kD
let 2 1 b S D /U
Case 2: 1<2 rU kU C Ab
Keep the conc of reactant A as low as possible
Diluting the feed with inerts
Recyle reactor product
CSTR is used
 The sensitivity of the selectivity to the
temperature can be determined from the
reaction rates ratio
k D AD [( ED EU ) / RT ]
S D /U e
kU AU
Case 3: ED>EU
kD and rD with temperature than Ku
Keep temperature as high as possible
Case 4: EU>ED
Operate at low possible temperature
 6.3 Reactions in series
For the sequence where B is the desired product
A B C
k1 k2

If the first reaction is slow and the second

reaction is fast it will difficult to produce B
If the first reaction is fast and the second
reaction is slow large yield of B can be
achieved
For series reactions space time (in flow
reactor) and real time in batch reactor is the
most important variable
 The reactions can be rewritten as
A B and B C
k1 k2

Applying on A and B mole balance, rate law,

stoichiometry, combine and evaluate
algorithm
C A C A0 e k1
e k1 e k2
C B k1C A0
k 2 k1
C

CC A0 k 2 (1 e k1 ) k1 (1 e k2 )
k 2 k1

CC C A0 C A C B
Optimum yield of B (maximum CB)
dCB k1C A0 e k1 '
0 (k1 k2e k2 ' )
d ' k2 k1
At this maximum value of CB , W and X can be
solved for as follows
1 k1
'opt ln
k1 k2 k2
0 k
Wopt ln 1
k1 k2 k2
C A0 C A k '
X opt 1 e 1 opt
C A0
k k1 /(k1 k2 ) k1
k1 /( k1 k 2 )

X opt 1 exp ln
1
1
k2 k2
 6.4 Complex Reactions
The algorithm for complex reactions is
1. Number each reaction
2. Write mole balance on each and every species
3. Write the net reaction rate for each species
4. Write rate law for one species in every reaction
5. Relate the reaction rates for each species
6. Combine the rates in terms of conc
7. Write stoichiometry (conc in terms of flow rates)
8. Write pressure drop in terms flow rates
9. Combine and solve ODE
 The net reaction rate for species j is the sum
of all reaction rates in which j appears
Where q is the number of reactions
q
rj rij
Rate law is required fori one species in each
reaction
rij kij f i (C A , CB C j Cn )

For the reaction aA bB cC dD

The reaction rate of each species can be
related to eachrother
r
as
r r
iA iB
iC
iD
ai bi ci di
 For liquid phase Cj
Fj
0

For gas phase FT 0 Fi P T0

Cj
Fi P T0
CT 0
0 FT P0 T FT P0 T
n
FT F j
j 1

P0
CT 0
RT0

F1 F2 Fj
r1 fn1 (C1 , C2 C j ) fn1 (CT 0 , CT 0 CT 0 )
FT FT 0 FT 0
Then Fj
F1 F2
r2 fn2 (C1 , C2 C j ) fn2 (CT 0 , CT 0 CT 0 )
FT FT 0 FT 0
Where fn represents the net rate of formation
 6.5 Multiple Reactions in PFR/PBR
Combining mole balance, rate laws, and
stoichiometry for species 1 to j in the gas
phase
dF1 m
F1 Fj
r1 ri1 fn1 CT 0 , CT 0
dV i FT FT

dF j q
F1 Fj
rj rij fn j CT 0 , CT 0
dV i FT FT

Coupled j ODEs must be solved simultaneously

using numerical package (Polymath)
 6.6 Multiple Reactions in CSTR
Recall the design CSTR equation F j 0 F j rjV

For q gas phase reactions with N species, the following set

of algebraic equations
F1 FN
F10 F1 r1V V . f1 CT 0 , , CT 0
FT FT

F1 FN
FN 0 FN rNV V . f N CT 0 , , CT 0
FT FT
These equations must be solved simultaneously using
numerical package (Polymath)