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Scope:
Limited to Qualitative treatment
Design aspects not included

What is a multiple reaction ?


Require rate w.r.t. more than one species
Require more than one stoichiometric
equation and equilibrium expression
Classification:
Series (consecutive) reactions
ARS
Parallel (competing) reactions
AR
AS
Series Parallel reactions

Criteria for selecting the reactor:


Good product distribution
Size of the reactor
Good product distribution could be the dominant
criteria in many cases.
The above two criteria are contradictory to each
other. Good design w.r.t one requirement may be
poor w.r.t. the other.
An economic analysis will give the best
compromise.
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Selectivity:
A R (desired reaction)
A S (undesired reaction)
Selectivity = rdesired/rundesired
The selectivity should be maximum for the
chosen reactor.
Yield = rdesired /-rA

Parallel reactions

Series reactions

Series-Parallel reactions

Parallel reactions
A R (desired reaction)
A S (undesired reaction)
dC R
rR
k1C A
dt
S

dC S
rS
k 2C A
dt

dC R k1
CA
dC S k 2

k1, k2, , are all constant for a specific system


at a given temperature.
How to maximize S ??
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How to decide the concentration level??


dC R k1
S
CA
dC S k 2

Case 1: > , ndesired > nundesired


High concentration is desirable as it
maximizes the selectivity.
Case 2: < , ndesired < nundesired
Low concentration is desirable as it
maximizes the selectivity.
Case 3: = , ndesired = nundesired
Concentration level does not affect
the selectivity.

Concentration can be maintained low:


Using a CSTR
Designing for high conversions
Increasing inerts in the feed
Decreasing pressure in gas phase reactions
Concentration can be maintained high:
Using a PFR
Designing for low conversions
Decreasing inerts in the feed
Increasing pressure in gas phase reactions

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How to decide the temperature level??


dC R k1
S
CA
dC S k 2

S is maximized at higher k1/k2

Case 1: ED > EU
High temperature is desirable as it
maximizes the selectivity.
Case 2: ED < EU
Low temperature is desirable as it
maximizes the selectivity.
Case 3: ED = EU
Temperature level does not affect
the selectivity.

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Example: A + B R (desired reaction)


A + B S (undesired reaction)
dC R k1 1 1 2 2
S
C A CB
dC S k 2

Case 1: 1 > 1 and 2 > 2


Maintain both CA and CB high.
Case 2: 1 < 1 and 2 < 2
Maintain both CA and CB low.
Case 3: 1 = 1 and 2 = 2
CA and CB levels will not affect S.

Temperature levels can be decided based on the


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activation energies

Contacting patterns for batch operation:

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Contacting patterns for continuous operation:

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Conclusions:
For parallel reactions, the concentration level of
the reactants is the key to control product
distribution.
High reactant concentration favors the higher
order reaction
Low reactant concentration favors the lower
order reaction
Similarly high temperature favors the reaction
with high activation energy
Low temperature favors the reaction with low
activation energy

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Series reactions:
A R S (I order at constant density)
Batch Reactor:
topt

ln(k 2 / k1 )

1 / klog mean
k 2 k1

C R ,max
C A0

k1


k2

k2

( k 2 k1 )

Plug Flow Reactor:

opt

ln(k 2 / k1 )

1 / k log mean
k 2 k1

C R ,max
C A0

k1


k2

k2

( k 2 k1 )

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CSTR:

C A0 C A C A0 C A C A 1 k
1

C A0
rA
k1C A
Material balance for species R:
vCR0 = vCR + (-rR)V
0 = vCR + (-k1CA+ k2CR)V
0 = CR + (-k1CA + k2CR)
CR(1 + k2) = k1CA

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k1C A0
k1C A
CR

1 k 2 (1 k1 )(1 k 2 )
For maximum concentration of R: dCR/d = 0

C R ,max
C A0

opt

k 2 / k1 1

1
k1k 2
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PFR

CSTR

Consecutive I-order reactions


CB exhibits a maximum at opt
CB,max (PFR) > CB,max (CSTR)

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Conclusions:
For series reactions, the time of reaction /
space time is the key for obtaining the maximum
concentration of the desired product.
For higher order reactions and series-parallel
reactions, such analytical derivations for
optimum space time would be tedious.
In such cases, optimization methods can be used
to find the optimum space time and the
corresponding maximum concentration of the
desired product.
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Assignment:
1. Find expressions for optimum space time and
maximum concentration of R for the following
series reaction, if k1 = k2 in both CSTR and
PFR
A R S (I order at constant density)
2. Find expressions for optimum space time and
maximum concentration of R for the following
series reaction, if k1 = 2k2 in both CSTR and
PFR
A R S (I order at constant density)
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ANY
CLARIFICATIONS ?

Berrill, N.J.
A great teacher is not simply one who imparts knowledge to his
students but is one who awakens their interest in the subject and
makes them eager to pursue it for themselves. An outstanding
teacher is a spark plug, not a fuel line.

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