Chemical Reaction Engineering-I CL 303 Multiple Reactions

Chemical Reaction Engineering-I
CL 303
Multiple Reactions
Dr. Raghvendra Gupta
Assistant Professor
Department of Chemical Engineering
Indian Institute of Technology, Guwahati
July 10, 2017 IIT, Guwahati 1

Lecture 19
Series Reactions
First order followed by first oder
PFR
CSTR
Comparison of reactors
Zero order followed by first order
Tutorial 6.3
First order followed by zero order
DIY

Irreversible reactions in series: PFR/ batch reactor
Recall the analysis we did for batch reactor in chapter 3.

Replace reaction time (t) with the space time (t).

Irreversible first order reactions in series:
PFR/ batch reactor
Max concentration of intermediate (R):
Time at which max concentration occurs:
What would be the expressions when k1 = k2?

PFR/ batch reactor
Concentration-time curves Relative concentrations of

reaction components
For varying k2/k1 values
CSTR
Find CA, CR and CS vs time curves?
What time: Does not CSTR operate at

steady state?
Write material balance for reactant A and get
Write material balance for R and get
And, how do we get CS?

CSTR
Find maximum concentration of R:

Irreversible first order reactions in series
PFR CSTR
tPFR < tCSTR for CR,max when k1 k2

The difference (between times to achieve max CR in two reactors)
becomes larger when k1/k2 ratio becomes larger than unity.

Yield of R is always higher for

PFR than CSTR for any X.
If k2/ k1 << 1 (A R), design for
high conversion of A.
If k2/ k1 >> 1 (A S), design for
a very small conversion of A per
pass, separation of R and recycle of
unused reactant.

Series reactions (Qualitative)
Reaction proceeds only in the presence of light

Consider two different schemes of treating the reactants:
Scheme 1 Scheme 2

Series reactions (Qualitative)
To maximise the intermediate production (for irreversible reactions):
Do not allow to mix fluids of different compositions and at
different stages of conversion
PFR and batch reactor no mixing of fluid streams of different
compositions give a maximum R yield.
CSTR a fresh stream of pure A is mixed continuously with an
already reacted fluid in the reactor Yield is lower.

FAVORABLE CONTACTING PATTERNS FOR IRREVERSIBLE
REACTIONS IN SERIES
Calculate and verify this.
Laminar Turbulent

FAVORABLE CONTACTING PATTERNS FOR IRREVERSIBLE
REACTIONS IN SERIES

First order followed by zero order reaction

Zero-order followed by first order reaction

Irreversible series-parallel reactions
OR
Example: Successive substitutive halogenation/nitration of hydrocarbons

Lecture 20

Irreversible, bimolecular, constant density
For some qualitative understanding,

consider following mixing patterns:
Add A slowly to B
Add B slowly to A
mix A and B together rapidly

1. Add A slowly to B
With each addition of A, a bit of R is produced.

R reacts with B to form S.

2. Add B slowly to A
3. Mix A and B rapidly

For reactions in parallel
Concentration of reactant determines product distribution
High reactant concentration favours reaction of higher order
Low reactant concentration favours reaction of lower order
No concentration effect for reaction of same order
For reactions in series
Mixing of fluids of different composition is important
mixing of reactants of different composition and different stage of
conversion low intermediate formation

For reactions in parallel
CB has no effect as reactions are of same order
For reactions in series
When A is kept uniform in composition, R forms.

When fresh A is mixed with partly reacted mixture no R
forms
Series-parallel reactions can be analysed in terms of constituent

series and parallel reactions
Irreversible series-parallel reactions: PFR
Product distribution: eliminate time variable from two
rate equations

Irreversible series-parallel reactions:PFR
We obtained CR as a function of CA.

How about concentration of other components (B, S).
Of course, you still need to solve design equation for a component.
An A balance,
This will give CS.
Balance for B,
Moles of B consumed = Moles of R formed + 2*Moles of S formed

Irreversible series-parallel reactions: CSTR
Write the design equation for A and R
substitute the rate equations and rearrange to get
Notice the similarity with PFR equation

Rearranging above gives
and

How can we calculate CS?

k2/k1 may be found by analysing the products of a reaction from
a experiment and locating the point on the above charts

-DCB-DCR
-DCA-DCR
Lines of slope 2, why?

go through example 8.2

Denbigh Reactions
The performance equations for this reaction scheme reduce

directly to several special cases, such as

Denbigh Reactions: PFR
Integrate the performance equations to give

Denbigh Reactions:PFR
For the special case when CR0 = CS0 = CT0 = CU0

Denbigh Reactions: PFR

Denbigh Reactions: CSTR
Note the typo in the book.

Verify it.

C-t curves: mechanisms and rate constants
Initial slope of the curves
Zero slope: compound is not directly forming from A
Initial slope can help determine rate constants ( CA0 known)
Measure the final concentration of all the components
If final concentration (except that of A and B) is approaching
zero- it might be an intermediate
Find when an intermediate reaches max concentration (and Cmax)
Make runs at different CA0 and CB0/CA0
Make runs starting with intermediates, if possible.

C-t curves: mechanisms and rate constants
If two steps of first order reactions in series have very different
values, we can approximate the overall behaviour.

Example

Example
Notice initial slopes

Concentration of final products
Think of a reaction scheme
Evaluate rate constants

CA :(k1+k2+k3)
Initial rate of formation of R: k2
Initial rate of formation of S: k1

Example
For k4
from



Denbigh Reactions
Apply the performance equations to give

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Chemical Reaction Engineering-I

July 10, 2017 IIT, Guwahati 1

July 10, 2017 IIT, Guwahati 2

Recall the analysis we did for batch reactor in chapter 3.

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Max concentration of intermediate (R):

Time at which max concentration occurs:

What would be the expressions when k1 = k2?

Concentration-time curves Relative concentrations of

What time: Does not CSTR operate at

Write material balance for reactant A and get

Write material balance for R and get

And, how do we get CS?

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tPFR < tCSTR for CR,max when k1 k2

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Yield of R is always higher for

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Reaction proceeds only in the presence of light

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Calculate and verify this.

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Example: Successive substitutive halogenation/nitration of hydrocarbons

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Irreversible, bimolecular, constant density

For some qualitative understanding,

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With each addition of A, a bit of R is produced.

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3. Mix A and B rapidly

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CB has no effect as reactions are of same order

For reactions in series

When A is kept uniform in composition, R forms.

Series-parallel reactions can be analysed in terms of constituent

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We obtained CR as a function of CA.

This will give CS.

Moles of B consumed = Moles of R formed + 2*Moles of S formed

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Write the design equation for A and R

substitute the rate equations and rearrange to get

Notice the similarity with PFR equation

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How can we calculate CS?

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Lines of slope 2, why?

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The performance equations for this reaction scheme reduce

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