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

July 10, 2017 IIT, Guwahati 2

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).

July 10, 2017 IIT, Guwahati 3

 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?

July 10, 2017 IIT, Guwahati 4
Irreversible first order reactions in series:
PFR/ batch reactor

Concentration-time curves Relative concentrations of

reaction components
For varying k2/k1 values
July 10, 2017 IIT, Guwahati 5
 Irreversible first order reactions in series:
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?

July 10, 2017 IIT, Guwahati 6

 Irreversible first order reactions in series:
CSTR
Find maximum concentration of R:

July 10, 2017 IIT, Guwahati 7

 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.

July 10, 2017 IIT, Guwahati 8

July 10, 2017 IIT, Guwahati 9
Irreversible first order reactions in series

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.

July 10, 2017 IIT, Guwahati 10

Series reactions (Qualitative)

Reaction proceeds only in the presence of light

Consider two different schemes of treating the reactants:

Scheme 1 Scheme 2

July 10, 2017 IIT, Guwahati 11

 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.

July 10, 2017 IIT, Guwahati 12

FAVORABLE CONTACTING PATTERNS FOR IRREVERSIBLE
REACTIONS IN SERIES

Calculate and verify this.

Laminar Turbulent

July 10, 2017 IIT, Guwahati 13

FAVORABLE CONTACTING PATTERNS FOR IRREVERSIBLE
REACTIONS IN SERIES

July 10, 2017 IIT, Guwahati 14

First order followed by zero order reaction

July 10, 2017 IIT, Guwahati 15

Zero-order followed by first order reaction

July 10, 2017 IIT, Guwahati 16

 Irreversible series-parallel reactions

OR

Example: Successive substitutive halogenation/nitration of hydrocarbons

July 10, 2017 IIT, Guwahati 17

Lecture 20

July 10, 2017 IIT, Guwahati 18

Irreversible series-parallel reactions

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

July 10, 2017 IIT, Guwahati 19

Irreversible series-parallel reactions
1. Add A slowly to B

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

R reacts with B to form S.

July 10, 2017 IIT, Guwahati 20

Irreversible series-parallel reactions
2. Add B slowly to A

3. Mix A and B rapidly

July 10, 2017 IIT, Guwahati 21

 Irreversible series-parallel reactions
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

July 10, 2017 IIT, Guwahati 22

 Irreversible series-parallel reactions
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
July 10, 2017 IIT, Guwahati 23
Irreversible series-parallel reactions: PFR
Product distribution: eliminate time variable from two
rate equations

July 10, 2017 IIT, Guwahati 24

 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

July 10, 2017 IIT, Guwahati 25

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

July 10, 2017 IIT, Guwahati 26

Irreversible first order reactions in series

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

July 10, 2017 IIT, Guwahati 27

Irreversible first order reactions in series

-DCB-DCR

-DCA-DCR

Lines of slope 2, why?

go through example 8.2

July 10, 2017 IIT, Guwahati 28

Denbigh Reactions

The performance equations for this reaction scheme reduce

directly to several special cases, such as

July 10, 2017 IIT, Guwahati 29

Denbigh Reactions: PFR
Integrate the performance equations to give

July 10, 2017 IIT, Guwahati 30

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

July 10, 2017 IIT, Guwahati 31

Denbigh Reactions: PFR

July 10, 2017 IIT, Guwahati 32

Denbigh Reactions: CSTR

Note the typo in the book.

Verify it.

July 10, 2017 IIT, Guwahati 33

 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.

July 10, 2017 IIT, Guwahati 34

 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.

July 10, 2017 IIT, Guwahati 35

Example

July 10, 2017 IIT, Guwahati 36

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

July 10, 2017 IIT, Guwahati 37

Example
For k4

from

July 10, 2017 IIT, Guwahati 38

Denbigh Reactions: CSTR

July 10, 2017 IIT, Guwahati 39

Denbigh Reactions: CSTR

July 10, 2017 IIT, Guwahati 40

Denbigh Reactions
Apply the performance equations to give

July 10, 2017 IIT, Guwahati 41