CL 208

Chemical Reaction Engineering-I

 Potpourri of Reactions

This chapter considers all sorts of reactions where the product formed may react further.

Here are some examples:

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Series reactions (Qualitative)
IRREVERSIBLE FIRST-ORDER REACTIONS IN SERIES

Reaction proceeds only in the presence of light

Consider two different schemes of treating the reactants:
Scheme 1 Scheme 2
small stream is continuously withdrawn from the
the contents are uniformly irradiated beaker, irradiated, and returned to the beaker

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 Series reactions (Qualitative)

 This rule can help in evaluating the effectiveness of different reactor systems.
 PFR and batch reactor should both give a maximum R yield because there is no mixing of
fluid streams of different compositions.
 CSTR should not give as high yield of R because a fresh stream of pure A is mixed
continuously with an already reacted fluid in the reactor  Yield is lower.
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Problem 8.1
Favorable Contacting Patterns for Irreversible Reactions in Series

The left pattern is better, in fact it

is the best possible flow scheme

From chapter 6: the left is closer

to plug flow for both first and
second order reactions. Generalize
this to any positive order reactions

The right pattern is better because

it is closer to plug flow

Turbulent flow has less

intermixing of fluids of different
Laminar Turbulent ages, less by passing, hence the
right scheme is better
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 Series Reactions

 First order followed by first order

 PFR
 CSTR
 Comparison of reactors
 Zero order followed by first order
 First order followed by zero order

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 Plug flow and batch reactor: Similarity

Batch reactor

Plug flow reactor

 Notice the similarity between the design equations of two reactors.

 If we replace the reaction time by the space time, equations developed for batch
reactor can be used for PFR.
 For batch reactor: reaction proceeds with time
 For PFR: reaction proceeds along the length

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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)’.

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 Irreversible first order reactions in series: PFR/ batch reactor

Max concentration of intermediate (R):

Time at which max concentration occurs:

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Irreversible first order reactions in series: PFR/ batch
reactor

Concentration-time curves Relative concentrations of reaction

components
For varying k2/k1 values
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 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?

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

Concentration-time curves Relative concentrations of reaction 12

components
 Irreversible first order reactions in series

PFR CSTR

 PFR always requires a smaller time than that for CSTR to achieve max concentration of
R: The difference becomes progressively large as k2/k1 departs from unity.
 For any reaction, the maximum obtainable concentration of R in a PFR is always higher
than that in a CSTR.
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Irreversible first order reactions in series

 Yield of R is always higher for PFR than CSTR for any X.

 If k2/ k1 << 1, design for high conversion of A.
 If k2/ k1 >> 1, design for a very small conversion of A per
pass, separation of R and recycle of unused reactant.

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First order followed by zero order reaction

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Zero-order followed by first order reaction

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 Irreversible series-parallel reactions

OR

Example: Successive substitutive halogenation/nitration of hydrocarbons

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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

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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.

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

3. Mix A and B rapidly

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 Irreversible series-parallel reactions
For reactions in parallel
 CB has no effect as
• Concentration of reactant determines product distribution reactions are of same
• High reactant concentration  favours reaction of higher order order

• Low reactant concentration  favours reaction of lower order

• No concentration effect for reaction of same order

For reactions in series

When A is kept uniform in
• Mixing of fluids of different composition is important composition, R forms.
• mixing of reactants of different composition and different
 When fresh A is mixed with
stage of conversion  low intermediate formation partly reacted mixture no R forms

Series-parallel reactions can be analysed in terms of constituent series and 21

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

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 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, CB1 = CR + CR Used (=CS)

CB2 = CS

CBtotal = CR+2CS

Moles of B consumed = Moles of R formed + 2*Moles of S formed 23

 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

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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
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Irreversible first order reactions in series

-DCB-DCR

-DCA-DCR

 Lines of slope 2, why?

 go through example 8.2

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Example

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 Denbigh Reactions

Denbigh (1958)was the first to treat the followingrather general reaction scheme

 The performance equations for this reaction scheme reduce directly to several
special cases, such as

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Denbigh Reactions: PFR
 Integrate the performance equations to give

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

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Denbigh Reactions: PFR

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 Denbigh Reactions: CSTR

Using the mixed flow performance equation

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Denbigh Reactions: CSTR

At the optimum

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 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.
 If two steps of first order reactions in series have very different values, we can
approximate the overall behaviou
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 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.

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Example EVALUATE THE KINETICS FROM A BATCH EXPERIMENT

 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

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