Table of Contents

1. Introduction to Denbigh Reactions and Series Reactions............................................................2

2. Denbigh Reaction Scheme...........................................................................................................2

3. How to Control Product Distribution in Series Reactions?.........................................................3

3.1 Role of Rate Constants...........................................................................................................3

Maximizing Intermediate B.........................................................................................................3

Maximizing Final Product C........................................................................................................3

Minimizing Side Product D.........................................................................................................3

3.2 Effect of Temperature............................................................................................................3

3.3 Effect of Catalyst...................................................................................................................4

4. Selection of Reactors for Series Reactions to Control Product Distribution...............................4

4.1 Batch Reactor.........................................................................................................................4

4.2 Continuous Stirred-Tank Reactor (CSTR).............................................................................5

4.3 Plug Flow Reactor (PFR).......................................................................................................5

5. Comparison of Reactors for Series Reactions.............................................................................6

6. Conclusion...................................................................................................................................6

References........................................................................................................................................7
1. Introduction to Denbigh Reactions and Series Reactions
In chemical reaction engineering, reactions often do not happen in isolation. Instead, they
proceed through multiple steps, leading to intermediate and final products. Such reactions are
called series reactions.

One of the most well-known kinetic schemes describing series reactions is Denbigh Reaction
Scheme. This scheme is widely used in chemical industries where multiple products can form
from the same reactant through consecutive steps.

2. Denbigh Reaction Scheme

The Denbigh Reaction Scheme represents a general type of series-parallel reaction in which a
reactant A can follow multiple pathways, leading to different products. The general form is:

Here:

 A is the starting reactant.

 B is an intermediate product that can convert to the final product C.
 D is a side product, formed directly from A in a parallel reaction.
 k1, k2 and k3 are rate constants for each reaction step.

This scheme is common in catalytic reactions, polymerization, and pharmaceutical synthesis,

where selectivity between B, C, and D is critical.
3. How to Control Product Distribution in Series Reactions?

3.1 Role of Rate Constants

The key to controlling product distribution lies in adjusting the rate constants k1,k2 and k3. The
relative magnitudes of these rates determine the yield of each product. The following strategies
can be used:

Maximizing Intermediate B

 The goal is to increase k1 while decreasing k2 so that more B is formed and

does not quickly convert to C.
 This can be done by lowering temperature (if k2 has a higher activation
energy) or using catalysts selective for A→B

Maximizing Final Product C

 Increase k2 so that once B is formed, it rapidly converts to C.

 Use a catalyst that favors the second reaction step.

Minimizing Side Product D

 Decrease k3 by controlling reaction conditions (e.g., choice of solvent,

inhibitors, or specific catalysts).

3.2 Effect of Temperature

From the Arrhenius equation, the rate constants are given by:

where Ea is the activation energy, R is the gas constant, and T is temperature. By changing T,
one can selectively accelerate or decelerate certain steps in the reaction.

 If k2 has a much higher Ea than k1, increasing temperature will favor B→C more than
A→B.
  If k3 is temperature-sensitive, reducing temperature can suppress A→D.

3.3 Effect of Catalyst

Catalysts selectively lower the activation energy of a specific step. Choosing a catalyst for A→B
while deactivating A→D ensures a high yield of B.

4. Selection of Reactors for Series Reactions to Control Product

Distribution
The choice of reactor is critical in optimizing product selectivity. Below, we analyze different
reactor types and their impact on series reactions.

4.1 Batch Reactor

A batch reactor is a closed system where reactants are allowed to react for a set time. Its
characteristics:

 Time-dependent conversion: The longer the reaction runs, the more BBB converts to
CCC.
 Best for maximizing intermediates B: If we stop the reaction at the optimal time, we
can collect B before it converts to C.
 Difficult to scale up because stopping at the right time is challenging.

Equation for product concentration over time in a batch reactor:

These equations allow us to predict the concentration of each species at any given time.

4.2 Continuous Stirred-Tank Reactor (CSTR)

A CSTR operates with continuous feed and outflow, maintaining uniform concentration inside.

 Best for maximizing C: If reaction times are long, most B will convert to C.
 Minimizes intermediates B unless multiple reactors are used in sequence.

Mass balance equations for a CSTR:

where:

 Fin, Fout = Flow rates in and out.

 CA = Concentration of A.
 RA = Reaction rate.
 V = Reactor volume.

4.3 Plug Flow Reactor (PFR)

A PFR moves reactants through a pipe, allowing reaction progress along the length.

 Best for controlling selectivity because concentration varies along the reactor.
 If reaction stops midway, we can maximize intermediate B.
 If long enough, we get mostly C.

Mass balance equation for a PFR:

where V is reactor volume and F is molar flow rate.

5. Comparison of Reactors for Series Reactions

Reactor Type Best for Maximizing Control Strategy

Batch Reactor Intermediate BBB Stop reaction at the right time
CSTR Final product CCC Long residence time
PFR Intermediate or final product Control reactor length

6. Conclusion
Controlling product distribution in series reactions requires careful selection of:

1. Reaction conditions (temperature, catalysts).

2. Rate constants (via kinetics and thermodynamics).
3. Reactor type (batch, CSTR, or PFR).

By using a combination of kinetic control, catalyst selection, and reactor engineering, we can
optimize the yield of desired products in industrial applications.
References
[1] O. Levenspiel, Chemical Reaction Engineering, 3rd ed. New York, NY, USA: Wiley, 1999.

[2] H. S. Fogler, Elements of Chemical Reaction Engineering, 5th ed. Upper Saddle River, NJ,
USA: Pearson Education, 2016.

[3] J. M. Smith, Chemical Engineering Kinetics, 3rd ed. New York, NY, USA: McGraw-Hill,
1981.

[4] G. F. Froment, K. B. Bischoff, and J. De Wilde, Chemical Reactor Analysis and Design, 3rd
ed. Hoboken, NJ, USA: Wiley, 2010.

[5] J. R. Bourne, "Mixing and the selectivity of chemical reactions," Organic Process Research
& Development, vol. 7, no. 4, pp. 471-508, 2003.

[6] M. Baerns and G. D. Moeller, "Fundamentals of chemical reaction engineering: Reactor

selection and design," in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed., Weinheim,
Germany: Wiley-VCH, 2011.

[7] D. T. Allen and D. R. Shonnard, Green Engineering: Environmentally Conscious Design of

Chemical Processes, Upper Saddle River, NJ, USA: Prentice Hall, 2001.

[8] A. Varma, M. Morbidelli, and H. Wu, Parametric Sensitivity in Chemical Systems,

Cambridge, UK: Cambridge University Press, 1999.

[9] L. D. Schmidt, The Engineering of Chemical Reactions, 2nd ed. Oxford, UK: Oxford
University Press, 2005.

[10] J. Villermaux, "The potential of reactor engineering concepts for improving selectivity,"
Chemical Engineering Science, vol. 42, no. 4, pp. 925-933, 1987.