MULTIPLE

REACTIONS
GALORE, VOLUME I

MULTIPLE
REACTIONS
GALORE, VOLUME I
TYPES, USE AS TOOL AND APPLICATIONS

DR. KAL RENGANATHAN SHARMA

Multiple Reactions Galore, Volume I: Types, Use as Tool and Applications

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First published in 2016 by
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ISBN-13: 978-1-60650-809-1 (print)
ISBN-13: 978-1-60650-810-7 (e-book)
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DOI: 10.5643/9781606505014
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DEDICATION
This book is dedicated to my eldest son, Chi. R. Hari Subrahmanyan
Sharma (alias Ramkishan), who turned 14 on August 13, 2015.

ABSTRACT
More than one rate expression is needed in order to describe multiple reactions. Multiple reactions may occur amongst 3-7 species and they may
react in series, in parallel, in circular manner with input and/or output, in
rectangular manner, in a triangular manner, sometimes occur in more than
one phase and may be reversible. Multiple reactions can be classified into
(1) Trambouze scheme, (2) consecutive-competitive reactions, (3) Denbigh scheme, and (4) reaction pathways. Femtosecond spectroscopy was
used by Nobel Laureate Zewail to confirm the formation of butane as
intermediate when ethylene is transformed into butane. Kinetics of the
reactions may be elementary or may follow the Michaelis and Menten
scheme or free radical scheme or other schemes. Enzyme catalytic reactions and President B. Obamas clean power plan initiatives can use better
understanding of multiple reactions. CO2 emissions can be reduced by
methods of capture and fixation.
Mathematical expressions can be written for the reaction probability
for surface-specific reactions in liquids. Denaturation and renaturation of
DNA involved reversible reactions. Mathematical models are provided for
prediction of melting temperature of DNA and entropic changes. Hysterisis phenomena seen during melting can be accounted for by hyperbolic
diffusion models. Sharma2 has discussed damped wave diffusion and
relaxation models. Michaelis and Menten kinetics can be studied experimentally using microarray analysis. The enzymesubstrate kinetic scheme
is given in Eq. (2.16). In Figure 2.2 is shown how kinetic information is
obtained from raw microarray data. The solution to the MichaelisMenten
kinetic equations is made implicit using Taylor series expansion of the
derivatives as shown in Eq. (2.21). Eq. (2.26) was found to be a reasonable approximation to the exact solution of Eq. (2.20) for short times. Sideby-side comparison of the Taylor series solution and exact solution is
shown in Figure 2.3. Mucientes and de la Pena6 have shown that the concentrationtime integral method can be used to study parallel consecutive

viii ABSTRACT

reactions with a reversible first step. Kindly note that the scheme of reactions shown in Figure 2.4 is a special case of the WeiPrater scheme of
reactions (Froment and Bischoff), as shown in Figure 2.5. The kinetic rate
expressions for the scheme of reactions shown in Figure 2.4 were integrated and presented as Eqs. (2.42) to (2.44). The dimensionless species concentrations, uA, uB, and uC, are plotted as a function of time in Figures 2.6
and 2.7. A practical application of the scheme of reactions shown in
Figures 2.4 and 2.5 is in the interpretation of reaction pathways expected
during the decomposition of cyclo(glycylglycine). Hydrolysis and cyclodehydration of glycylglycine occur simultaneously, leading to the formation
of glycine and cyclo(glycylglycine). The state-space form of the rate expressions is given by Eq. (2.56). The criteria for when subcritical damped
oscillations in concentration can be expected to occur in the system as a
function of the reaction rate constant ratios are given by Eq. (2.59). Strong
Keesom forces lead to the formation of hydrogen bonding. Chlorinated
PVC forms permanent dipole with phenol functional groups. Florys equilibrium rate constant KA to describe j repeat units in the polymer that participate in hydrogen bonding is given by Eq. (2.49). The fraction of OH
functional groups that can be attributed to participate in the hydrogen
bonding may be related to the equilibrium rate constants K2 and KA, and is
given by Eq. (2.52). Infrared methods can be used to obtain the equilibrium constant of interassociation Keesom interactions. Equilibrium rate
constants representing self-association and interassociation can be
obtained from experimental data. The fraction of free carbonyl groups,
fFC = 0, can be estimated and is given by Eq. (2.54). Reactive mixing is
defined by Bourne10 as the process of bringing reagents together on a
molecular scale.
Biomass can be pyrolyzed into char, chemicals, bio-oil, and syn-gas.
Computer simulations are used to study the kinetics of reactions that occur
during pyrolysis of cellulose. The scheme of reactions that are believed to
occur during pyrolysis of cellulose is given in Figure 52. The scheme of
reactions shown in Figure 52. was proposed by Wooten et al.3 A is the cellulose, R is the activated cellulose, P is the product, S and U are the primary and secondary tar, and T is the secondary gas. The secondary char from
cellulose is formed from the polymerization of anhydrosugars, also called
levoglucosan. Levoglucosan undergoes vapor phase polymerization. The
kinetic rate expressions of the reactions shown in Figure 52. are given by
Eqs. (3.1) to (3.6). The kinetic rate equations given by Eqs. (3.1) to (3.6)
were made dimensionless for the six species and seven reaction rate
constants. The state-space model for kinetic rate expressions are given by

ABSTRACT ix

Eq. (3.14). The eigenvalues are 0 thrice: ( + ), ( + + ), (1 + ).

Negative signs for eigenvalues indicate a stable system. Eqs. (3.8) to
(3.13) can be solved for by the method of Laplace transforms. The model
solutions are given by Eqs. (3.23) to (3.28). The product distributions are
shown in Figure 53 for a typical set of reaction rate constants. The intermediate product species, activated cellulose, R, and primary tar, S, can be
seen to undergo a maximum concentration as a function of time. The
secondary tar and secondary gas begin to form after a lag time. The concentration of product P rises and reaches an asymptotic plateau. The
dimensionless concentration of species R, S, P, and T + U is plotted as a
function of conversion of A in Figure 54.
The scheme of reactions shown in Figure 55. is an extension of the
general scheme of reactions called the Denbigh scheme of reactions. This
scheme is shown in Figure 55. The kinetic rate equations for the 4 reactions shown in Figure 55 in dimensionless form are given by Eqs. (3.31)
to (3.35). The kinetic rate expressions are solved for by the method of
Laplace transforms. The dimensionless species concentration as a function
of dimensionless time for the five species A, R, S, T, and U are given by
Eqs. (3.41) to (3.45). The distribution of products as dimensionless concentrations of the five species as a function of dimensionless conversion
of reactant A is shown in Figure 56.
Reclamation of value in the rubber portion of the waste tires may be
more profitable and more environmentally benign compared with incineration and fuel use methods. Devulcanization and depolymerization reactions can lead to recovery of polybutadiene and butadiene monomer.
Competing parallel reactions after the devulcanization step is studied in
more detail. The dynamics of the general Denbigh scheme of reactions in
a CSTR are studied. The composition of the species involved is obtained
as a function of time from model solutions. A general state-space form is
proposed for simultaneous series-parallel reactions. Types of instability
that may arise depend on the eigenvalues of the system. The eigenvalues
of the sparse matrix indicate that the system is of the integrating type.
Solutions can be obtained from the eigenvalues for seven species. Information from the model solution can be used to optimize the yield of rubber during reclamation of rubber from waste tires.
A scheme is selected from molecular orbital calculations to represent
the multiple reactions that occur during formation of biodiesel from
Jatropha Curcas oil using excess methanol and is shown in Figure 3.8.
The reactions are consecutive-competitive type. They are transesterification reactions. Methanol is used to convert triglycerides present in

x ABSTRACT

Jatropha oil to diglycerides, monoglycerides and glycerol with FAME,

fattyacid methyl ester produced in each intermediate step. When excess
methanol is used they reactions shown in Eq. (3.48) can be assumed to
obey the pseudo first-order kinetics. They are assumed to be irreversible
under the temperature and pressure of operation. The kinetic rate expressions (3.49) for this scheme were made dimensionless. Solution was
obtained by the method of Lapace transforms. The product distribution
curves are shown in Figure 3.9. The species R and S start with zero concentration, form and rise in concentration, reach a maxima and fall in species concentration as time progresses. Products S and T are found to
undergo a short period of gestation. The concentration vs. time graph
was seen to undergo a change in curvature from convex to concave. At
certain values of reaction rate constant ratios there was seen a cross-over
of more T formation compared with species S. The centrifugal separation
of glycerol and biodiesel is simulated using MS Excel spreadsheet. For a
given density ratio and viscosity ratio, the power needed for the rotor as a
function of RPM is obtained from the simulations and found to be log
linear, as shown in Figure 8. A plot was obtained for 29 different values of
the agitator RPM and two liquids with different viscosities. The layer formation may become unstable at certain volume fractions of the feed.
Cell proliferation during cancerous growth can be modeled using
Monod kinetics. Eqs. (3.66) to (3.73) are written for the concentration of
biomass, rates of reactions of nutrient, RNA, DNA, and cell growth.
Review of stem cells, cancer, and CSCs was presented by Reya et al. The
cell division processes symmetric, asymmetric, formation of progenitor
cells, and lysis are given in Eqs. (3.66) to (3.73). The progression of cancer is captured in the rate of CSC formation in Eq. (3.75). Simulations of
these multiple reactions were performed in a HP Compaq Elite 8300 computer using MS Excel spreadsheet for Windows 2010. Examples for simulation results are shown in Figure 3.13. A concave-to-convex change in
curvature can be seen for large times in Figure 3.13.
The scheme of reactions that occur during degradation of carotene is
shown in Figure 65. Degradation of -Carotene has been studied by kineticists. Isomerization and oxidation followed by homolytic cleavage are the
events that are believed to happen. The schemes shown in Figure 65 are
special cases of Figure 2.1 in Chapter 2.
A mass transfer model can be used to evaluate the fate of pesticide
between water and soil, soil and water, and vapor phases. This can be derived from performing mass balance over a thin slice. The important
transport operations are shown in Figure 66. The pesticide mass transfer

ABSTRACT xi

between soil and water, water and soil, water and air, soil and air, and the
regions of soil that has reached steady state or still undergoing transient
diffusion is depicted in Figure 66.
Herbicides and pesticides can be added to prevent harm to the grass in
the lawn or crops in the farm. Transient diffusion and simultaneous reactions take place. In such cases, finite speed diffusion models can be considered.99 Breakthrough curves can be better explained using hyperbolic
models. Two regions are noted in the soil. One region is characterized by
reversible reactions for partitioning. The second region is characterized by
mass transfer by transient diffusion. The model solutions shown by Cryer
(2015) are given by Eq. (3.85).
The reactions that occur during N-acylation with mixed carboxyliccarbonic anhydride intermediates can be reduced to the scheme of seriesparallel reactions shown in Figure 67. This scheme of reactions where the
Denbigh scheme is applied to N-acylation reactions is shown in Figure 68.
The kinetic rate expressions are written for the scheme shown in Figure
68. The model solutions to the kinetic rate expressions are given in Eqs.
(3.90) to (3.93). The distribution of products as dimensionless concentrations of the four species as a function of dimensionless conversion of reactant A is shown in Figure 69.

KEYWORDS
Multiple Reactions; Trambouze Scheme; Denbigh Scheme; Reaction
Pathways; Enzyme Catalysis; President B. Obamas Clean Power Plan;
Biodiesel; Jatropha Curcas; Transesterification; Cellulose Pyrolysis; Monomer Reclaimation from Waste Tires; Lawn Care Transport Models;
N-Acylation Reactions; Cancer Cell Proliferation Model; Monod Kinetics;
DNA Melting; -carotene degradation; Centrifuge design; layer separation; log-linear correlation; State space model; multiplicity; consecutivecompetitive reactions; Michaelis and Menten Kinetics; Microarray Analysis;
Wei-Prater Scheme; Second Order Reactions; Graphical Procedure;
Proteomics; Taylor series and more useful solution; hydrogen bonding;

CONTENTS
LIST OF FIGURES

XV

LIST OF TABLES

XIX

PREFACE

XXI

1.

2.

INTRODUCTION TO MULTIPLE REACTIONS

1.1

Elementary Chemical Reactions

1.2

Intermediates

1.3

Classification of Types of Multiple Reactions

1.3.1

Trambouze Scheme

1.3.2

Consecutive-Competitive Reactions

1.3.3

Denbigh Scheme

1.3.4

Reaction Pathways

1.4

Enzyme Catalytic Reactions

11

1.5

Regulatory Compliance

13

1.6

Reversible Reactions

17

1.7

Summary

17

References

19

MULTIPLE REACTIONS AS STUDY TOOL

21

2.1

Surface Reactions

21

2.2

Melting Temperature of DNA

22

2.3

Proteomics and MichaelisMenten Kinetics

27

2.4

Parallel Consecutive Reactions

32

2.5

WeiPrater Scheme of Reactions

35

2.6

Quantitation of Keesome Interactions in Polymers

41

xiv CONTENTS

2.7
2.8
3.

Manifestation of Micromixing in Mass Transfer

Characteristics

44

Summary

45

References

46

APPLICATIONS

49

3.1

Pyrolysis of Cellulose

49

3.1.1

Kinetic Model

52

3.1.2

State-Space Model

53

3.1.3

Method of Laplace Transforms

54

3.1.4

Model Results

56

Denbigh Scheme of Reactions

58

3.2.1

59

3.2
3.3
3.4

Products Distributions by Laplace Transforms

Application of Denbigh Scheme to Waste

TiresTired Old Problem

61

Biodiesel

67

3.4.1

Biodiesel Production Forecast

68

3.4.2

Next Generation Sequencing

71

3.4.3

Genetic Modification and Cultivability

75

3.4.4

Consecutive-Competitive Reactions

80

3.4.5

Conclusion

85

3.5

Metastatic Cancer Spread

87

3.5.1

Kinetic Model for Progression of Cancer

90

3.6

Thermal Degradation of -Carotene:

Pink Grapefruit Juice Composition Effects

92

3.7

Fate of Pesticides during Lawn Care

93

3.8

Scale-Up Tool by Quantitation of CO2 Evolution

During Different Parts of the Reaction Scheme

97

3.9

Summary

References

100
103

ABOUT THE AUTHOR

109

INDEX

111

LIST OF FIGURES

Figure 1.1.

Free Radical Initiation, Propagation, and Termination Random Copolymerization Reactions during
the formation of Grafted SAN (Styrene and Acrylonitrile) Chains and Matrix SAN Chains

Trambouze Scheme of ReactionsReactant A

forms Three Products, R, S, and T

Chlorination of Methane to Carbon Tetrachloride

by Successive Chlorination

Transesterification of Triglycerides to form

Diglycerides, Monoglycerides, and Glycerol with
Fatty Acid Methyl Ester made in Each Step

Denbigh Scheme of Reactions in Series and

Parallel for Five Species, A, R, S, T, and U

Citric Acid Cycle Represented as Reactions in

Circle

Figure 1.7.

DYKAT Reaction Scheme

Figure 1.8.

Diffusion-Limited Binding of Basic Leucine

Receptor Protein

10

Reaction Scheme during Formation of Products

using Enzyme Catalysis

13

Fixation of CO2 by Conversion into Organic

Compounds

15

Simultaneous Adsorption and Reaction at Vapor

Liquid Surface

22

Obtaining Kinetic Information from Raw

Microarray Data

29

Figure 1.2.
Figure 1.3.
Figure 1.4.

Figure 1.5.
Figure 1.6.

Figure 1.9.
Figure 1.10.
Figure 2.1.
Figure 2.2.

xvi LIST OF FIGURES

Figure 2.3.

Taylor Series Solution and Exact Solution for

Dimensionless Concentration

32

Parallel Consecutive Reactions with First Step

Reversible

35

Parallel Consecutive Reactions with First

Reversible Step as Special Case of WeiPrater
Mechanism

35

Dimensionless Species Concentrations uA, uB, and

uC vs. Time. Reaction Rate Constants: k1 = 4 sec1;
k2 = 2 sec1; k3 = 1.5 sec1; and k4 = 2 sec1

37

Dimensionless Species Concentrations uA, uB, and

uC vs. Time. Reaction Rate Constants: k1 = 0.165
sec1; k2 = 0.528 sec1; k3 = 0.14 sec1; and
k4 = 0.098 sec1

38

WeiPrater Mechanism during Cyclodehydration,

Decomposition and Hydroylsis Network Reactions

38

WeiPrater Scheme of Reactions with Three

Reversible Reactions on a Triangle

39

General Scheme of Reactions to Describe

Pyrolysis of Cellulosic Biomass. ACellulose,
RActivated Cellulose, PProduct, SPrimary
Tar, USecondary Tar, and TSecondary Gas

50

Dimensionless Concentrations of Celluose (A),

Activated Cellulose (R), Primary Tar (S), Primary
Char (P), and Secondary Gas (T) + Secondary Tar
(U) as a Function of Dimensionless Time

56

Dimensionless Concentrations of Activated

Cellulose (R), Primary Tar (S), Primary Char (P),
and Secondary Gas (T) + Secondary Tar (U) as a
Function of Conversion of Cellulose (A)

57

Figure 3.4.

Denbigh Scheme of Reactions

58

Figure 3.5.

Dimensionless Concentration of Species R, S, T,

and U as a Function of Conversion of A

60

Flow Diagram for Continuous Production of

Biodiesel and Glycerol from J. curcas Shrub Fuel
Crop in Semiarid Farms

76

Figure 2.4.
Figure 2.5.

Figure 2.6.

Figure 2.7.

Figure 2.8.

Figure 2.9.
Figure 3.1.

Figure 3.2.

Figure 3.3.

Figure 3.6.

LIST OF FIGURES xvii

Figure 3.7.
Figure 3.8.
Figure 3.9.

Figure 3.10.

Figure 3.11.

Figure 3.12.

Figure 3.13.
Figure 3.14.
Figure 3.15.

Figure 3.16.

Figure 3.17.
Figure 3.18.

Recombinant Plasmid FormationCPI Replaces

CaMV 35s Promoter in Plasmid pBI121

77

Transesterification Catalyzed Reactions from

Triglycerides to Glycerol and FAME

81

Triglyceride (A), Diglyceride (R), Monoglyceride

(S), Glycerol (T), and FAME (P) Product
Distribution in Progressive Methanolysis44 at
= 0.75 and = 0.4

84

Triglyceride (A), Diglyceride (R), Monoglyceride

(S), Glycerol (T), and FAME (P) Product
Distribution in Progressive Methanolysis at
= 0.75 and = 0.6

85

Triglyceride (A), Diglyceride (R), Monoglyceride

(S), Glycerol (T), and FAME (P) Product
Distribution in Progressive Methanolysis at
= 0.75 and = 0.25

86

Triglyceride (A), Diglyceride (R), Monoglyceride

(S), Glycerol (T), and FAME (P) Product
Distribution in Progressive Methanolysis at
= 0.75 and = 0.35

87

Cancer Stem Cells Proliferation and Decay as a

Function of Time

92

Scheme of Reactions during Degradation of

Carotene

93

Mass Transfer of Pesticide between Water and

Soil, Soil and Water, and Vapor Phases. Transient
and Equilibrium Regions in Field

95

Scheme of Reactions during N-Acylation.

AAminoacid; RMixed Anhydride;
UUndesired Product; and DDesired Product

97

Denbigh Scheme Applied to N-Acylation

Reactions

98

Dimensionless Species Concentrations of

Naphthyl Alanine, Carboxylic-Carbonic
Intermediate, Asymmetric Anhydride, Symmetric
Anhydride

99

LIST OF TABLES

Table 3.1.

Ratios of reaction rate constants during pyrolysis

56

Table 3.2.

Ratios of reaction rate constants during pyrolysis

58

Table 3.3.

Reaction rate constants used in illustration of

denbigh scheme of reactions

61

Next generation sequencers commercially

available

72

Protein translation from normal and diseased cells

showing SNP

88

Reaction rate constant ratios in the illustration of

N-acylation reactions

99

Table 3.4.
Table 3.5.
Table 3.6.

PREFACE
The book Chemical Reaction Engineering, John Wiley, 1999, Hoboken,
NJ, has been cited 9,747 times in Google Scholar. The term multiple reactions returns 4,128 times in Google Patents. The availability of computing resources has increased tremendously over the past 50 years. Ahmed
Zewail received the Nobel Prize for pioneering work in femtosecond spectroscopy. The formation of ethylene from cyclobutane goes through the
formation of butane. Intermediates may form, rise and fall in concentration, and vanish during the course of the transformation of reactant to
product(s) in the train of reactors, separations, and other unit operations
used in the chemical process industry.
This two-volume book discusses the engineering design issues involved when multiple reactions occur in the considered process. Design
issues such as products distribution, and profitability and the sensitivity of
important quantities such as yield, selectivity to rate constant ratios need
to be spelled out in detail. Concentration time curves can be convex or
concave, or the curvature can change during the course of the reaction.
Linear relations can be seen for the zeroth-order rate. Gestation period and
cross-over in selectivity of intermediates were found in some cases that
could not be expected from qualitative considerations.
MS Excel Spreadsheet is used to seek numerical solutions by Runge
Kutta higher-order methods. By-product is becoming important in some
processes. Traditional textbooks in reaction engineering seldom discuss
the yield of by-product. When closed-form analytical solutions are not
possible, qualitative discussions are provided. Quantitative analysis is
possible, and the book discusses how to use desktop computer simulations
to obtain the desired objectives.
The mathematical level expected to read the book needs some calculus, linear algebra, and numerical solution methods. Calculus can be used
to solve ordinary differential equations. Numerical solutions such as
RungeKutta higher-order methods can be sought when necessary. Meth-

xxii PREFACE

od of Laplace transforms and solution of simultaneous systems of ordinary

differential equations (ODEs) using auxiliary algebraic equations and integrating factors can be used to obtain closed-form analytical solutions.
Taylor series solution is also used. Most of the systems discussed in the
book are homogeneous in phase, but several reactions do occur. Quantitative analysis is within reach even for problems that were once considered
formidable. Graphical procedures have paid rich dividends in the past and
continue to be emphasized. Microsoft Excel 2013 is used to generate the
84 illustrations used in the book. New perspectives and not intuitively
obvious recommendations can come about after the analysis of multiple
reactions. Maxima, gestation period, curvature change from convex to
concave, sigmoidal shape curve, and crossover are seen to come about.
Reactions in circle are introduced without violation of the law of microscopic reversibility. Multiple reactions are classified into the Trambouze scheme, Denbigh scheme, consecutive-competitive reactions, and
reaction pathways. Case studies of processes that use enzyme catalysis,
CO2 fixation and CO2 capture, propanediol by enantiomeric catalytic
transformation, methionine cycle, Calvin cycle, styrene/acrylonitrile/vinyl
polybutadiene terpolymer, alphamethyl styrene/acrylonitrile/styrene terpolymer, methyl methacrylate/alpha-methylstyrene, ternary azeotrope of
MMA/ODMA/DDMA, application of oligomer as coatings, shift in reaction mechanism during thermal reversible terpolymerization, betamethylstyrene/acrylonitrile copolymer, DNA melting, proteomics and
Michaelis and Menten kinetics, WeiPrater scheme, Keesome interactions
in polymers, pyrolysis of cellulose, biodiesel production, metastatic cancer
progression, thermal degradation of carotenoids, fate of pesticides during
lawn care, and N-acylation reactions are illustrated.
New topics covered in polymer reaction engineering are state-space
model for multicomponent copolymer composition, sequence distribution,
polyrate, and molecular weight. The mathematical expressions used in
product design are derived. Grafting selectivity is introduced. Case studies
from the Nobel lectures of William Knowles, Ahmed Zewail, Ei-Ichi Nigichi, A. G. Macdiarmid, and Yuan Tseh Lee are discussed.

CHAPTER 1

INTRODUCTION TO MULTIPLE
REACTIONS
CHAPTER OBJECTIVES

Types of Multiple Reactions

Scheme of Multiple Reactions
Denbigh Scheme
Trambouze Scheme
Free Radical Propagation Chain Reactions
Reaction PathwaysCitric Acid Cycle, Calvin Cycle, EMP
Pathway
Wei and Prater Triangular Schemes
DYKAT Quadrangular Schemes
Reaction with Mass Transfer

1.1 ELEMENTARY CHEMICAL REACTIONS

More than one rate expression is needed to describe multiple reactions.
The study of material transformations is a large part of what goes on in the
hallowed halls of university chemistry buildings. In 1986, in the Nobel
lecture about elementary chemical processes, laureate Y. T. Lee clarified
that all macroscopic chemical processes consist of many elementary
chemical reactions that are themselves simply a series of encounters between atomic or molecular species.
Chemical engineers design chemical process flow diagrams that can
be used to build storage tanks for raw materials, chemical reactors to perform the reactions dictated by chemistry, absorption towers, distillation

2 MULTIPLE REACTIONS GALORE, VOLUME I

columns for separating the unconverted reaction mass from the products,
other unit operations that may be applicable, and pumps and pipes to recycle the separated raw materials to the storage tanks and hoppers. These
chemical manufacturing units can be used to use the novel chemistry discovered in the laboratory to make useful products on a large scale at the
lowest cost in a safe manner without tipping the environmental and ecological balance in the universe. Pilot plants can be used to scale up from
bench-scale chemistry laboratories to manufacturing units. Chemical reactions are exploited for commercialization of new products or for cutting
the total cost of production of existing products.
Oftentimes, the industrial chemistry used may comprise several steps.
Focus is applied to sorting out all of the elementary chemical reactions
that are involved in a macroscopic chemical process and determining their
respective rates.

1.2 INTERMEDIATES
Intermediates may form, rise and fall in concentration, and vanish during
the course of the transformation of reactant to product(s) in the train of
reactors, separations, and other unit operations used in the chemical process industry. Some of the intermediates formed may sell for more dollars
compared with other species. Some intermediates may be contaminants
and therefore undesirable, and hence the formation may need to be minimized. Removal and separation of intermediates of interest can lead to
more yield and more profit.
Information about the rate of chemical reactions, time dependence of
chemical change as a function of temperature, is of paramount importance
for the successful manufacture of novel materials. Heat released during
exothermic reactions is removed using jacket cooling or by evaporation of
hot liquids into the vapor phase. Water from the jacket along with water
from the overhead condenser in the distillation column on reaching a
higher temperature is contacted with dry air in a hyperbolic cooling tower.
The dry air gets humidified.
The chemical process engineer needs to understand these systems better. Qualitative discussions about product distributions can be augmented
by detailed quantitation using computer simulations. The availability of
computing resources has increased tremendously over the past 40 years.
Design issues such as product distribution, reactor choice, economic analysis, yield, and selectivity and their dependence on rate constant ratios can

INTRODUCTION TO MULTIPLE REACTIONS 3

be spelled out in greater detail. Numerical solutions can be sought when

necessary. Method of Laplace transforms and solution of simultaneous
systems of ordinary differential equations (ODEs) using auxiliary algebraic
equations and integrating factors can be used to obtain closed-form analytical solutions. Quantitative analysis is within reach even for problems that
were once considered formidable.
The chemical process engineer this time and age makes products at
lowest cost, with less pollution from a variety of raw materials using
CSTRs (continuously stirred tank reactors) operated in batch, semi-batch,
and continuous mode, and PFRs (plug flow reactors) in continuous mode.
Oftentimes a number of reactions take place between the reactant and the
product. Interest in by-product recovery is growing. When a new product
or process is found to be successful, more plants are planned to be built
either by retrofit of existing similar plants or by construction of a large
plant. Scale-up of novel chemistries through pilot plants and construction
of new plants needs a good understanding of the issues involved in multiple reactions. They may be in series, in parallel, form a circle, or may be
reversible. Each step may be of a different order or may obey a different
kinetic expression. The availability of desktop computers can facilitate a
detailed treatment of these reactions and thereby help the United States to
stay ahead of other countries in reaction and transport phenomena. Selectivity, yield, reactor size, and optimization need to be quantitated. Students
will be able to learn how to treat intermediate products during a complex
reaction scheme in their project. Case studies are drawn from different
processes.
Chemical reactions at a molecular level involve elemental rearrangement during bimolecular or trimolecular collisions. Collisions are associated
with momentum change. Newtonian force is associated with momentum
change. Acted upon over a finite area, this force becomes the mechanical
stress that can be viewed as the fundamental event that reactions seen by the
laboratory chemist arise from. The dynamic course of reactions can be studied systematically by listing all the multiple reactions that occur. Sometimes
more than one set of plausible reactions can be written and one set selected
based on experimental data. Scheme of reactions can be evaluated using
quantum mechanical considerations. Quantum mechanical analysis added
depth to the understanding provided by Arrhenius in general with particular
reference to the exponential dependence of temperature of the reaction rate
constant.

4 MULTIPLE REACTIONS GALORE, VOLUME I

k = k0 e

E
a
RT

(1.1)

where Ea is the activation energy and k0 is the pre-exponential factor.

Interaction potential as a function of interatomic distances is estimated
using quantum mechanics. Potential energy surface is used to calculate the
classical trajectories. Dynamics of elementary chemical reactions can be
studied experimentally. Products that arise from unimolecular collisions
were tested in the spectroscopy laboratory for nascent quantum-state distributions. Chemical lasers, fluorescent spectroscopy, and linear and nonlinear laser spectroscopy may be used for the study. Crossed molecular
beams were found most suitable for the identification of complex reaction
mechanisms involving macro atomic radicals, looking at reaction intermediates, studying the formation and decay of intermediates, and better
understanding why the chemical reactivity changes. Molecular velocity
distributions and molecular orientations during the chemical reaction were
measured. Motion of individual atoms during collisions that cause the
reaction can be observed experimentally.
In this book, mathematical model solutions are obtained to describe
the product distributions and evolution of species with time.

1.3 CLASSIFICATION OF TYPES OF MULTIPLE

REACTIONS
Multiple reactions can be classified as follows:
1.3.1 TRAMBOUZE SCHEME
Reactions that occur in parallel fall under this scheme. For example, during the continuous mass polymerization and manufacture of HIPS (high
impact polystyrene) and ABS (acrylonitrile butadiene styrene), peroxide
initiators are used to start the polymerization reactions. The propagation
reactions and termination reactions yield polymers of desired molecular
weight and molecular weight distribution. Narrow high molecular weight
polymers can be viewed as an intermediate in a series of reactions.
According to the bench chemists who come up with the industrial chemistry
for the processes, the initiator decomposes into free radicals. These free
radicals can either initiate polymerization on polybutadiene grafting sites
or can initiate polymerization in bulk monomer phase. Depending on

INTRODUCTION TO MULTIPLE REACTIONS 5

where the initiation begins, the graft chains and matrix chains form. In the
case of HIPS, homopolymer of styrene forms in the graft and matrix phases.
A RPPS (rubber phase particle size) with an average size of about 2 m is
allowed to form. The styrene monomer combines with the decomposed
peroxy radical on the polybutadiene graft site. As the free radical reactions
proceed, the graft chains form and graft phase forms and goes from a solution in monomers and solvent to a larger continuous phase to a smaller
dispersed phase. Some of the peroxy-decomposed radicals diffuse to the
bulk of the monomer phase and form the matrix homopolymer chains. In
the case of continuous mass polymerization process to manufacture ABS,
two monomers styrene and acrylonitrile participate in the graft chain formation and matrix chain formation. Sometimes a third termonomer such
as butyl acrylate is used. The choice of the third monomer depends on the
values of the reactivity ratios and the amount of internal plasticization
needed. These initiator reactions in the rubber phase and matrix phase are
said to react in parallel (see Figure 1.1). The Trambouze scheme is shown
in Figure 1.2.1

Figure 1.1. Free Radical Initiation, Propagation, and Termination Random

Copolymerization Reactions during the formation of Grafted SAN (Styrene and
Acrylonitrile) Chains and Matrix SAN Chains

1.3.2 CONSECUTIVE-COMPETITIVE REACTIONS

Sometimes, multiple reactions occur in sequence with a common species
between the sequence elements. These reactions may be simple and reversible. The orders of the reactions can be zeroth, first, second, third, or

6 MULTIPLE REACTIONS GALORE, VOLUME I

fractional orders. Kinetics may be complex, such as MichaelisMenten

kinetics, Monod kinetics, or nuclear runaway reactions of free radical
propagation polymerization reactions. One example of reactions in series
is the chlorination of methane. Useful products are carbon tetrachloride,
chloroform, methylene chloride, and methyl chloride. This scheme is
shown in Figure 1.3.

Figure 1.2. Trambouze Scheme of Reactions

Reactant A forms three Products, R, S, and T

Figure 1.3. Chlorination of Methane to Carbon Tetrachloride by Successive

Chlorination

INTRODUCTION TO MULTIPLE REACTIONS 7

The elementary reactions in series sequence shown in Figure 1.3 can

be written as follows:
k1

CH 4 + Cl 2 CH 3 Cl
k2

CH 3 Cl + Cl 2 CH 2 Cl 2
k3

(1.2)

CH 2 Cl 2 + Cl 2 CHCl 3
k4

CHCl 3 + Cl 2 CCl 4

The rate constants for the simple irreversible first-order reactions in

the reaction sequence given in Eq. (1.2) are k1, k2, k3, and k4 for the chlorination of (1) methane to methyl chloride, (2) methyl chloride to methylene chloride, (3) methylene chloride to chloroform, and (4) chloroform
to carbon tetrachloride.
Another example of a scheme of consecutive-competitive reactions
can be seen in the production of biodiesel from Jatropha curcas oil by
transesterification reactions in excess methanol. This will be discussed in
further detail in Chapter 3. The scheme is shown in Figure 1.4.

Figure 1.4. Transesterification of Triglycerides to form Diglycerides, Monoglycerides, and Glycerol with Fatty Acid Methyl Ester made in Each Step

1.3.3

DENBIGH SCHEME

A hybrid scheme of reactions in series and parallel was discussed by Denbigh.2 The general reaction scheme they treated is shown in Figure 1.5.

8 MULTIPLE REACTIONS GALORE, VOLUME I

Figure 1.5. Denbigh Scheme of Reactions in Series

and Parallel for Five Species, A, R, S, T, and U

All the five reactions shown in Figure 1.5 are simple and irreversible
and can be of any order from 0, 1, 2, or 3. Sometimes the order of reaction
may assume fractional values. Scientists are down to describing intermediate species formation to the femtosecond level. Zewail received the Nobel
Prize for pioneering work in femtosecond spectroscopy. The formation of
ethylene from cyclobutane goes through the formation of butane. Seldom
can species combine at orders more than three. Oftentimes two molecules
combine to form a third. When reaction rate varies with concentrations of
reactant species and all other effects can be lumped into a term that stays
relatively the same through the reaction, the rate expression can revert to a
pseudo first-order rate expression. For example, there are a number of free
radical reactions that take place during polymerization. The radical species
is active, and the rate of radical species can be assumed to be zero. This
means that the concentration of the radical species is a constant. A plausible second-order rate expression with the monomer and radical species
may revert to a pseudo first-order rate expression. More about the stability
of the reaction scheme shown in Figure 1.5 and other schemes will be discussed later. The product distributions of the five species will be shown as
graphs for typical values of the four rate constants in a later chapter.
1.3.4 REACTION PATHWAYS
The enzyme-catalyzed reactions and some other set of reactions such as
the reaction pathways belong to the category of what are called complex
reaction schemes. Reactions in circle are the term that may be used to
describe reactions that can be expected to occur in the citric acid cycle
(Figure 1.6). These schemes need an external source of energy and material. Otherwise, spontaneous generation of the starting material A after
several steps will violate the principle of microscopic reversibility.

INTRODUCTION TO MULTIPLE REACTIONS 9

Figure 1.6. Citric Acid Cycle Represented as Reactions in Circle

Figure 1.7 shows a scheme of reactions that can lead to the formation
of stereoisomeric products from stereoisomeric starting materials. The
formation of r-/s-propanediol from l-/d-lactic acid will be discussed in
Chapter 3. DYKAT (dynamic kinetic asymmetric transformation) processes are defined as the desymmetrization of racemic or diastereomeric
mixtures involving interconverting diastereomeric intermediates. Four
types of DYKAT reactions are discussed by Draux et al.3 Deracemization
of enantiomers can be represented using DYKAT I and DYKAT II types.
The catalysts are chiral intermediate complexes.

Figure 1.7. DYKAT Reaction Scheme

10 MULTIPLE REACTIONS GALORE, VOLUME I

The regulation action in biochemical pathways depends, to some extent, on the relative rates of diffusion and intrinsic reaction rates. The transcription process in DNA is facilitated by RNA polymerase. Transcription
factors are proteins that are found to bind to specialized regions of DNA
(deoxyribonucleic acid). The binding process is diffusion limited. Damped
wave diffusion effects may become important.4 Basic leucine zipper
(bZIP) proteins are one example. It comprises three domains: (1) c terminal leucine zipper domain, (2) basic region that binds to DNA, and (3)
transcriptional regulation domain. Monomer and dimer pathways, as
shown in Figure 1.8, are seen to participate in the stable association of
bZIP dime with DNA molecule. The binding processes of both the monomer and the dimer are known to be diffusion limited. In other words, the
overall rate of the process depends on the diffusion rate that is slower and
forms the rate-determining step. Kinetic analysis of the pathways shown
in Figure 1.8 reveals that the monomer pathway provides an overall kinetic advantage during transcriptional regulation. Transcriptional activity
requires dimerization of bZIP factors. Dimerization occurs a priori to the
DNA-binding process. Reactions 2 and 3, binding of dimer shown in Figure 1.8, are fast reactions. Dimerization reaction is not necessary for functionality of bZIP factors. Binding of the monomer is more rapid compared
with that of the dimer. Sliding of monomers can occur along the side chain
of the DNA backbone. This is an opportunity for bZIP proteins to perform

Figure 1.8. Diffusion-Limited Binding of Basic Leucine Receptor Protein

INTRODUCTION TO MULTIPLE REACTIONS 11

a one-dimensional search of the DNA strand. The target is found rapidly

by the transcription factor due to faster searching. Binding to the target is
stabilized by dimerization of bZIP at the target site. The one-dimensional
diffusion in the function of the DNA-binding proteins has been studied
with the restriction endonuclease EcoRV, which cleaves the DNA polymer after recognizing a specific restriction site on the DNA strand. EcoRV
recognizes and cleaves GAT/ATC sites on DNA. The overall rate of
cleavage was determined for PCR-amplified DNA sequences of different
lengths, but each containing one restriction site. The role of linear diffusion in the overall kinetics of cleavage can be modeled.5

kon L ( nPs)
= e
k+1 1

where kon is the overall rate of association with the target site at positions.
k+1 is the rate of association of EcoRV with a site n, and P is the probability
that the enzyme will diffuse one base pair along the DNA rather than dissociate from the DNA polymer. P is equal to the ratio of the rate constant
for diffusion (kdiff) to the rate constant for dissociation (koff).

1.4 ENZYME CATALYTIC REACTIONS

Cells in living species contain many chemical compounds. How are the
chemicals manufactured? How do some reactants combine at moderate
temperature and pressure? How are some decompositions governed by
enzyme catalysis? Enzymes are globular proteins. They have been found to
catalyze more than 5,000 biochemical reactions types. In 1897, Buchner
first extracted certain enzymes from living cells. In 1894, E. Fisher proposed that both the enzyme and substrate take complementary geometric
shapes that fit into each other admirably and presented the lock and key
model. One shortcoming of this model is that it does not explain the intermediates that are now known to form in different pathways. The set of enzymes made in a cell can determine which metabolic pathways occur in
that cell. Enzymes are said to convert substrates into products. They act as
a catalyst. A catalyst, by definition, is a substance that is known to increase
the rate of a chemical reaction, without undergoing permanent chemical
change. It affects the rate of the reaction. It does not affect the chemical
equilibrium of the reactants and products. During enzymatic action, the
activation energy of the reaction undergoes a reduction in value. This can

12 MULTIPLE REACTIONS GALORE, VOLUME I

be seen in the synthesis of glucose-6-phosphate from glucose-1-phosphate.

The number of hot molecules that can participate in the reaction6 is larger
when the activation of energy of the reactions is lowered on account of
enzymatic action.
Catalysts that are found to be active within the living cell can be made
active outside the living cell such as in a bioreactor. Sumner isolated the
first enzyme in 1926. Since then the number of known enzymes is greater
than 1,500. Microarray analysis and next-generation sequencing (NGS)
machines7 can be used to study gene transcription and gene translation
processes and other biochemical reactions with increased accuracy. Potentially, 3,000 to 4,500 enzymes may be present in the human anatomy. The
Enzyme Commission (EC) identified six classes of reactions that are
known to be catalyzed by enzymes. These are as follows:
1.
2.
3.
4.
5.
6.

Hydrolases
Transferases
Lyases
Ligases
Oxidoreductases
Isomerases

The enzyme urease, for example, catalyzes the decomposition of

urea. Oxidative dehydrogenation of alcohol is catalyzed by alcohol dehydrogenase. Familiar names among enzymes are pepsin, trypsin, which are
found in the human digestive tract, rennin, used in cheese factories, and
old yellow enzyme, which causes browning of apple slices.
Oftentimes the reaction mechanism occurring within the cell is not
well known. Experiments are conducted. At first, a guess is made of the
elementary reactions taking place. The reaction intermediates that are
formed are noted. Then an expression for the overall reaction rate is developed. This expression is checked against the experimental observations
made. The iterative process of guess and estimation and verification can
continue till a reasonable fit is obtained. Cofactors add on to apoenzyme
that are not active and become catalytically active halo enzyme active
complex. Metals and coenzymes can be cofactors. The MichaelisMenten
kinetics discussed in 1.3.2 is applicable to describe enzymatic processes.
The typical scheme of enzyme catalytic process is shown in Figure 1.9.

INTRODUCTION TO MULTIPLE REACTIONS 13

Figure 1.9. Reaction Scheme during

Formation of Products using Enzyme
Catalysis

1.5 REGULATORY COMPLIANCE

Environmental considerations can be another design criterion. For example, President Obama has called for a reduction in greenhouse gases emissions from power plants. Under the Clean Power Plan, he has called for a
32% reduction of CO2 emissions by 2030 compared with the 2005 level.
According to estimates of the Environmental Protection Agency (EPA), in
the year 2005, 2.7 gigatons of CO2 were emitted per year. In 2011, these
emissions have been reduced to 2.15 gigatons per year. EPA sees the connection between natural disasters such as drought, floods, forest fires, and
global warming with CO2 emissions. The CO2 emissions arise from 2,100
power plants that use fossil fuel such as coal and oil, steel mills, ceramic
kilns, and glass melting.
The Kyoto protocol, signed in December 1997 at Kyoto, Japan, identified CO2, methane, nitrous oxide, perfluorocarbons (PFCs), hydrofluorcarbons (HFCs), and sulfur hexafluoride (SF6) as pollutants. A novel
method to extract substantial portions of West Virginia, high-ash, bituminous coal using N-methyl-2-pyrrolidone as super solvent under mild conditions was discussed.8 The author flew to Maastricht, Netherlands from
Morgantown, WV, to present a paper at the International Coal Science
Conference in October 1987. The clean coal extract contains 0.01% ash
and virtually no pyritic sulfur. The extraction yield was 70% on a mineral
and ash-free basis. Since then progress has been made, and the coal extract
has been dehydrogenated into solvent extract carbon.9 These can be used
as electrodes in a direct carbon fuel cell to give higher open-circuit voltages compared with hydrogen fuel cell.10 When used as power plants, these
would have zero carbon emissions. Solid oxide fuel cells (SOFCs) can be
used to construct mini power plants with zero carbon emissions, according

14 MULTIPLE REACTIONS GALORE, VOLUME I

to K. R. Sridhar, CEO of Bloom Energy, Sunnvale, CA. Nuclear power

plants, windmills, and solar power plants (either photovoltaic or concentrated solar power) are examples of obtaining electrical energy without
carbon emissions.
CO2 emissions can be reduced by either fixation or capture. Chemical, electrochemical, and biological methods can be employed for the
reduction of CO2 emissions. Biological methods include the use of aquatic
plants, microalgae, microphytes, and sea weeds and sea pores. President
Obama and EPA announced the Clean Power Plan in August 2015.11 This
is an opportunity in disguise. Under this plan, the President has called for
(1) a 32% reduction of CO2 emissions by 2030, (2) a 17% cut in CO2
emissions by 2020, and (3) a 25% to 28% reduction of CO2 emissions by
2025. The President is in favor of hammering out a global climate change
treaty. They have called for a 17% cut by 2020 and a 26 to 28% cut by
2025 of CO2 emissions.
Enzyme catalytic reactions can be performed under dense CO2 surroundings. Commercial quantities of biodiesel from cellulosic biomass,
r-/s-propanediol from l-/d-lactic acid using enzyme catalysis are now in
vogue. In the presence of supercritical CO2, polymers can be synthesized
and fluoropolymers can be prepared. CO2 can be fixed using processes
encountered within organisms, such as the CalvinBensonBassham (CBB)
cycle in leaf carbon metabolism, Krebs cycle, and WoodLjungdahl pathway. CO2 and water combine with three ribulose 1,5-biphosphate to form
glyceraldehyde. The enzyme that serves as a catalyst is ribulose diphosphate
carboxylase. The ATP cycle offers the necessary energy. CO2 goes into the
preparation of Na2CO3 laundry detergent, carbonated beverage, fire extinguishers, chemical lasers, bread dough, lead paint pigment, and dishwashing
compounds. The capture of CO2 can be accomplished by the following processes:
(i) Absorption towers with either monoethanolamine (MEA) solvent
or alkali carbonate-based solvents such as hot K2CO3, potassium
carbonate.11
(ii) Adsorption beds with molecule sieves of 5 nm diameter made
from serpentinite (Magnesium silicate hydroxide) with surface
area, 2,500 m2/g.12
The sequestered CO2, after regeneration of the solvent, can be stored
underground at 14 MPa pressure. Storage of CO2 can be made robust by
use of HCPS, hydro phase liquid phase sintering. MEA-CO2 adduct forms

INTRODUCTION TO MULTIPLE REACTIONS 15

during the absorption process. Separation of MEA from MEA-CO2 adduct

can be bettered by using serpentinite reactions.
In the Solvay process to manufacture Na2CO3, two moles of CO2
along with brine and ammonium hydroxide are taken in, and along with
Na2CO3, ammonium chloride and one mole of CO2 and H2O are produced.
CO2 gets fixed. The process uses CO2 as starting material.
2CO2 + 2NaCl + 2NH4OH 2NH4Cl + Na2CO3 + CO2 + H2O

(1.3)

Limestone can be the starting material to manufacture Na2CO3. CO2 is

recovered and utilized by dry reforming of methane. Liquefied natural gas
(LNG) comprises 65% to 70% methane and 30% to 35% CO2. The carbon
monoxide formed during the reformation process can be noxious and has
to be reacted away in large measure. A direct route to prepare methanol
from CO2 by hydrogenation has been patented in Japan in the rapid iterative testing and evaluation (RITE) process. Copperzinc (CuZn) can be
used as catalyst and La2Zr2O7 as promoter in the synthesis of methanol
from CO2. Advances made in genome sequencing using microarray analysis, and dynamic programming may lead to genetically modified crops
that can be tailored to consume CO2 at higher volumes. Third-generation
biofuels are expected to stem from microalgae. In 2009, Exxon Mobil
pledged US$600 million for research in photosynthetic algae biofuels. The
CO2 species undergoes mass transfer from the atmosphere to microalgae.
Here microalgae biomass is formed. Bioethanol can be produced. Formic
acid, formaldehyde, methanol, and methane are some organic compounds
that can be produced from CO2 and H2O. The fixation scheme is shown in
Figure 1.10.

Figure 1.10. Fixation of CO2 by Conversion into Organic

Compounds

Ethylene oxide can be combined with CO2 to make epoxides. Cement

formulations can use CO2 for hardening. Capture of CO2 may be performed

16 MULTIPLE REACTIONS GALORE, VOLUME I

in a fluidized bed. Flue gas from power plants can be carbonated in a fast
fluidized bed. The solvent is then regenerated. One hundred and ten million
tons per year of CO2 is used as raw material for the production of urea,
methanol, acetic acid, polycarbonates, cyclic carbonates, and salicylic acid
carbonates.
Polyformaldehyde has oxygen and carbon in its backbone. Carbon
monoxide (CO) can be polymerized to form polyketone. In 2000,
polymerization of acetylene to conducting polymers led to the award of
the Nobel Prize to A. J. Heeger, H. Shirakawa, and A. G. MacDiarmid.
The polymer science of CO needs to be better understood. Boudard reaction can be used to make CO from CO2. Oxycarbons in an alternating
fashion in the polymer backbone may not be stable.13 Ketone density in
polymers, however, can be increased.
Rutgers University obtained a sequestration patent.14 Solvent regeneration in the absorption scheme with MEA solvent was expensive. Long-term
storage of CO2 runs the risk of not meeting the objectives. MEA solvent is
used to absorb the CO2 emissions. The following multiple reactions are expected to occur:
2CaSiO3 + 4NaOH Na4SiO4 + 2Ca(OH)2

(1.4)

Wollastonite reacts with caustic soda to form slaked lime and tetrasodium silicate.
MEA-CO2 + Na4SiO4 + 2Ca(OH)2 2CaCO3 + Na4SiO4 + MEA (1.5)
The resulting product, from a high-pressure, high-temperature treatment, has a core-shell morphology. Sometimes laughing gas can be
formed during the sequestration process. For example,
NH4OH + CO2 (NH4)2CO3

(1.6)

Ca(NO3)2 + (NH4)2CO3 CaCO3 + NH4NO3

(1.7)

NH4NO3 N2O + H2O

(1.8)

Riman and Li15,16 have patented a 5-nm molecule sieve adsorbent to

capture CO2 emissions. This adsorbent can be used for biogas upgrading,
natural gas purification, coal-bed methane purification, and refining operations. The adsorbent capacity is 50 cc of CO2 per gram adsorbent.
CO2 can react with calcium oxide (CaO) to form calcium carbonate
(CaCO3). Serpentinite reactions can be used in the sequestration of CO2.

INTRODUCTION TO MULTIPLE REACTIONS 17

Olivine is a miscible mixture of forsterite and fayalite. Serpentine

(Mg3Si2O5(OH)4) can be formed by the hydration of olivine. The CO2 can
be captured by contact with serpentine and produce magnesium carbonate,
silicon dioxide, and water.

1.6 REVERSIBLE REACTIONS

Sharma13 discussed polymerization reactions that are reversible at certain temperatures and pressures. Interest in the kinetic study of reversible polymerization and reversible copolymerization is growing. The energy considerations
and kinetic considerations are both important. Recently, the superconductivity
record was broken by Alexander P. Drozdov, in Germany, using a reversible
reaction. Drozdov demonstrated superconductivity at 203 K in a substance
whose chemical formula is given by H3S, trihydrogen sulfide.
highP

3H 2 S 2H 3S + + S + 2e

(1.9)

The high pressure needed for this reversible reaction from hydrogen
sulfide to superconducting trihydrogen sulfide is of the order of gigapascals. The record for superconductivity held previously was at 133 K for
CuHgCaBaO, copper-mercury-calcium-barium oxide. The 3s23p4 valence
shell of sulfur is seen to form three sigma bonds with hydrogen atoms for
trihydrogen sulfide. To maintain the octet configuration, one electron has
to be released from the sulfur atom.

1.7 SUMMARY
Elementary chemical reactions are simply a series of encounters between
atomic or molecular species. Multiple reactions are said to occur in your system, when more than rate expression is needed to describe them. Chemical
manufacturing units can be used to make useful products on a large scale
using the novel chemistry discovered in the laboratory, at the lowest cost, in a
safe manner, without tipping the environmental and ecological balance in the
universe. Intermediates may form, rise and fall in concentration, and vanish
during the course of the transformation of reactant to product(s) in the train
of reactors, separations, and other unit operations used in the chemical process industry. Some of the intermediates formed may sell for more dollars
compared with other species. Multiple reactions may occur among 3 to 7

18 MULTIPLE REACTIONS GALORE, VOLUME I

species, and they may be in series, in parallel, form a circle, form a rectangle,
form a triangle, sometimes occur in more than one phase, and may be reversible. Each step may be of a different order or may obey a different kinetic
expression. Mechanical stress may be the fundamental event that causes reactions to occur. Uni-, bi-, and trimolecular collisions cause momentum change
and stress. The dynamic course of reactions can be studied systematically by
listing all the multiple reactions that occur. Quantum mechanical analysis
added depth to the understanding provided by Arrhenius. Plausible mechanisms can be tested using spectroscopy for nascent quantum-state distributions, concentrations of macro atomic radicals.
Multiple reactions can be classified into (1) Trambouze scheme,
(2) consecutive-competitive reactions, (3) Denbigh scheme, and (4) reaction pathways. Reactions that occur in parallel fall under the Trambouze
scheme. Industrial systems that obey the Trambouze scheme are a continuous mass polymerization process to make ABS, HIPS, SAN, and polystyrene. Grafting and matrix polymerization reactions are shown in Figure 1.1.
A common species between sequential reactions are seen in consecutivecompetitive reactions. Examples are chlorination of methane to form
methyl chloride, methylene chloride, chloroform (more profitable), and
carbon tetrachloride. Depending on per barrel oil prices, biodiesel may be
manufactured from lower-cost feedstocks such as Jatropha Curcas oil via
transesterification reactions. This is another example of a set of consecutive-competitive reactions. Triglycerides can be reacted with excess methanol to form diglycerides, monoglycerides, and glycerol with fatty acid
methyl ester (FAME) formed in each reaction step. The FAME and glycerol mixture can be separated using centrifugation. The Denbigh scheme
is a hybrid scheme of reactions in series and parallel. Femtosecond spectroscopy was used by Nobel Laureate Zewail to confirm the formation of
butane as intermediate when ethylene is transformed into butane. A pseudo first-order rate expression can be arrived at by lumping together all the
other effects, including the concentration of species that remain steady.
For example, the radical concentration during polymerization and methanol concentration during the formation of biodiesel can be lumped together with the reaction rate constant. Examples of reactions pathways are the
Krebs cycle, the Calvin cycle, the RUMP pathway, and the methionine
cycle. Reactions in circle scheme are introduced without violation of the
laws of thermodynamics. A DYKAT reaction scheme is an example of
multiple reversible reactions on a rectangle. Simultaneous damped wave
diffusion and intrinsic reaction rates are important considerations when
studying the regulation action in biochemical pathways.

INTRODUCTION TO MULTIPLE REACTIONS 19

The reaction scheme during the formation of products using enzyme

catalysis is shown in Figure 1.9. Enzymes act as a catalyst during the conversion of the substrate into useful products. A catalyst increases the rate
of reaction and does not undergo permanent chemical change. It does not
affect the equilibrium. During enzymatic action the activation energy of
the reaction undergoes a reduction in value. Under the Clean Power Plan,
President Obama has called for a 32% reduction in CO2 emissions by
2030 compared with the 2005 level. Mini power plants can be constructed
from SOFCs, direct carbon fuel cells made from solvent-extracted carbonaceous matter from coal subsequently dehydrogenated, and windmills.
Solar photovoltaic power plants and some concentrated solar power plants
built in the Mojave Desert have a capacity of approximately 392 MW.
These and nuclear power plants with capacities in the 1 GW range are
known for their zero carbon emissions. CO2 emissions can be reduced by
either fixation or capture. CO2 can be fixed using processes encountered
within organisms, such as the CBB cycle in leaf carbon metabolism, the
Krebs cycle, and the WoodLjungdahl pathway. CO2 and water combine
with three ribulose 1,5-biphosphate to form glyceraldehyde. Capture of
CO2 may be accomplished by absorption using dipotassium carbonate or
monoethanolamine, which are adsorption beds made from high surface
area materials such as serpentinite. Third-generation biofuels are expected to
stem from microalgae. The fixation scheme of CO2 is shown in Figure 1.10.
One hundred and ten million tons per year of CO2 is used as raw material
for the production of urea, methanol, acetic acid, polycarbonates, cyclic
carbonates, and salicylic acid carbonates. Polyformaldehyde has oxygen
and carbon in its backbone. CO can be polymerized to form polyketone.
The study of reversible reactions can find applications in the manufacture of oligomers with 560 carbon atoms in its chain that can make
durable coatings. It can also lead to formation of trihydrogen sulfide from
hydrogen sulfide by pressurization and use as 203 K superconductors.

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1.
2.

O. Levenspiel. 1999. Chemical Reaction Engineering (Hoboken, NJ:

John Wiley & Sons).
K. G. Denbigh. 1961. Instantaneous and Overall Reaction Yields,
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20 MULTIPLE REACTIONS GALORE, VOLUME I

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K. Drauz, H. Groger and O. May. 2012. Enzyme Catalysis in Organic

Synthesis, Vol I., (Hanau, Germany: Wiley-VCH).
K. R. Sharma. 2005. Damped Wave Transport and Relaxation
(Amsterdam, Netherlands: Elsevier).
A. Pingoud and A. Jeltsch. 2001. Structure and Function of Type II
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J. E. Bailey and D. F. Ollis. 1986. Biochemical Engineering Fundamentals (New York, NY: McGraw Hill Professional).
K. R. Sharma. 2014. Microarray Analysis: Biochips and Eradication
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K. Renganathan, J. W. Zondlo, E. A. Mintz, P. Kneisl and A. H. Stiller.
1988. Preparation of an Ultra-Low Ash Coal Extract under Mild Conditions, Fuel Processing Technology 18, no. 3, pp. 2738.
K. R. Sharma. 2014. Graphene Nanomaterials (New York, NY:
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G. A. Hackett, J. W. Zondlo and R. Svensson. 2007. Evaluation of
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rule (Environmental Protection Agency). EPA-HQ-OAR-2013-0602.
http://gpo.gov/fdsys/search/home.action
K. R. Sharma. 2007. Principles of Mass Transfer (New Delhi, India:
Prentice Hall of India).
K. R. Sharma. 2010. Nanostructuring Operations in Nanoscale Science and Engineering (New York, NY: McGraw Hill Professional).
K. R. Sharma. 2012. Polymer Thermodynamics: Blends, Copolymers
and Reversible Polymerization (Boca Raton, FL: CRC Press).
R. E. Riman and Q. Li. 2011. Sequestration of a Gas Emitted by
an Industrial Plant, US Patent 20110158873 A1. (Piscataway, NJ:
Rutgers University).
J. D. Carruthers, M. A. Petruska, S. M. Wilson and E. A. Sturm. 2014.
Adsorbent Having Utility for CO2 Capture from Gas Mixtures, US
Patent 2014/0298992. (Danbury, CT: Advanced Technology Materials,
Inc.).

INDEX
A
Abdul Kalam, A. P. J., 69
Acrylonitrile butadiene styrene
(ABS), 4, 5
Activated cellulose, 5657, 60
Adenosine triphosphate (ATP), 27
Agrobacterium tumefaciens, 77
Alcohol dehydrogenase, 12
Alkaline catalyst, 71
American Cancer Society, 87
Arabidopsis thaliana, 78, 79
B
B&P Process, 71
Basic leucine zipper (bZIP), 1011
Bayesian genotype likelihood
model, 79
BeerLambert law, 42
-carotene, 92
Big rollover theory, 70
Biodiesel, 6787
consecutive-competitive
reactions, 8085
continuous production of
glycerol and, 76
definition of, 68
genetic modification and
cultivability, 7580
global production of, 68
next generation sequencing, 71
75
production forecast, 6871
Bone-marrow transplantation, 90

C
CalvinBensonBassham (CBB)
cycle, 14
Cancer
biopsy method to diagnose, 88
markers, 89
Cancer stem cells (CSCs), 90, 91, 92
Carotene, degradation of, 93
Catalyst, 12, 19, 69
alkaline, 71
definition of, 11
Cellulose
molecular weight of, 51
pyrolysis of, 4958
Cell wall, 5051
Center for Surface Transportation
Technology, 62
Centrifugal separation, 71, 86
Charge-coupled device (CCD), 28,
29
Chemical lasers, 4
Chlorination, 6
Cisgenic gene transfer, 75
Citric acid cycle, 8, 9
Citrus paradise. See Pink
grapefruit juice
Clapeyron equation, 67
for polymerization, 65
Clean Power Plan, 13, 14, 19
CO2 emissions
fixation of, 15
in power plants, 1314, 16
reduction of, 13, 14

112 INDEX

Computer simulations, 49
Consecutive-competitive reactions,
57, 8085
Continuously stirred tank reactors
(CSTRs), 3
Crumb rubbers, 63, 64
Curcin gene, 76, 85
D
DebyeHckel theory, 26
Denaturation, 22
Denbigh scheme, 78
applied to N-acylation reactions,
98
of reactions, 5861
to waste tires, 6167
Deoxyribonucleic acid (DNA),
2425
charge distribution on, 25
compressibility of, 26
double-stranded, 22
fragments, 75
hysteresis in, 26
at low concentrations, 25
melting temperature of, 2227
microarrays, 75
osmotic pressure of, 25, 26
screening length of, 26
sequence, 88
single-stranded, 22
Department of Transportation
(DOT), 61
Devulcanization, 66, 67
Diglycerides, 80, 81, 8487
Dimensionless concentration, 30
of intermediate product species,
5657, 60
Taylor series solution and exact
solution for, 32
of species vs. time, 37, 38
Dimerization, 1011
Disease-specific cartridges, 75
Dof proteins, 7778

Double-stranded DNA (dsDNA),

2223
Dynamic kinetic asymmetric
transformation (DYKAT)
reaction scheme, 9, 18
E
Electrostatic interactions, 26, 28
Environmental Protection Agency
(EPA), 13, 61
Enzyme catalytic reactions, 1113,
14
Enzyme Commission (EC), 12
Equation of state (EOS), 25, 6667
Equilibrium rate constants, 42, 43
Escherichia coli, 77
Ethylene-vinyl acetate, 63
Ethylene vinyl alcohol (EVOH),
43
F
Fatty acid methyl ester (FAME),
68, 69, 80, 81, 8487
Femtosecond spectroscopy, 8, 18
Flowering Locus T (FT) gene, 79
Fluorescent spectroscopy, 4
Fourier transform infrared (FTIR)
spectroscopy, 42, 97
G
-butyrolactone, 66
Gasliquidsolid fluidized bed, 66
Gauss law, 26
Gene ontology, 78
Genetic modification and
cultivability, 7580
Global warming, 13, 70
Glycerol, 80, 81, 8487
continuous production of
biodiesel and, 76
Greenhouse gases emissions,
reduction in, 13

INDEX 113

H
Hematopoietic stem cells (HSCs),
90
Hemicelluloses, 50, 51
Herbicides, 93
High-density polyethylene
(HDPE), 64
High impact polystyrene (HIPS),
4, 5
Homo sapiens
genominomics of, 67
human genome in, 24
Horseradish peroxidases (HRPs), 27
Houston Chronicle, 61, 62
Hubbert curve, 70
Hubbert, M. K., 70
Hybridization, 24
Hybrid strain, 67
I
Illumina Next Generation
Sequencing technology, 78
Infrared methods, 43, 46
Irreversible thermodynamics, 24, 25
J
Jatropha curcas, 7, 18, 6768, 69,
76, 78, 86
Jatropha oil, 6768, 69, 80, 87
K
Keesom forces, 4144
Kinetic model, 5253
for progression of cancer, 9092
Kinetic rate expression, 32, 33, 35,
39, 52
L
Laplace transforms, 3, 94
method of, 5456
products distributions by, 5961
Levoglucosan, 51
Lignin, 51

Lignocellulosic biomass, 49
Linear laser spectroscopy, 4
Lycopene, 92
Lymph system, 8788
M
Macroions, 26
Mass balance equation, 94
Mass transfer characteristics, 4445
Mean-field approximation, 25
Melting temperature, of DNA,
2227
Metastasis, 88
Metastatic cancer, 8792
Methylation experiments, 51
MichaelisMenten kinetics, 6, 12
proteomics and, 2732
Microalgae biomass, 15
Microarray analysis, 12, 88, 89
Microions, 26
Microspotting operations, 28
Monod kinetics, 6, 89, 90
Monoethanolamine (MEA), 14, 19
Monoglycerides, 80, 81, 8487
Multiple reactions
applications of
biodiesel, 6787
Denbigh scheme of reactions,
5861
Denbigh scheme to waste tires,
6167
metastatic cancer spread, 8792
pesticides during lawn care,
fate of, 9396
pyrolysis of cellulose, 4958
scale-up tool by quantitation of
CO2 evolution during, 9799
thermal degradation of
-carotene, 9293
classification of types of, 411
consecutive-competitive
reactions, 57
Denbigh scheme, 78

114 INDEX

Multiple reactions, (continued)

reaction pathways, 811
Trambouze scheme, 45
elementary chemical reactions,
12
enzyme catalytic reactions, 1113
intermediates, 24
regulatory compliance, 1317
reversible reactions, 17
as study tool
melting temperature of DNA,
2227
micromixing in mass transfer
characteristics, 4445
parallel consecutive reactions,
3235
proteomics and Michaelis
Menten kinetics, 2732
quantitation of Keesome
interactions in polymers,
4144
surface reactions, 2122
WeiPrater scheme of
reactions, 3541
N
N-acylation
Denbigh scheme applied to, 98
reaction rate constant ratios in, 99
scheme of reactions during, 97
National Human Genome
Research Institute (NHGRI), 67
National Science Day, 69
Next-generation sequencing
(NGS), 12
Nicotiana tabacum, 7677
N-methyl-2-pyrrolidone, 13, 66
Nonlinear laser spectroscopy, 4
North American Recycled Rubber
Association (NARRA), 64
O
Oil reserves, 70
Oligosaccharides, 5152

Onnes, K. Kamerlingh, 65
Ordinary differential equations
(ODEs), 3, 49, 94
Organization for Economic
Cooperation and Development
(OECD), 69
Osmotic pressure, of DNA, 25, 26
Oxidative dehydrogenation, 12
Ozone treatment, of rubber tires, 66
P
Paraffin oil, 63
Parallel consecutive reactions,
3235
Pectins, 5051
Pesticides, during lawn care,
9396
Phase partitioning, 93
Phosphogypsum, 63
Pilot plants, 2, 50
Pink grapefruit, 9293
Plant genetic engineering, 76
Plug flow reactors (PFRs), 3
PoissonBoltzmann equations, 26
Poly-alpha-methyl styrene, ceiling
temperature of, 65
Polyanhydrosugar, 51
Polybutadiene (PBD), 6465
ceiling temperature of, 65
depolymerization of, 66
polymerization of, 66
Polymerization, 46, 8, 17, 51, 66
of acetylene, 16
Clapeyron equation for, 65
Polymers, Keesome interactions
in, 4144
Polyvinyl chloride (PVC),
chlorinated, 41
Polyvinyl phenol (PVP), 43
Potential energy surface, 4
Primary char, 5657
Primary tar, 5657, 60
Proteomics
defined, 27

INDEX 115

and MichaelisMenten kinetics,

2732
Pulse decay, 93
Pyrolysis, 71
of cellulose, 4958
definition of, 49, 50
reaction rate constants during,
56, 58

Solvent extraction, 66
State-space model, 5354
Stem cells, definition of, 90
Stone mastic asphalt (SMA)
concept, 62
Subgenic gene transfer, 75
Surface reactions, 2122
Sustainable engineering, 70

Q
Quantum mechanical analysis, 3, 18

T
Techno-economic analysis, 66
Texas Commission on
Environmental Quality
(TCEQ), 61
Tire-added latex concrete (TALC),
63
Trambouze scheme, 45, 6, 18
Transesterification, 71
catalyzed reactions, 81
of trigylcerides, 7, 69, 80
Transgenic gene transfer, 75
Triglycerides, 18, 80, 81, 8487

R
Rapid iterative testing and
evaluation (RITE) process, 15
Raw microarray images, 29
Reaction pathways, 811, 5152
Reaction selectivity, 97
Reactive mixing, 44
Regulatory compliance, 1317
Renaturation, 26
definition of, 22
Reversible reactions, 17, 22, 39
Ribosome-inactivating protein
(RIP), 76
RNA polymerase, 10, 88
Rubber phase particle size (RPPS), 5
RungeKutta method, 49, 94
S
Scanning electron microscope
(SEM), 63, 64
Screening length, of DNA, 26
Secondary gas, 5657, 60
Secondary tar, 5657, 60
Single nucleotide polymorphism
(SNP), 88
Single-stranded DNA (ssDNA),
2223
Solid oxide fuel cells (SOFCs),
1314
Solid-state shear extrusion (SSSE)
pulverization, 64

U
Ultrasound treatment. See Ozone
treatment
V
Vulcanization, 65
Vulcanized rubber scrap, 6263
W
Waste tire recycling problem,
6162
WeiPrater scheme of reactions
during cyclodehydration,
decomposition and hydrolysis,
38
parallel consecutive reactions
with first reversible step, 35
reaction rate constants, 3638
with three reversible reactions on
triangle, 3941

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