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REACTIONS
GALORE, VOLUME I
MULTIPLE
REACTIONS
GALORE, VOLUME I
TYPES, USE AS TOOL AND APPLICATIONS
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
x ABSTRACT
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.
1.1
1.2
Intermediates
1.3
1.3.1
Trambouze Scheme
1.3.2
Consecutive-Competitive Reactions
1.3.3
Denbigh Scheme
1.3.4
Reaction Pathways
1.4
11
1.5
Regulatory Compliance
13
1.6
Reversible Reactions
17
1.7
Summary
17
References
19
21
2.1
Surface Reactions
21
2.2
22
2.3
27
2.4
32
2.5
35
2.6
41
xiv CONTENTS
2.7
2.8
3.
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
54
3.1.4
Model Results
56
58
3.2.1
59
3.2
3.3
3.4
61
Biodiesel
67
3.4.1
68
3.4.2
71
3.4.3
75
3.4.4
Consecutive-Competitive Reactions
80
3.4.5
Conclusion
85
3.5
87
3.5.1
90
3.6
92
3.7
93
3.8
97
3.9
Summary
References
100
103
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
Figure 1.7.
Figure 1.8.
10
13
15
22
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.
Figure 2.3.
32
35
35
37
38
38
39
50
56
57
Figure 3.4.
58
Figure 3.5.
60
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.
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.
77
81
84
85
86
87
92
93
95
97
98
99
LIST OF TABLES
Table 3.1.
56
Table 3.2.
58
Table 3.3.
61
72
88
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
CHAPTER 1
INTRODUCTION TO MULTIPLE
REACTIONS
CHAPTER OBJECTIVES
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
k = k0 e
E
a
RT
(1.1)
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
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
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.
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.
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.
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
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).
Hydrolases
Transferases
Lyases
Ligases
Oxidoreductases
Isomerases
(1.3)
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)
(1.7)
(1.8)
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
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.
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
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
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
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
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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