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Chemical Product Formulation Design and

Methods, Techniques, and Case Studies

Navid Omidbakhsh
Hesham Alhumade
Optimization

Keyvan Nowruzi
Thomas Duever
Ali Elkamel
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Authors All books published by WILEY-VCH are carefully
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University of Waterloo contained in these books, including this book,
Department of Chemical Engineering to be free of errors. Readers are advised to keep
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Prof. Hesham Alhumade

King Abdulaziz University Library of Congress Card No.: applied for
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Cover Image: Shutterstock
Print ISBN: 978-3-527-33264-9
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v

Contents

Preface ix
About the Authors xi

1 Introduction 1
1.1 Chemical Product Engineering 1
1.2 Chemical Product Design 2
1.3 Product Design and Computer-Aided Product Design 4
References 6

2 Some Typical Applications of Chemical Product Design and

Intellectual Property 7
2.1 Natural Fiber Plastic Composites 7
2.2 Wheat Straw Polypropylene Composites 10
2.3 Modeling Natural Fiber Polymer Composites 12
2.4 Graphene Composites 14
2.5 Corrosion Protection Using Polymer Composites 15
2.6 Intellectual Property 17
References 19

3 Mathematical Principles for Chemical Product Design 23

3.1 Factorial and Fractional Factorial Design 23
3.2 Response Surface Methods and Designs 25
3.3 D-Optimal Designs 26
3.4 Bayesian Design of Fractional Factorial Experiments 27
3.5 Regression Analysis 27
3.6 Artificial Neural Networks 28
3.7 Mixture Design of Experiments 31
3.8 Multiway Principal Component Analysis 35
3.8.1 Model-based Principal Component Analysis (MB-PCA) 37
3.8.2 MPLS Analysis Using NIPALS 38
References 39

4 Disinfectant Formulation Design 41

4.1 Introduction 41
4.2 Disinfectants Characteristics 42
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vi Contents

4.2.1 Antimicrobial Tests 42

4.2.2 Stability Tests 43
4.2.3 Corrosion Tests 43
4.3 Toxicity of Disinfectants 44
4.3.1 Harmful (Xn) 45
4.3.2 Severe Eye Damage, Xi (R41) 45
4.3.3 Eye Irritant, Xi (R36) 46
4.3.4 Skin Irritant, Xi (R38) 46
4.3.5 Respiratory Irritant, Xi (R37) 47
4.4 Experimental Design for Antimicrobial Activity 47
4.4.1 Prior Knowledge 48
4.4.2 Historical Data Augmentation 49
4.4.3 Linear Least Squares Regression Analysis 49
4.4.4 Artificial Neural Networks 51
4.5 Experimental Design for Stability of Hydrogen Peroxide 54
4.5.1 Historical Data Analysis 54
4.5.2 Historical Data Augmentation Using Bayesian D-optimality
Approach 55
4.6 Experimental Design for Corrosion 61
4.6.1 Preliminary Experimental Design 62
4.6.2 Response Surface Methodology 63
4.6.3 Artificial Neural Networks 64
4.7 Final Formulation Optimization 66
4.7.1 Optimization 67
4.7.2 Optimized Formulation Verification 69
4.7.3 Comparing the Optimized Formulations to an Available Product 70
4.8 Conclusion 70
References 71

5 Streptomyces Lividans 66 for developing a Minimal Defined

Medium for Recombinant Human Interleukin-3 73
5.1 Introduction 73
5.2 Materials and Methods 74
5.2.1 Microorganism and Medium 74
5.2.2 Analytical Methods 74
5.2.3 Experimental Design and Data Analysis 76
5.3 Results and Discussion 78
5.3.1 Starvation Trails 78
5.3.2 Screening Mixture Experiments 80
5.3.3 Defined Medium Optimization by Mixture Design Method 82
5.4 Conclusion 87
References 87

6 Multivariate Modeling of a Chemical Toner Manufacturing

Process 91
6.1 Introduction 91
6.1.1 Process and Data Description 92
6.1.2 Model Cross-Validation 93
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Contents vii

6.2 Results and Discussion 97

6.3 Conclusion 101
References 102

7 Wheat Straw Fiber Size Effects on the Mechanical Properties

of Polypropylene Composites 105
7.1 Introduction 105
7.2 Materials and Methods 108
7.2.1 Materials 108
7.2.2 Fiber Preparation and Size Measurement 108
7.2.3 Fiber Thermal and Chemical Analysis 109
7.2.4 Composite Sample Preparation and Properties Measurement 109
7.3 Results and Discussions 110
7.3.1 Fiber Fractionation and Size Measurement 110
7.3.2 Fiber Thermal and Chemical Analysis 113
7.3.3 Fiber Size Reduction During Compounding Process 114
7.3.4 Composite Flexural Properties 117
7.3.5 Composite Impact Properties 118
7.3.6 Composite-Specific Properties 120
7.4 Conclusion 122
References 122

8 Framework for Product Design of Wheat Straw Polypropylene

Composite 125
8.1 Introduction 125
8.2 Product Design Framework for WS-PP Composite 128
8.3 Response Surface Models 130
8.3.1 The Design of Mixture Experiment 131
8.3.2 Materials and Methods 133
8.3.3 Results and Discussion 134
8.3.3.1 Flexural Modulus 134
8.3.3.2 Izod Impact Strength 136
8.3.3.3 Other Properties 137
8.4 Case Study 138
8.5 Conclusion 144
References 145

9 Product Design for Gasoline Blends to Control Environmental

Impact Using Novel Sustainability Indices: A Case Study 147
9.1 Introduction 147
9.2 Methodology 148
9.2.1 The Impacts of Gasoline Blends on Octane Number (ON) 148
9.2.2 The Impacts of Blending Ethanol and Gasoline on Mileage 149
9.2.3 The Effects of Ethanol, Methanol, and Isooctane on the Octane Number
of Gasoline Blends 150
9.2.4 The Impacts of E5, M5, and I5 on Heat Value, Mileage,
and Price 150
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viii Contents

9.2.5 Impacts of E5, M5, and I5 on Environment in Potential Environmental

Impacts (PEIs) 152
9.2.6 The Impacts of E5, M5, and I5 on Safety Risk 154
9.2.7 Selecting the Best Blend Through the Analytic Hierarchy
Process (AHP) 155
9.3 Results 158
9.4 Conclusion 160
References 161

10 Corrosion Protection of Copper Using

Polyetherimide/Graphene Composite Coatings 163
10.1 Introduction 163
10.2 Experimental 164
10.2.1 Material 164
10.2.2 Composite Preparation, Coating, and Curing 165
10.2.3 Morphology Characterization 165
10.2.4 Adhesion 165
10.2.5 Electrochemical Measurement 166
10.3 Results and Discussion 167
10.3.1 Morphology 167
10.3.2 Adhesion 170
10.3.3 Potentiodynamic Measurements 170
10.3.4 Impedance 174
10.4 Conclusion 177
References 177

11 Optimization of Mechanical Properties of Polypropylene

Montmorillonite Nanocomposites 181
11.1 Introduction 181
11.2 Methodology 183
11.3 Mathematical Models 183
11.4 Optimization Mechanism 183
11.5 Results and Discussion 185
11.5.1 Minimizing the Cost of PP-OMMT 185
11.5.2 Minimizing the Variance Between Desired Properties 187
11.6 Conclusion 192
References 193

12 Product Selection and Business Portfolio for Long-Range

Financial Stability: Case Study from the Petrochemical
Industry 195
12.1 Introduction 195
12.2 Manufacturing Strategy and Product Selection Tools 196
12.3 Model Development 199
12.4 Illustrative Case Study 201
12.5 Conclusion 205
References 205

Index 207
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ix

Preface

Chemical product design is a very important topic in the chemical industry. While
commodity chemicals have been the main area for chemical engineering focus in the
past several decades, specialty chemicals have been gaining more and more attention
in recent years. Therefore, accelerating the development process and optimizing the
formulation of chemical products would be of great benefit. With this change already
happening in the industry, chemical engineering education and training have not
changed enough to train engineers to fill positions in the product design field.
This book aims at providing the reader with a detailed understanding of the
product design, related statistical techniques, and optimization, and gives real-life
case studies for disinfectant formulations, optimization of defined medium, the
formulation of biocomposites, etc. This book can be used as a supplemental text-
book for chemical engineering students in a chemical product design course or to
R&D product formulation engineers so that they become familiar with the efficient
techniques used in developing new formulations. The book contains 11 chapters as
follows:
● Chapters 1 and 2: Introduction to the current product design process
● Chapter 3: Background to the related mathematical and statistical techniques
● Chapters 4–12: Cases studies
Chapters 1 and 2 introduce the reader to the current methodologies used for
designing new products in chemical industries and outlines the disadvantages of
the current processes and the need for improvement.
Chapter 3 gives a background about the theories of the methodologies used
to accelerate new product development. These methodologies include factorial
designs, mixture designs, optimal designs, linear and nonlinear regression analysis,
machine learning techniques (i.e. artificial neural networks), and multi-way
principal component analysis.
Chapters 4–11 present seven case studies to illustrate the process of product
design and its practical implications. The first case study covers optimization of
a disinfectant formulation, the second one presents optimization of a defined
medium, the third case deals with product improvement in a chemical toner
manufacturing process using multivariate modeling, the fourth case presents over
two chapters the design of wheat straw polypropylene composites, the fifth case
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x Preface

employs simulation to formulate gasoline blends, the sixth case presents the design
of a corrosion protection coating using polyetherimide/graphene composites,
and finally the seventh case study deals with the optimization of the mechanical
properties of polypropylene-organically modified montmorillonite (PP-OMMT)
nanocomposites. The book ends with Chapter 12 that illustrates how to proceed in
selecting products to invest for business sustainability.
All chapters are equipped with clear illustrations, figures, and tables to help the
reader understand the included topics.
Many people contributed directly or indirectly to this book. We wish to pay our
gratitude and our respects to the late Professor Park Reily with whom we have
collaborated on research articles related to the topics in this book and have learned
a great deal from him. Also, this book would not have been possible without the
interactions we had with past graduate students. Although we give credit and refer-
ences in the appropriate chapters, we would like to vouch our words of appreciation
to Rois Fatoni, Hossein Ordouei, Youssef Al Herz, and Hassan Khorami. Special
thanks go also to the Wiley publishing team (Elke Maase, Katherine Wong, and
Lesley Jebaraj) for their professional work and for being patient with us. Last but
not least, we extend great appreciation to our friends and families.
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xi

About the Authors

Ali Elkamel is Professor of Chemical Engineering at the University of Waterloo.

He is also cross-appointed in Systems Design Engineering. Prof. Elkamel holds a
BSc in Chemical Engineering and a BSc in Mathematics from Colorado School of
Mines, MSc in Chemical Engineering from the University of Colorado-Boulder, and
PhD in Chemical Engineering from Purdue University – West Lafayette, Indiana.
His specific research interests are in computer-aided modelling, optimization, and
simulation with applications to energy production planning, carbon management,
sustainable operations, and product design. Prof. Elkamel supervised over 90
graduate students (of which 35 are PhDs) and more than 30 post-doctoral fel-
lows/research associates, and his trainees all obtain good jobs in the chemical
process industry and in academia. He has been funded for several research projects
from government and industry. Among his accomplishments are the Research
Excellence Award, the Excellence in Graduate Supervision Award, the Outstanding
Faculty Award, the Best Teacher Award, and the Industrial engineering and
Operations Management (IEOM) Outstanding Service and Distinguished Educator
Award. He has written more than 370 journal articles, 145 proceedings, and 45
book chapters and has been an invited speaker on numerous occasions at academic
institutions throughout the world and at national and international conferences.
He is also a co-author of five books; two recent books were published by Wiley and
entitled Planning of Refinery and Petrochemical Operations and Environmentally
Conscious Fossil Energy Production.
Hesham Alhumade is a skilled engineer with experience in chemical industry
and enthusiastic assistant professor of chemical and material engineering with
extensive research, teaching, supervision, and administration experience. He is
meticulous and methodical in approach to all tasks, guaranteeing high-quality
results in line with learning specifications. Dr. Alhumade was recently appointed as
the president of the chemical engineering chapter of the Saudi Council of Engineers.
His research interests include polymer nanocomposites, renewable energy, catalyst,
solar systems, and fuel cell. He is currently working on developing pyrolysis
techniques for biomass conversion to biofuel to meet the growing global demand for
alternative and green sources of energy in addition to the current industrial demand
for adequate waste management process. In oil and gas industry, he has conducted
promising research in the field of synthesis and functionalization of catalyst for
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xii About the Authors

hydrocarbon conversion and oil upgrading purposes. His research interests include
modeling and simulation of fluid dynamics in porous media and synthesis of
nanocomposites materials for various electrochemical applications including fuel
cells, supercapacitors, batteries, and corrosion mitigation. Dr. Alhumade received
the SABIC Distinguished Award in 2006.
Navid Omidbakhsh is Director of Early R&D and Advanced Research for
Advanced Sterilization Products (ASP), where he leads the innovation and techni-
cal feasibility of new concepts for future products. Prior to joining ASP, Navid was
Vice President of Open Innovation and Intellectual Property for Virox Technologies
and held a key role in the development of Virox’s globally registered products
and company’s exponential growth. Before Virox, Navid was an R&D engineer
for Henkel in surface technology field. Navid has earned his PhD in chemical
engineering from the University of Waterloo, Waterloo, Ontario, Canada, where his
main research area was on the development of a systematic method to optimize
chemical products/formulations. Navid holds several patents and peer-reviewed
publications in the area of product design, disinfectants, and sterilization formu-
lations and systems. Navid is also an alumnus of Harvard Business School, where
he completed programs on business, management, and innovation. He is also a
licensed professional engineer of Ontario, Canada.
Keyvan Nowruzi is a principal scientist at ASP. He has a BS in chemical engi-
neering from Sahand University of Technology, Tabriz, Iran; an MSc in chemical
engineering from Tehran Polytechnic University; and a PhD in biochemical engi-
neering from the University of Waterloo, Canada. Prior to joining ASP, he has served
as a post-doctoral fellow at the University of Guelph, Canada for four years and a
staff scientist for Akkim Kimya San. Ve Tic. A. Ş. for one year. He has been with ASP
for six years. Dr. Nowruzi has contributed in few inventions patented worldwide and
has several publications in peer-reviewed journals and international conferences.
Thomas Duever is Dean of the Faculty of Engineering and Architectural
Science and a professor of chemical engineering at Toronto Metropolitan University
(TMU). Prior to his role at TMU, Dr. Duever served as chair in the Department
of Chemical Engineering at the University of Waterloo for nine years, navigating
the department toward unprecedented growth. He has also taught industrial short
course in experimental design and polymer reaction engineering.
Dr. Duever is an accomplished researcher with interests including applied statis-
tics, experimental design, polymer reaction engineering, and product development.
He has written more than 100 articles in journals and conference proceedings to his
credit and has supervised the research projects of over 35 graduate students.
Dr. Duever is a registered professional engineer in the Province of Ontario, a
fellow of the Chemical Institute of Canada, and a fellow of the Canadian Academy of
Engineering. He holds PhD, masters, and bachelor degrees in chemical engineering
from the University of Waterloo.
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1

Introduction

1.1 Chemical Product Engineering

Current globalization trends have resulted in a fierce competition between
multinational companies for gaining more market share. Startup companies, on the
other hand, also try to play in this game by offering differentiated or disruptive prod-
ucts that would potentially change the game and dynamics in each market segment.
The main tool for technological companies to compete, however, remains their
product offerings, and how they can serve the customers and address their needs.
Any profitable market invites new entrants which creates competition. Companies
try to accelerate their product development processes to launch more differentiated
products to stay ahead of the game, while even reducing their costs. This is of
course not a trivial task for scientists and engineers to take on. Furthermore,
customers nowadays have been poised to see newer products and can quickly
switch to other companies with better product offerings if the “newer” products are
not commercialized quick enough, as the life cycle of the current products keeps
becoming shorter. Brand loyalty does not exist as it used to be a few decades ago,
and customers can quickly switch if they find a product with better features. An
obvious example is the smartphone market, and that companies fiercely compete
to introduce new products every year. Imagine one of the incumbents misses one
product launch by a few months, and how catastrophic financial outcome they can
encounter. In many cases, these new products are only simple modifications to
existing technologies, but even these “small modifications” should carry enough
value proposition to convince buyers among all choices they have. This competition
is of course not limited to electronics market and is widespread in all industries,
from cosmetics to pharmaceuticals and consumer to agriculture. In all these market
segments, research and development teams work closely with their marketing
counterparts to identify market needs and trends to stay ahead of the curve. There
is no exaggeration to say that in the current market, innovation is like oxygen for
the business, and without that any business will soon become irrelevant. Naturally,
innovation can only be monetized if it is translated into a new product and capture
revenue. This is why freshness index, i.e. the ratio of new products contributing
to the revenue of the company over total revenue, is considered as a key success
metric for most companies. A faster commercialization cannot be achieved without
Chemical Product Formulation Design and Optimization: Methods, Techniques, and Case Studies,
First Edition. Ali Elkamel, Hesham Alhumade, Navid Omidbakhsh, Keyvan Nowruzi, and Thomas Duever.
© 2023 WILEY-VCH GmbH. Published 2023 by WILEY-VCH GmbH.
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2 1 Introduction

a lean and agile product development process, and therefore it is very important
that companies spend their R&D dollars very wisely and try to avoid less efficient
development methodologies.
Product design can have various interpretations, among them is the definition
as the entire procedures required to deliver a product with defined properties that
serve a specific need in society or industry based on inputs from various segments.
For instance, inputs from the industry of how the product may serve and what spec-
ifications should be considered during the manufacturing process. Items that can be
considered include environmental and regional regulations. An example of environ-
mentally friendly product design is the manufacturing of a greenhouse ventilation
system, where the house is designed to attenuate energy consumption and maintain
required rate of fresh air exchange. In such a process of product design of a household
air exchanger, various elements need to be considered including heat and humidity.
In addition, material selection is a significant factor in the manufacturing of such a
device to take into consideration environmental impacts such as energy conserva-
tion, corrosion, and exhaust gases, if any. The topic of product design has become
even more important with the growing changes in industry and regulation to pro-
tect the environment. For example, the manufacturing process of synthetic textile
fiber has been continuously developing since 1950. Starting wth a global produc-
tion of less than 10 million mt in the 1950 and undergoing a 10-fold increase by
2017, the effective utilization of fibers in various applications was achieved through
product design studies that were caried out on the development of various proto-
types utilizing statistical software packages. In general, the process of product design
encompasses the following steps: market needs, ideas, material selection, and finally
manufacturing and process control and optimization.
Many of the products we touch and feel today have come out of a chemical plant
one way or another. These products cannot be missed even in any quick visit to a
grocery store. Consumer products (e.g. detergents), cosmetics, health care products
(e.g. disinfectants, sanitizers), adhesives, pharmaceuticals, etc., are all examples of
chemical products. Therefore, chemical product design (CPD) is a very important
market segment and deserves enough attention in improving product development
methodologies. Chemical product engineering is the science and art of creating
chemical products, a much larger concept encompassing CPD. In other words,
chemical product engineering can be seen as the general background of knowledge
and practice supporting the concrete task of designing chemical products and their
manufacturing processes.

1.2 Chemical Product Design

One of the crucial challenges facing modern corporations and industry is the
growing competitive and dynamics market. A successful business requires con-
tinuous monitoring of consumers’ needs and delivering valuable products at
competitive prices and high quality, while addressing environmental regulations.
Therefore, researchers from various fields of industry including but not limited
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1.2 Chemical Product Design 3

to management, marketing, and engineering design always devote attention to

development of new products and issues associated with the fabrication of the
products such as environmental concerns. When designing a new product, different
factors are usually combined such as strategic and technical effort. Here, strategic
planning is required to deliver a successful launch of the product, while technical
effort focuses on design, manufacturing, control, and process optimization aspects.
Therefore, a growing number of researchers from different fields of engineering
including chemical engineering have devoted attention to the area of efficient
design of new products.
Specialty chemical products include petrochemicals, pharmaceuticals, green
chemicals, food products, household care consumables, and cosmetics. In differ-
ent sectors, chemical products are undergoing continuous changes to meet the
expectations of the consumers in addition to continuously stricter environmental
requirements. The fabrication of a chemical product is a multistage process starting
from synthesis, design, optimization, operation, and control. The successful execu-
tion of the previous steps would transform raw materials into valuable products.
Furthermore, the design of a chemical product requires deep understanding of
the properties of the materials and usage functions. Chemical products can be
classified into six categories as follows: specialty chemicals, bioproducts, formulated
products, devices, technology-based products, and virtual chemicals, where each
category has a special identity. For example, specialty chemicals can be defined
as pure compounds that are delivered in small quantities and may serve specific
functions. Formulated products such as cosmetics and food represent a large
market and can be defined as combined systems where various raw materials are
blended together to deliver a multifunctional product with specific appearance and
properties. Continued development in health care applications triggers the need
to develop bioproducts that include biomaterials, tissue, and metabolic elements.
Most of pharmaceutical drugs are now derived from biological sources rather than
traditional synthetic chemicals. Moreover, products that cannot be classified as pure
compounds, mixture, or fabricated biomaterials may include devices that carry out
a physical or chemical transformation.
There have been major changes in the chemical industry during the last two
decades. The dominance of commodity chemicals has been eroded by a newer
emphasis on products such as specialty chemicals [1]. These chemicals include but
are not limited to detergents, cosmetics, pharmaceutical drugs, fertilizers, adhe-
sives, and many more. Today, there are many companies and industries that have
focused on developing such products and are in fierce competition with each other
for market share. Chemical process industries have always launched successful new
products. However, the dynamic and demanding markets require companies to
adopt a more systematic approach to bring the new product to the market faster and
cheaper to guarantee competitiveness. Chemical Product Design and Engineering
is becoming more important as a consequence of this change. While customer
needs and product differentiation for competition purposes are significant drivers
to faster develop products, global warming and climate change require newer
products to have less environmental impact. Increased awareness by both people
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4 1 Introduction

and governments, and media’s increased attention to this important topic, has led
governments to impose more stringent environmental regulations which puts even
more pressure on companies to try to reduce waste and carbon footprint. It would
be obvious for companies to try to optimize processes and product formulations to
deliver the same performance using “less” chemicals in a faster time and using less
resources. The million-dollar question to ask is how to achieve this, or simply how
to do more with less? In this book, we are trying to answer this question partially
and our focus will be on chemical and biological product mixtures.
In summary, the dynamic nature of the chemical and biochemical industries,
intense competition for market share, and emergence of more strict environmental
regulations require deployment of innovative product development methods to
address increasing demands for faster, leaner, and optimized products.

1.3 Product Design and Computer-Aided Product Design

CPD can be defined as a systematic procedure or framework of methodologies
and tools whose aim is to provide a more efficient and faster design of chemical
products able to meet market demands. From the practical standpoint, Cussler and
Moggridge [2] simply defined product design as a procedure consisting of four steps:
(i) defining the needs, (ii) generating ideas to meet the needs, (iii) selecting the best
ideas, and (iv) manufacturing the product. Generating ideas and selecting the best
ideas are the most time-consuming steps. These two steps traditionally involved
an exhaustive search by trial-and-error methods which often ended up with no
significant results. One way to overcome this problem is by using computer-aided
techniques to identify very quickly a set of promising candidates and select a subset
of likely final products, from which the desired properties can be identified through
experiments (Figure 1.1).
The first step in Figure 1.1 is the predesign, or problem formulation step. Steps 2
and 3 represent, respectively, two types of product design problems: molecular
design and mixture/blend design. In the molecular design, the objective is to find a
chemical product that exhibits certain functional properties. The invention of new
fuel additives and solvents in organic synthesis are examples of this type of design.
In the mixture/blend design, the objective is to find a recipe of chemical ingredients
which give desirable final product properties. Examples of this type of design are
the design of fuel blends and polymer blends, including polymer composites and
additives. The associated computer-aided designs for the two CPDs are called
computer-aided molecular design (CAMD) and computer-aided mixture/blend
design (CAMb D).
Chemical products are judged by consumers not from their technical specifica-
tions but rather by the functional and performance attributes which are usually
described by a set of performance indices. These indices are determined by three fac-
tors: (i) the composition and physicochemical properties of materials that constitute
the product; (ii) product structure, which is dependent on the manufacturing
process; and (iii) product usage conditions. The relationship between performance
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1.3 Product Design and Computer-Aided Product Design 5

Product design Process-product design

CAMD
Generate alternatives
Predesign
Process design
Needs and goals
Product manufacturing and testing

CAMbD
Generate alternatives

Figure 1.1 The design process for product design.

Property prediction:

Given: Obtain:

Information on compound
Properties of the compound
structure

CAMD & CAMbD

Given: Obtain:
Information on desired Compound structures having
properties and type of the desired properties and
compound their “recipe”

Figure 1.2 Chemical product design (CAMD, CAMb D) are “reverse” of property prediction
problems.

indices and product composition, product ingredients’ properties, and product

structure has been mathematically systematized through the concept of property
function. In generic terms, the CPD can be defined as: given a set of desired
(target) needs, determine a chemical product (molecule or mixture) that satisfies
these needs. Based on this definition and the concept of property function, the
CPD problem can be described as a “reverse property prediction,” as illustrated in
Figure 1.2, where the needs are defined through product properties [3].
A simple framework for CPD is illustrated in Figure 1.3. Different aspects of CPD
are represented by methods for CAMD, CAMb D, analysis, and model validation,
while different calculation options are represented by tools of process simulation,
pure component property estimation, mixture property estimation, and search
engines for data retrieval from databases. Although the two-directional arrows in
Figure 1.3 show the connection between two adjacent methods or tools, they are
meant to indicate that all the tools and methods are connected to each other.
In any CPD problem, property functions and property models play important
roles. While the framework is flexible enough to handle a large range of CPD
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6 1 Introduction

Figure 1.3 A simplified

Process simulation CAMD
framework for computer-aided
chemical product design.
Pure component
CAMbD
properties

Mixture properties Analysis

Database Model validation

problems, the currently available methods and tools can only solve a relatively
small percentage of these problems. This is because the property models that are
currently available are unable to predict the needed properties within an acceptable
limit of uncertainty.
The framework, however, can give a great contribution to creating property mod-
els and database development in a systematic way. This will reduce time and effort
in the early stages of the product design process and subsequently bring the product
to the market cheaper and faster.
The remainder of this book is organized as follows: Chapter 2 surveys a variety
of applications associated with CPD, while Chapter 3 covers tools commonly used
to accelerate product development. Chapters 4–12 provide illustrative case studies
related to CPD and formulation.

References

1 Lee, N.-J. and Jang, J. (1997). Performance optimisation of glass fibre mat
reinforced polypropylene composites using statistical experimental design. Polym.
Test. 16: 497–506.
2 Cussler, E.L. and Moggridge, G.D. (2011). Chemical Product Design. Cambridge
University Press. ISBN: 9781139035132.
3 Halvarsson, S., Edlund, H., and Norgren, M. (2008). Properties of medium-density
fibreboard (MDF) based on wheat straw and melamine modified urea
formaldehyde (UMF) resin. Ind. Crops Prod. 28: 37–46.
 Visit https://ebookmass.com
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7

Some Typical Applications of Chemical Product Design and

Intellectual Property

2.1 Natural Fiber Plastic Composites

The use of natural fibers as reinforcement in composite materials dates back to
3000 years ago when ancient Egyptians used clay reinforced with wheat straw as
materials to build walls of their houses. In the automotive industry, Henry Ford
developed the first prototype composite car made from hemp fibers in 1942. Due to
economic constraints at that time, however, the car was not commercially produced.
Since then, numerous attempts have been made to incorporate natural fibers into
automotive components. The pressure to produce fuel-efficient, low-polluting
vehicles has become the major driving force for the increasing use of natural fibers
in automotive parts. The inclusion of natural fibers will make it possible to reduce
the utilization of petroleum-based polymeric materials. It will also increase the fuel
efficiency due to car’s lighter weight and will result in an easier product end-of-life,
i.e. waste management. Today, several car manufacturers are using natural fiber
composites in their products. Some examples of the applications are presented in
Table 2.1.
Both thermoplastic and thermoset resins were being used in automotive
industries. However, since thermoplastic resins are easily recyclable, they exhibit
less environmental impact than the thermoset resins. Therefore, industries such as
automotive industry is using more thermoplastics than thermosets. For automotive
industry, the key advantage of thermoplastics is that they can be reprocessed or
recycled, thus reducing the amount of scrap material during manufacturing and
allowing easy recovery and recycling of materials at the end-of-life cycle. Due to the
lower thermal stability of natural fibers, the number of thermoplastics which can be
used to make composite materials is limited to those thermoplastics with processing
temperatures that do not exceed the temperature for degradation or burning the
plant fibers (typically below 210 ∘ C). Polypropylene (PP) and polyethylene are
the most commonly used thermoplastic polymer matrices with plant natural
fibers.
There are various natural fibers with broad ranges of sizes and properties
available to be used as fibers in composites, such as cotton, jute, flax, hemp, sisal,
coir, bamboo, wood, pineapple, ramie, coconut leaves, and so on. The choice of
fibers mainly depends on the final composite product specifications and their
Chemical Product Formulation Design and Optimization: Methods, Techniques, and Case Studies,
First Edition. Ali Elkamel, Hesham Alhumade, Navid Omidbakhsh, Keyvan Nowruzi, and Thomas Duever.
© 2023 WILEY-VCH GmbH. Published 2023 by WILEY-VCH GmbH.
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8 2 Some Typical Applications of Chemical Product Design and Intellectual Property

Table 2.1 Automotive manufacturers, model, and components using natural fibers [1].

Manufacturer Model and application

Audi A2, A3, A4, A4Avant, A6, A8, Roadstar, Coupe: Seat back, side and
back door panel, boot lining, hat rack, spare tire lining
BMW 3, 5, and 7 series and others: Door panels, headliner panel, boot
lining, seat back
Daimler-Chrysler A, C, E, S class: Door panels, windshield/dashboard, business table,
piller cover panel;
A class, Travego bus: exterior under body protection trim; M class:
Instrumental panel
(Now in S class: 27 parts manufactured from biofibers, weight 43 kg)
Fiat Punto, Brava, Marea, Alfa Romeo 146, 156
Ford Mondeo CD 162, Focus: Door panels, B-piller, boot liner
Opel Astra, Vectra, Zafira: Headliner panel, door panels, pillar cover
panel, instrumental panel
Peugeot New model 406
Renault Clio
Rover Rover 2000 and others: Insulation, rear storage shelf/panel
Saab Door panels
SEAT Door panels, seat back
Volkswagen Golf A4, Passat Variant, Bora: Door panel, seat back, boot lid finish
panel, boot liner
Volvo C70, V70
Mitsubishi Space star: Door panels; Colt: Instrumental panels

application. However, flax, hemp, and kenaf fibers are favored, because they have
excellent combinations of economic and functional properties [1].
The basic rule of reinforcement is that stresses to the material must be transmit-
ted from the polymer matrix to the fiber. To get the optimum reinforcement to the
polymer matrix, a fiber must have certain attributes. The length of the fibers and
the aspect ratio (length/diameter) of the fibers should be controlled to each specific
type of resin and application. Much of the research in the area of fiber-reinforced
plastics has been done using glass fibers. Glass fibers have uniform diameter and
can be made to any required length. Therefore, the length and aspect ratio are easily
controlled in the case of glass fibers. The fiber alignment is also a significant factor
for composite strength. Fibers randomly oriented will lose their reinforcement effect
by up to 80%. In cases where usage of continuous fibers is prohibited due to process
constraints, discontinuous fibers are used. In this case, stress cannot be transmitted
from the matrix polymer to the fibers across the fiber ends. Fibers with the size longer
than a critical minimum length lc are required for these discontinuous fibers [2].
Since stresses must be transmitted across the boundaries between polymer matrix
and the fiber, the properties of fiber–polymer composites are influenced by the
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 Climate

As might be expected, the climate of the country is similar to that

of Colombia, with corresponding variations for altitude: tropical to
about 2000 feet; above that to 7000 temperate; still higher, cold, with
mean annual temperatures ranging from 60° to zero or less on the
high mountains. The hot region, tierra caliente, includes the coastal
plains with the Maracaibo district, the llanos, a large part of the
Guayana Highlands, and a few of the lower mountain valleys. The
islands are the coolest, the llanos the warmest part of the tropical
region; the hottest section of the latter is south and west, the farthest
from the sea. Along the coast the temperature ranges from 64°-68°
to 93°-95°. The temperate region includes the most thickly settled
sections at moderate elevation, while the cold mountain heights have
comparatively few inhabitants. On the llanos the dry season is from
November to May, or June, the rainy following to November. The
coast has two rainy seasons, December and January, and April to
July. The Orinoco Delta and parts of the Guiana section are the most
unhealthful; the lowest death rate, rather strangely, is in the cities of
the llanos, the next lowest in the regions of the Andes and the
Caribbean Mountains.
 CHAPTER IX
VENEZUELA: CAPITAL, STATES, TERRITORIES, CHIEF CITIES

The Capital

Caracas, the capital of the Republic, founded in 1567, is a very

attractive city with a delightful climate. Only occasionally does the
temperature go below 60° or above 80°. Eight miles in a straight line
from its port, La Guaira, from which it is 23 miles by rail, the city is at
an altitude of 3036 feet on the south side of the outer Coast
Cordillera. The city is in the usual Spanish American style, with
beautiful plazas and promenades. Exceptionally, the streets, which
are at right angles, are numbered instead of named, but the old
names are in general use. Notable buildings are the Capitol covering
more than two acres, the Miraflores Palace, the Cathedral,
University, National Pantheon, Masonic Temple, called the best in
South America, a beautiful theatre, etc. A fine view is had from the
hill Calvario, 200 feet above, the slopes of which are arranged as a
public garden. Caracas is up to date in modern conveniences, water
supply, street cars, etc., and has a good and cheap cab service. The
city is near the west end of a rich valley 12 miles long and 3 wide,
which slopes towards the southeast. The Guaire River below the city
flows into the Rio Tuy.

Individual States

The Coastal States follow with the Island State, and Lara, which
is neither coast, llano, nor mountain, though having some hills. The
coast line extends over 1800 miles.
Zulia, the large State (23,000 square miles) occupying the
northwest corner of the Republic, has Colombia on the west and
northwest, the Gulf of Venezuela northeast, Falcón, Lara, and Trujillo
east, and Mérida with a little of Táchira south. This State, of which
Maracaibo is the capital, is one of the wealthiest in the Republic,
though still sparsely inhabited. The Maracaibo Plain, the most
conspicuous and important section occupying the greater portion of
the State, lies between the two great branches of the East Cordillera.
The lake itself is a sheet of water about 150 miles long and half as
wide, the water sweet in the southern half of the lake, but brackish
towards the north. The precipitation in this district amounts to 70
inches annually. Thus an enormous amount of fresh water from the
Cordillera is continually entering the lake through its various
affluents; of these the Catatumbo with its tributary Zulia, and the
Escalante, are navigable for steamboats. The lake has a depth of 30
feet and is served by several lines of steamers as well as by sailing
craft. A few small towns on the lake receive agricultural products
from their vicinity; along the shore cacao is cultivated with great
profit. There is a fine goat farming district; fishing is carried on; there
are many settlements of Indians inhabiting huts on piles in the lake in
the ancient fashion. North of the city, Maracaibo, are salinas or salt
deposits, from which several thousand tons are taken annually.
Southwest of Maracaibo, a peculiar tree is found in the forest, the
arbol de vaca, or palo de leche, the sap of which, though slightly
thicker, may be used in every way as cow’s milk. In the forests are
valuable timber, useful creepers, and trees which furnish various
gums or resins. Around the lake are found outcrops of coal, also
petroleum and asphalt.
COLOMBIA, VENEZUELA, GUIANA, ECUADOR, NORTH BRAZIL
The capital city, Maracaibo, is a busy place, and prosperous. With
some good buildings, and other ordinary requirements, it is in need
of better paving, a suitable drainage system, and a good water
supply, in order to lower its high death rate and to measure up to its
favorable location, although this may be called hot.
Falcón, east of Zulia, extends along the coast of the Gulf of
Venezuela (also called Maracaibo) past the Paraguana Peninsula,
which it includes, and around to the east, so far that the next coast
State, Yaracuy, is on the south together with the State of Lara farther
west; these three States include the Segovian Highlands; the first
two, coast lands also. This section is the oldest part of Venezuela
except for the town of Cumaná.
An immensely profitable industry here followed is the raising of
goats, which feed on the cactus plains. The extensive coal deposits
and salinas count for little in comparison. The northern part of the
State is rather barren, but the highlands at the south are forest clad,
with fertile valleys raising a variety of agricultural products, chiefly for
home consumption. There is one considerable river, the Tocuyo,
several hundred miles long, which rises in the mountains of Lara,
flows north, then east through Yaracuy and Falcón to the sea. With
many affluents, the two of importance are the Carora and the
Baragua on the left. The Rio Tocuyo comes down through a long
valley, while many short rivers rising on the outer range descend
rapidly to the sea. The situation is excellent for the cultivation of
cocuiza and other aloes from which sacks and hammocks are now
being made. Other industries are soap making and cigarettes; in
some sections excellent tobacco is raised.
Coro, the capital of Falcón, the second oldest town in the
Republic, contains the first cathedral in the new world. Located on
the plains at the base of the Paraguana Peninsula, it is 8 miles from
its seaport La Vela and 200 miles west of Caracas.
The important port Tucacas is at the mouth of the Tocuyo River.
The Dutch island, Curaçao, lies not far off the coast, with which it
has close connection; some smuggling is said to be carried on.
Yaracuy, a small State with a very short coastal strip, is between
Falcón on the north and Carabobo southeast, with Lara southwest. It
is noted for its copper mines at Aroa.
Besides the capital, San Felipe, where a cloth factory has lately
been organized, the chief towns are Nirgua, population 3000, at the
south, amid fertile plains with varied agricultural products, and
Yaritagua 20 miles west, where good tobacco is raised, as well as
sugar and coffee which grow everywhere.
Lara, an interior State, borders on Falcón, Yaracuy, Cojedas,
Portuguesa, Trujillo, finishing with Zulia on the west. Besides the
usual agricultural products, there is fibre from aloes, employed in
manufacturing sacks, hammocks, and bridles, for which
Barquisimeto is noted. The fertile hills and slopes, many now
undeveloped, the virgin forests of valuable timber, with areas where
petroleum is indicated, will receive attention now that better
transportation is afforded.
 Barquisimeto, the capital, 2000 feet above the sea, and 90 miles
from Puerto Cabello, is the most important city of this section, a
centre of traffic for the northern Andes region as well as for the State
of Lara.

East of the Segovia Highlands are the States belonging to the

Centro, the section near and including the Federal District. These
are Carabobo, Aragua, and Miranda.
Carabobo, east of Yaracuy, has a considerable coast line, with
Aragua east, and Guárico and Cojedes south. Carabobo, like the
states following, is traversed by the Maritime Andes, having fertile
valleys between the two ranges. At the south are grassy plains
pasturing large herds of cattle. There is virgin territory with forest
products of wild rubber, timber, and dye woods; to the east the
country is more thickly settled. The state has many agricultural and
pastoral products, with marble quarries in the hills. Near Guacara
200,000 plants of sisal hemp are cultivated, here harvested in three
years (usually in four), and said to be superior to the best in Mexico.
Valencia, the capital, is a pleasant city, well situated in a beautiful
and fertile valley, much of which is occupied by Lake Valencia 30
miles long, with a steamboat service. Having an altitude of 1600 feet
the city has a mild climate and enterprising inhabitants. The state
contains the best port in the Republic, Puerto Cabello, linked by rail
with the capital, which has another railway connecting it with
Caracas. A small seaport, Ocumare de la Costa, is celebrated for the
excellence of the cacao grown in the vicinity.
Aragua stretches from the coast down to the southeast between
Carabobo and Miranda, with Guárico south. In the state is the east
end of Lake Valencia, near which is the important town of Maracay,
population 6000, in the midst of rich grazing land with pará grass; a
splendid farming and stock raising country, its dairies produce a
famous cream cheese. Goats, and excellent swine for the tropics are
also raised. 15 miles south of Maracay stands Villa de Cura, in the
main pass across the inner range to the llanos. Here are many big
ranches, the altitude being less than 2000 feet.
La Victoria,[4] the capital, on the Aragua River and also on the
Valencia-Caracas Railway, is 19 miles east of Maracay and 53 miles
from Caracas. It is a prosperous town with small factories of various
kinds.
[4] Very recently Maracay has been made the capital.
The Federal District comprises a long stretch of coast land with
the port, La Guaira, as well as a fertile valley with fine gardens of
luscious fruits, and coffee and sugar plantations. Some of the coffee
trees are said to yield as much as 20 pounds annually, which seems
a large story; it is probably two.
Miranda, south of the Federal District, has a long strip of coast
land farther east. Anzoátegui is southeast, Guárico south, and
Aragua west.
Ocumare del Tuy, the capital, about south of Caracas, is on the
Rio Tuy, into which the Guaire flows at Santa Teresa. The broad Tuy
valley, here and easterly towards the coast, is full of sugar cane and
cacao. To Guapo farther east come hides and other animal products
from the llanos as well as rich agricultural produce from the vicinity.
Rio Chico, a town near the coast, is a flourishing manufacturing
place.
Anzoátegui, east both of Miranda and Guárico, is a very large
State with a moderate coast line, but with a deep and wider interior
extending down to the Orinoco and Bolívar; the coast State of Sucre
and a long stretch of Monagas are on the east. In Anzoátegui the
llanos come up to the sea, though the mountains begin again in
Sucre.
Barcelona, the capital, is quite a town by the sea, three miles up
the Neveri River, but it makes use of the port, Guanta, 12 miles
distant. Coal mines are near, owned and operated by Venezuelans,
of which fact they are proud, as many of the industries are in the
hands of foreigners. Coffee and animal products are exported.
 Sucre, occupying the northeast corner of the Republic, is the last
State on the Caribbean; having the sea west, north, and east, and
the States of Monagas and Anzoátegui south. Here again we find the
double range of the Caribbean Hills extending across the State.
Cumaná, the capital, dating from 1513, is the oldest European
settlement on the continent; it was the birthplace of the celebrated
patriot, Antonio José de Sucre. The city is on the south side and at
the entrance of the Gulf of Cariaco, an arm of the sea 50 miles long
and 6-7 wide, which extends east and west, separated from the sea
by the narrow peninsula, Araya. In colonial days rich and
prosperous, the town, population 12,000, has now less than half as
many inhabitants; twice it has been destroyed by earthquakes. The
neighborhood is famous for its fine fruits, especially grapes,
pineapples, and mangoes. The usual products are brought from the
interior for export. The waters of the eastern, the inner end of the
gulf, are covered with a variety of wild fowls, caught by the peasants
for their plumage; formerly killed by drowning, the men diving with
them under water. Slaughter of birds for their egrets is now
prohibited, other methods for taking the plumes being practicable.
On the west end of the peninsula are extensive salinas, exporting
6000 tons of salt yearly; on the south are oil springs.
In this State is the port Carúpano, a city of 11,000, half way
between the peninsulas, Araya and Paria, each a long point of land,
the latter together with the Island of Trinidad forming the broad Gulf
of Paria. Between the Paria Peninsula and Trinidad, celebrated for
its pitch lake 100 acres in area, is the Bocas del Drago (Dragon’s
Mouths) named by Columbus, through which ships from the north or
south pass to the Port of Spain, Trinidad, and to other points on the
Gulf, though for some the way is nearer through the Serpent’s
Mouth, the southern entrance to the Gulf. Near the extremity of the
finely wooded, mountainous Peninsula of Paria is Cristóbal Colon,
the most easterly port of Venezuela, opposite the Orinoco Delta.
Castro attempted to make this a rival of the Port of Spain, but the
roadstead is so poor that the money was expended to little purpose.
In Sucre a little north of the San Juan River and near Guanoco is the
great Bermudez Asphalt Lake ten times the size of the better known
Trinidad.
Nueva Esparta, the Island State, comprises the larger Margarita,
20 miles off shore, the smaller Cubagua, Coche half way between,
and other smaller islands. Once famous for its pearl fisheries which
are still in operation, the present production of ordinary fish, and from
Coche of salt is of equal importance.
La Asunción, the capital, founded in 1524, is in a valley at the east
end of Margarita, with a port, Pampatar, at which some European
liners call.

Llano States

Monagas, south of Sucre and east of Anzoátegui, is a large State,

having at the east a small shore on the Gulf of Paria with the Delta-
Amacuro Territory below; on the south is the State of Bolívar.
Maturín, the capital, population 16,000, a cheerful, healthful place
with the remarkably low death rate of 12 per 1000, is on the Rio
Guarapiche, which flows into the Gulf. This, the most eastern state of
the llanos, has probably the pleasantest part around Maturín, where
the grassy plain is well supplied with streams having deep cut
channels and well wooded banks. The climate too is agreeable. The
State, well watered and wooded, its forests near the northern hills, is
chiefly a cattle country; the owners live mostly in small towns or
villages near the streams, but some in single, primitive cottages or
huts. A hammock must be carried by the traveler, though food may
be procured.
Anzoátegui, a coast State as well as a llano, has already been
described.
Guárico, a very large State west of Anzoátegui and north of
Bolívar and Apure, is south of Miranda and Aragua, and has Cojedes
and Zamora west.
Calabozo, population 10,000, the capital and chief city, 125 miles
southwest of Caracas, is a hot place, but in a good grazing country.
The neighborhood is noted for electric eels.
Cojedes, a smaller State west of Guárico, borders on Carabobo,
Yaracuy, Lara, Portuguesa, and Zamora.
San Carlos, the capital, is said to be less flourishing than formerly.
Portuguesa, southwest of Cojedes, borders also on Lara, Trujillo,
and Zamora.
Near Guanare, the capital, coffee and cacao are cultivated as well
as the cattle industry.
Zamora, also west of Guárico, borders north, west, and south on
Cojedes, Portuguesa, the mountain States of Mérida and Táchira,
and Apure.
Barinas, the capital, is not very prosperous. Formerly there was
here a flourishing tobacco district.
Apure, farther south than the other llano States, is west of Bolívar;
with Guárico, Cojedes, Zamora, on the north, and a bit of Táchira at
the west; it has Colombia for a long distance on its southern
boundary.
San Fernando, the capital, with a mean annual temperature of 91°,
and Calabozo, are distinguished as the two hottest places in the
country.

The Andine States

These have been called attractive and interesting, but lacking

good means of locomotion have been little visited. Residents,
perhaps returning from Europe, have been obliged to ride several
days on muleback to reach their homes. Clean, pleasant towns, fine
climate and scenery, mineral wealth, rich forest lands on the upper
slopes of the mountains, people hospitable and energetic,
characterize the three States, but with poor facilities for travel
progress was impossible. Improvement has now begun in this
direction, as the need is realized.
 Táchira, the most southern of these States, has Zulia and Mérida
north, Zamora and Apure east, and Colombia south and west.
San Cristóbal, the capital, at an altitude of 3000 feet is a
considerable commercial town. With roads from the llanos, by which
cattle are brought, and others, to San Antonio on the Colombian
frontier, to Uracá, terminus of the Táchira Railway from Encontrados,
and to Mérida, it is evidently quite a centre of trade.
Mérida, preëminently the Mountain State, borders on Zulia,
Trujillo, Zamora, and Táchira. Here are elevated plains, deep valleys,
bleak paramos or high passes, one reaching 14,500 feet, and loftier
snowclad mountains; the last are east of the capital, Mérida.
Mérida, situated on a plateau a mile above the sea, has another
and lower range of mountains on the west. These mountain States
have the variety of products found in some States of Colombia:
tropical and temperate fruits, with coffee, cacao, cotton, wheat, wool,
etc.; in Mérida, gold and silver also.
Trujillo, with lower mountains, borders on Zulia, Lara, Portuguesa,
Zamora, and Mérida. The fertile valleys produce the finest cacao,
there are large sugar estates; wheat grows higher, cattle and goats
find suitable pasturage. Northwest are forests largely unexplored; oil
springs give promise of future wealth.
Trujillo, the capital, is a busy town with roads in several directions;
it is 19 miles from the railway station at Motatán. Other towns of
some importance are Valera, Bocono, and Carache.

The Guayana Highlands have a single State and one territory.

Bolívar, a great State, with an area of 90,000 square miles, twice
the size of Pennsylvania, has the Delta on the northeast; north
across the Orinoco, it has a bit of Monagas, a long stretch of
Anzoátegui, and a smaller extent of Guárico, to the point where the
Apure enters the Orinoco and the latter river turns east. There, west
of the Orinoco, is the State of Apure down to the entrance of the
Meta River, below which Colombia is west for a short space.
Amazonas is south of the west part of Bolivar, and west of the
southeast part, which last has Brazil on the south and British Guiana
east. Bolívar, largely covered with virgin forest, includes a vast extent
of unexplored territory, besides a gold region bordering on British
Guiana.
Ciudad Bolívar, the capital, perhaps a trifle hotter than the coast
ports, has a lower death rate. Two hundred and twenty-five miles
from the mouth of the river, which during a great part of its course is
two miles wide in the dry season and seven in the wet, the city is
located at a point where the river is narrowed to a mile. In
consequence of this, the water is liable to rise 50 feet in the wet
season, flooding the lower and poorer part of the city.
While the capital is the official port of entry, there is a city farther
down stream known as San Felix or Puerto Tablas, just beyond the
mouth and falls of the Caroni River. These falls, famed since first
seen by Sir Walter Raleigh, are an imposing spectacle: a huge mass
of water descending over a wall of black granite to the Orinoco
below, obviously a great source of electricity in the future. East of the
Caroni, which flows from the southern boundary, are the two most
populous districts of the State. This is explained by gold. Cart roads,
by which merchandise is carried south and balatá and hides are
brought north, extend through Upata, capital of the Piar District, to
Guasipati, 125 miles; but as the time of wheel traffic may be ten days
and upwards, the traveler usually hires a mule and arrives in a few
days. Guasipati has been the centre of the balatá industry, but as the
local operators lazily cut down the trees instead of tapping them, the
main production is moving south.
The town of El Callao, 3 hours ride farther, is over the famous
mine of that name. On the border of Guiana 60 or 70 miles south, a
section has been opened accessible by water only. The high cost of
transport, and the scarcity, the high price, and the poor quality of
labor, greatly interfere with the development of this region. With wide
spread indications of gold, there is little reason to doubt the
existence here of vast mineral wealth.
 Besides the forest clad hills of this section there are great
stretches of savannas occupied by or suitable for cattle ranches,
while plantations and mills for the production of sugar and rum are
also found.
Six hours east of Callao, near the forests, is the town Tumeremo,
a centre of the balatá industry, where the wholesale destruction of
trees still prevailing will end local production and the town as well.
The uplands of the Caroni River are yet unknown, but gold, and the
timber and vegetable products of the forest will doubtless one day
reward the hardy explorer, as in many other regions of the country.
Above Bolívar, on the Orinoco, there is at one point a narrow
gorge where the current is at times so strong as to drive back river
steamers. Farther on, the Caura River comes in from the south,
through savannas in the lower part and forests higher up. On a
western tributary of the Caura, the Nichare, there is said to be plenty
of good rubber. 130 miles up the Caura are falls or rapids
descending 200 feet, a splendid source of power for future saw mills.
Two days higher are more rapids in a narrow gorge. The lower part
of these Orinoco tributaries are infested with mosquitoes, sand flies,
etc., a torment to explorers, but decreasing upstream. Near the
Cuchivero, the next considerable river, are many cattle ranches; its
upper valley is rich in forest products.

Territories

The Amazonas Territory, beginning as previously stated

somewhat below the entrance of the Meta River into the Orinoco,
occupies the entire region south to Brazil. It extends farther down
than the State of Bolívar, having that State and Brazil on the east,
Colombia west, and Bolívar also on the north. Amazonas with
101,000 square miles is larger than Bolívar and still less known,
explorers having attempted little beyond the passage of a few
streams.
San Fernando de Atabapo, the capital, is a village where the
Atabapo flows into the Orinoco and that river begins to be the
boundary with Colombia; the Atabapo being the boundary for some
distance farther south. The Orinoco coming from the southeast, in its
upper reaches is entirely in Amazonas. About the same point as the
Atabapo, the Guaviare enters the Orinoco from Colombia, the white
waters of this stream contrasting with the clear black (one writer calls
it red) of the Atabapo, which latter, it will be remembered, often
indicates absence of mosquitoes with more comfort and better
health.
It is farther north, between the entrance of the Colombian rivers
Vichada and Meta, that the two great barriers to navigation on the
Orinoco occur, the Atures Rapids, the lower and the largest on the
river, and 50 miles south the Maipures. In each of these sections the
foaming river dashes among rocks and wooded islands in a fashion
magnificent to behold from the shore, but not inviting for a sail. With
the water power apparent, an electric railway connecting the service
of the lower Orinoco with that above the Maipures Rapids might not
seem too difficult; a contract has been made for the work to promote
the development of this region.
Amazonas contains a mountainous district with peaks 7000-8000
feet high, though the greater part is rather low land. There are tribes
of Indians, some gentle and timid, others so savage as to prevent
exploration, especially the Guaharibos, also called White Indians, far
up the Orinoco beyond Esmeralda. The territory has grassy plains
suited to cattle raising, but more forest land with rubber trees of the
first class, a few of which in small sections have been tapped; there
are natural cacao patches. Mineral wealth is indicated by the reports
and specimens from the Indians.
Forty miles above the confluence of the Atabapo and the
Guaviare, the great Ventuari tributary, 300 miles long, enters the
Orinoco from the east. 150 miles higher the famed Casiquiare or
Brazo leaves the Orinoco to join the Rio Negro and Amazon. An old
mission station, Esmeralda, 20 miles beyond, on the Orinoco, is the
last permanent settlement of the region. The watershed, here but a
slight bank along the left of the river, is entirely lacking where the
Casiquiare leaves it, taking a little of the water. Farther on the
diverging stream unites with the Guiania River in Colombia to form
the Negro, the chief northern tributary of the Amazon.
The Delta Amacuro Territory embraces the delta of the Orinoco,
with some mountainous country at the south before reaching the
boundary of British Guiana, which with the State of Bolívar is on the
south; Monagas is on the west. The coast line runs northwest
southeast from the Gulf of Paria, of which it forms the southern limit,
to Guiana; thus nearly the whole coast faces the Atlantic. Only one
settlement is found on the swampy shore, Pedernales on the Gulf, a
gloomy spot with unprepossessing inhabitants. Up the Caño
Pedernales there is beautiful foliage in the inundated forest, with
higher lands back, where live primitive wild Indians; farther on is
unflooded forest, or open savannas with rich grass for thousands of
cattle; on the banks a few scattered houses. One fine cacao ranch is
passed before reaching Tucupita, the capital, a dismal place, but
with some signs of commercial life. Soon after, the mountains of
Guayana are visible, and presently the town of Barrancas in
Monagas, the lowest town and port on the Orinoco proper.
 CHAPTER X
VENEZUELA: PORTS AND TRANSPORTATION

La Guaira, the chief port of the Centro, and the best known of
Venezuela, is rivaled by Puerto Cabello, which has a better natural
harbor. La Guaira, population 18,000 including its suburbs, as the
port of the capital, Caracas, attracts more travelers and at present
more trade, much of it coming from or going to other parts of the
country. The harbor, a rather open roadstead, was improved at great
expense by port works. Though these facilitate the increasing traffic,
ships at times are still exposed to heavy swells. The town is hot and
unhealthful with a mean temperature of 84.5°, but it has good rail
connection with its pleasant suburbs, cooler and more sanitary. The
port has good piers, vessels lying alongside. The depth of water is
28-30 feet.
Puerto Cabello, 65 miles west, in the State of Carabobo,
population 20,000, is said to have the best harbor, its depth 28 feet,
on the North Coast of South America. With a slightly lower
temperature than La Guaira, it has a higher death rate. To this port
comes most of the produce of its own State, of Yaracuy, of the Llano
States Cojedes and Portuguesa, and some from the Andes region.
The enterprise of the Venezuela Meat Syndicate, with new buildings
here, promotes stock farming and the traffic of the port. A floating
dock receives vessels of 2000 tons; a new one will accommodate
ships of 4000 tons.
Carúpano, far to the east of La Guaira, is the only other port of
importance which is visited by large ocean steamers. Although as
warm as Puerto Cabello, it has a much more healthful climate. With
no real harbor, merely an open roadstead, serving the State of
Sucre, it is a port of call for several lines of steamers. The cargo
must be transported in lighters.
Ciudad Bolívar, though far up the Orinoco River, as the official
port of entry for half the country, serves an extensive region. It
communicates with the outside world by weekly steamers of shallow
draught to the Port of Spain, as also by coasting vessels. The
steamers returning cross the Gulf of Paria, follow up the Caño
Macareo to the Orinoco, and up that river to Bolívar.
Maracaibo, the fifth port with foreign trade, though called a
seaport is not exactly on the sea; being located on the west shore of
a broad channel 6-12 miles wide and 30 long which connects Lake
Maracaibo with the Gulf of Venezuela. The city has fine wharves on
a beautiful bay, a smooth roadstead with water 30 feet deep; but
unfortunately the sand bar at the entrance of the channel confines
the passage to ships drawing only 11 feet, with conditions growing
worse. As the city is now the second port of the country with the
largest export trade including some from Colombia, it has been
proposed either to dredge one of the entrance channels, or to make
use of the fine natural harbor of Cojoro on the Gulf, capable of
accommodating the largest steamers, and to connect this port with
Maracaibo by a railway about 100 miles long. At present the foreign
trade is carried on by national, Dutch, and Spanish steamers, and by
American boats of the Red D Line. Freight not destined for the
United States is largely carried to the Dutch Island Curaçao, where
transfer is made to ships of other lines. Sailing vessels also carry
much produce.
These primary ports, except Carúpano, all have docks where
ships come alongside. A new freight and passenger service from
New Orleans to Venezuelan ports has been installed by the W. R.
Grace Company.
A number of smaller ports are served generally by smaller craft,
steam or sailing vessels, which transfer freight to the primary ports
for ocean traffic. Some of these are: La Vela (56 miles from
Curaçao), the port of Coro, capital of Falcón; Tucacas, in the same
State, important as serving the copper mines of Aroa; Carenero, in
Miranda, east of Caracas; Guanta, long the port of Barcelona and
neighboring coal mines; Cumaná in Sucre, a mile from the mouth of
the Manzanares River; and Pampatar on Margarita Island. At
Turiamo, a natural harbor between La Guaira and Puerto Cabello, a
public bonded warehouse is to be erected, and connection will be
made with the Grand Central Railway. At Ocumare de la Costa port
and harbor works are to be constructed by the Government and a
railway connecting the port with Maracay, 43 miles distant.

Inland Transportation

The railway development of Venezuela is small, the longest line

being 111 miles in length, and the total mileage about 650. There is
therefore a little over a foot of railway for each inhabitant. Most of the
lines are from a port to the interior; all are of narrow gauge, but of
varying widths. Most of the existing lines were laid, 1881-1893.
Unfavorable legislation prevented further construction until after a
change in the laws; later the Great War interfered. Rates are very
high on all the railways, yet most of them are unprofitable.
The La Guaira-Caracas Railway is exceptional, having a large
amount of traffic, more of import freight than of export. The British-
built Railway climbs to a height of over 3000 feet to surmount the
ridge on the south side of which is Caracas, a two hours’ ride, one of
intense interest and beauty. While the tracks of the Harbor
Corporation are of the same gauge as the railway, these cars do not
go to the steamer’s side, so that much freight is unnecessarily
handled twice. Railways now electrified serve the suburbs on either
side.
Caracas is served by two other railways, but these are of different
gauge.
The Central Railway, the station of which is two miles across the
city, runs from Caracas east and south towards Ocumare on the Tuy
River; 46 miles to San Francisco de Yare are completed; the
remaining 15 are in construction. Both of these roads were difficult to
build, the many bridges, tunnels, and viaducts needed making them
very expensive. The maximum grade is about 4 per cent. The latter
road follows down the Guaire valley, passing Petare, a town of
Miranda, only seven miles from Caracas.
If the River Tuy were followed down to the east and north, one
would come to the Carenero Railway which connects the small port
of that name with the towns, Higuerote, Rio Chico, a flourishing
manufacturing place, and Guapo, 34 miles, on the way to the llanos
of Guárico. From the llanos come hides and other animal products to
the port, and from the vicinity rich agricultural products including
cacao. The Railway runs a steamship line to La Guaira; small
schooners also serve.
The Great Railway of Venezuela, built by the Germans, is the
other line from Caracas, the longest and most costly in the country. It
runs west to Valencia, the second city of the Republic. Though as a
whole less difficult than some others, there is one stretch of 8 per
cent grade requiring cog wheels and there are many loops and
zigzags. The road traverses a fine farming and cattle country and
passes through the important towns of Victoria and Maracay in
Aragua, previously mentioned. 212 bridges and 86 tunnels in 111
miles may seem many for an easier road. A branch of 2¹⁄₂ miles runs
to the village of Guigüe.
The Puerto Cabello-Valencia Railway, 33 miles long, connects
Valencia directly with the sea, passing over the north ridge of the
mountains at a height of 2000 feet. Though the construction of the
road as a whole was less difficult than that of the La Guaira-Caracas,
to shorten it, a section 2.4 miles long has a cog rail with a maximum
grade of 8 per cent.
The Bolívar Railway, farther west, the first in Venezuela, was built
for the especial benefit of the copper mines of the State of Yaracuy.
It runs from the port of Tucacas, northwest of Puerto Cabello, to
Barquisimeto, 100 miles. The part built first is now a branch of the
road, leading from La Hacha to the rich copper mines at Aroa eight
miles distant. Both railway and mines are British properties, the latter
bringing in handsome returns. A company steamer carries freight to
and from Puerto Cabello, as Tucacas has no custom house. Another
branch of the railway, from Palma Sola to the capital of Yaracuy, San
Felipe, 25 miles, was opened in 1916. In this State are other copper
mines unworked, and fertile hills and plains uncultivated. The Rio
Tocuyo is navigable as far as Siquisique for steamboats, but traffic is
not sufficient to make their operation profitable.
 The La Vela-Coro Railway, 8¹⁄₂ miles long, connects Coro with its
port.
In the State of Zulia are three more railways:
The La Ceiba, 50 miles long, runs from that port on the Lake
toward the city of Trujillo as far as Motatán.
The Great Railway of Táchira, 75 miles long, goes from
Encontrados on the Catatumbo River west of the Lake, south
towards the capital of Táchira, now reaching San Felix or a little
beyond. It serves the Colombian Department of Santander as well as
Táchira. The many transfers of freight are a great disadvantage,
while freshets on the Catatumbo threaten to destroy Encontrados.
The Santa Barbara-El Vigia Railway, 37 miles long, is designed
to serve the city of Mérida. Santa Barbara is on the Escalante River;
and the road towards Mérida, which crosses several streams, has
had much trouble from the Chama River from inundations.
The Guanta-Naricual Railway, far to the east, leads from the port
of Guanta past the city of Barcelona, capital of Anzoátegui, to the
coal mines of Naricual. Guanta, though not a primary port, has an
excellent natural harbor, but the opening to navigation in 1915 of the
Neveri River on which Barcelona is situated has greatly diminished
the traffic of Guanta.
A few private railways exist, constructed for business purposes:
A railway 27 miles long of the Asphalt Mines of Inciarte in Zulia.
A railway of 10 miles of the Asphalt Mines of Guanoco, Sucre.
A two mile railway of Asphalt Mines of Guanipa, Monagas.
A railway 10 miles from San Lorenzo, Zulia, to oil wells of the
Caribbean Petroleum Company.
A railway 19 miles from Bobures, Zulia, to a sugar plantation.
A railway 19 miles from Rio Limón, Zulia, to coal fields 40 miles
west of Maracaibo, leased by the Caribbean Coal Company.