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 GREEN
CHEMISTRY
AN INCLUSIVE APPROACH

Edited by

BÉLA TÖRÖK
TIMOTHY DRANSFIELD
University of Massachusetts Boston, Boston, MA, United States
Elsevier
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 List of Contributors
Steven Ackerman University of Massachusetts
Boston, Boston, MA, United States
Karelle Aiken Georgia Southern University,
Statesboro, GA, United States
Nicholas D. Anastas United State Environmental
Protection Agency, Cincinnati, OH, United States
Paul T. Anastas Yale University, New Haven,
CT, United States
Gopalakrishnan Aridoss LG Life Sciences Ltd,
Daejeon, South Korea
Johannes Bader Beuth University of Applied
Sciences, Berlin, Germany
Nadine Borduas ETH Zurich, Zurich,
Switzerland
Christopher Brigham University of Massachu-
setts Dartmouth, North Dartmouth, MA,
United States
Gabriela Bueno University of Massachusetts
Boston, Boston, MA, United States
Timothy P. Canty University of Maryland,
College Park, MD, United States
Philip Coish Yale University, New Haven, CT,
United States
Kathryn E. Cole Christopher Newport
University, Newport News, VA, United States
John Collins IBM Thomas J Watson Research
Center, Yorktown Heights, NY, United States
Amy Costa Center for Coastal Studies,
Provincetown, MA, United States
Levente Cseri The University of Manchester,
Manchester, United Kingdom
Rupali Datta Michigan Technological University,
Houghton, MI, United States
Neil M. Donahue Carnegie Mellon University,
Pittsburgh, PA, United States
xi
Daniel P. Dowling University of Massachusetts
Boston, Boston, MA, United States
Timothy Dransfield University of Massachu-
setts Boston, Boston, MA, United States
Clifford J. Ellstrom University of Massachusetts
Boston, Boston, MA, United States
Natalia Escobar-Pemberthy University of Mas-
sachusetts Boston, Boston, MA, United States
Daniel M. Genest University of Massachusetts
Boston, Boston, MA, United States
Debanjana Ghosh Georgia Southern University,
Statesboro, GA, United States
Gerald E. Gilligan University of Massachusetts
Boston, Boston, MA, United States
Alain Goeppert University of Southern California,
Los Angeles, CA, United States
Gerald Gourdin Georgia Institute of Technology,
Atlanta, GA, United States
Robyn E. Hannigan University of Massachu-
setts Boston, Boston, MA, United States
Julie A. Himmelberger DeSales University,
Center Valley, PA, United States
William Horton University of Massachusetts
Boston, Boston, MA, United States
Patricia Hughes Center for Coastal Studies,
Provincetown, MA, United States
Maria Ivanova University of Massachusetts
Boston, Boston, MA, United States
Stefan D. Kalev Gulf Coast Research and
Education Center, University of Florida,
Wimauma, FL, United States
Daniel Kirk-Davidoff University of Maryland,
College Park, MD, United States
Anne Kokel University of Massachusetts Boston,
Boston, MA, United States
xii LIST OF CONTRIBUTORS
Kenneth K. Laali University of North Florida,
Jacksonville, FL, United States
Shainaz Landge Georgia Southern University,
Statesboro, GA, United States
Nicholas A. Lee University of Massachusetts
Boston, Boston, MA, United States
Alexandra Maertens Johns Hopkins Bloomberg
School of Public Health, Baltimore, MD, United
States
Enda McGovern Sacred Heart University,
Fairfield, CT, United States
Meaghan McKinnon University of Massachu-
setts Boston, Boston, MA, United States
Manisha Mishra University of Massachusetts
Boston, Boston, MA, United States
Ken T. Ngo University of Massachusetts
Boston, Boston, MA, United States
James Noblet California State University San
Bernardino, San Bernardino, CA, United States
George A. Olah University of Southern
California, Los Angeles, CA, United States
István Pálinkó University of Szeged, Szeged,
Hungary
Peter Pogany Gedeon Richter Plc., Budapest,
Hungary
Helen C. Poynton University of Massachusetts
Boston, Boston, MA, United States
Deyang Qu University of Wisconsin Milwaukee,
Milwaukee, WI, United States
Mayamin Razali The University of Manchester,
Manchester, United Kingdom
William E. Robinson University of Massachu-
setts Boston, Boston, MA, United States
Jonathan Rochford University of Massachusetts
Boston, Boston, MA, United States
Abhishek RoyChowdhury Stevens Institute of
Technology, Hoboken, NJ, United States
Heather A. Rypkema Heritage Strategies, INTL,
Washington, DC, United States
Ross J. Salawitch University of Maryland,
College Park, MD, United States
Dibyendu Sarkar Stevens Institute of Technology,
Hoboken, NJ, United States
Christian Schäfer University of Massachusetts
Boston, Boston, MA, United States
Laurel Schaider Silent Spring Institute, Newton,
MA, United States
Linda Schweitzer Oakland University, Rochester,
MI, United States
Abid Shaikh Georgia Southern University,
Statesboro, GA, United States
G.K. Surya Prakash University of Southern
California, Los Angeles, CA, United States
Gyorgy Szekely The University of Manchester,
Manchester, United Kingdom
Gurpal S. Toor University of Maryland, College
Park, MD, United States
Béla Török University of Massachusetts Boston,
Boston, MA, United States
Marianna Török University of Massachusetts
Boston, Boston, MA, United States
David M. Wilmouth Harvard University,
Cambridge, MA, United States
Julie B. Zimmerman Yale University, New
Haven, CT, United States
 Preface
The concept of this book was born in 2005
when we (along with Deyang Qu, who
wrote Chapter 3.23) taught Introduction to
Green Chemistry at UMass Boston. We team-
taught the course because none of us indi-
vidually had expertise in everything we
wanted to cover. We were lucky to have
faculty whose specialties included air pollu-
tion, novel battery technologies, and green
synthesis, but even with our combined
backgrounds, we felt unprepared to show
the true breadth of the field of Green
Chemistry. We searched for a textbook to
help us fill in the gaps, but we could not find
one. We successfully ran the course using an
environmental chemistry textbook and a lot
of primary literature, but from the outset, we
realized that the course deserved a textbook
designed around it.
This, then, is the textbook we wish had
been available to us. It is intended for a
broad audience, including industry and
academia. It is aimed to be a contemporary
and inclusive Green Chemistry text that can
be used in undergraduate and graduate ed-
ucation and as a resource for researchers.
The main goal of the work was to be as
broad as possible, including many aspects of
Green Chemistry. The book includes three
main parts. The first two parts are intended
for those who teach Green Chemistry: it
covers the basic definitions, environmental
chemistry, renewable energy, sustainable
synthesis, fundamental chemical toxicology,
and the effect of environmental factors on
our genetic information. These chapters
xiii
follow a textbook style, providing examples,
recommended reading, and problem sets.
The third part of the work is designed for
researchers, as it contains in-depth reviews
on selected topics. Our intention is that ed-
ucators, after covering the fundamentals laid
down in the first part, may select some of the
specialized research chapters as case studies
to further illustrate the state-of-the-art prac-
tice of Green Chemistry. Although the book
includes more topics than could be covered
in a typical undergraduate or even graduate
class, the variety of topics will provide op-
portunity for the faculty instructors to select
topics they are comfortable covering and can
fit into their schedules.
The centerpiece of the third part of the
book is Green Chemistry in practice. The
topics included in this part focus on special
areas of the field. Every chapter in this
part provides an up-to-date reference sec-
tion, together comprising thousands of
original papers and review articles. We
believe that by including experts in many of
the fields discussed, the book provides the
readers with “insider information”: the as-
pects or challenges of a given field that the
specialists consider the most important and
urgent. This way, we hope that the book
will serve as a primary resource for those
who are new to Green Chemistry or those
who intend to branch out and discover
other topics that are related to their own
research fields.
We would like to thank our distinguished
colleagues and authors, experts in their fields,
xiv PREFACE

for contributing to this unique endeavor.
We also thank Kathryn Morrissey and Laura
Kelleher, who helped us through the proposal
phase of the book, and Anitha Sivaraj,
who handled the galley proofs. We are
indebted to Emily Thomson, our Editorial
Project Manager, for her enormous help and
continuous encouragements throughout the
process.
Béla Török and Timothy Dransfield
Boston, May 1, 2017
 C H A P T E R

1.1
Green Chemistry: Historical
Perspectives and Basic Concepts
Béla Török, Timothy Dransfield
University of Massachusetts Boston, Boston, MA, United States

Chemists and chemistry, in general, have made an enormous contribution to the history of
humankind. Beginning with the early alchemists, these contributions include several devel-
opments that changed the course of history for the better or, in some cases, for the worse.
Many of them may seem to be simple by today’s standards, but at the time, they were
groundbreaking discoveries and inventions. The fabrication of simple soaps made the forma-
tion of large cities possible by improving the personal hygiene. The production of dyes and
paints contributed significantly to fashion and art over the centuries. As the usefulness of
chemistry became clear, more people decided to pursue such endeavors, which brought
exponential growth in this field. As Dalton, Avogadro, and Lavoisier made their famous dis-
coveries, chemistry became viewed more and more as science than as black magic. With sig-
nificant developments in chemical theory came the increased pace of new applications that
inspired yet further progress. However, not every step along the way was problem free.
Several inventions that were made with the best intentions backfired and caused health or
environmental issues. The use of freons as inflammable carrier gases in all sorts of sprays
in the 1960se70s seemed to be perfect, until Rowland and Molina published their findings
on the terrible effect of these chemicals on the ozone layer that protects the earth from harm-
ful ultraviolet radiation. Antibiotics were hot commodities after World War II, until it was
found that bacteria can develop resistance toward these compounds making them more diffi-
cult to fight against. Plastics seemed like a blessing until it was found that their degradation
takes over a thousand years. Dichlorodiphenyltrichloroethane (DDT) appeared to be an effec-
tive agent to fight malaria-spreading mosquitos, until it was found in fish around Antarctica,
proving that it lingers for a long time. Contemporary pesticides can leach into natural waters
and cause gender change in frogs. Many drugs have unintended harmful side effects. The list
is long. What is common in all these cases is that a product was developed for a certain pur-
pose without a careful analysis of its broader impact on the ecosystem. All these disasters
initiated a different chemical thinking that now we call green chemistry.

Green Chemistry
http://dx.doi.org/10.1016/B978-0-12-809270-5.00001-7 3 Copyright © 2018 Elsevier Inc. All rights reserved.
4 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

1.1.1 EMERGENCE OF GREEN CHEMISTRY

Early in the evolution of the chemical industry, scientists were already, although uncon-
sciously, applying some of the much later formulated principles of green chemistry. For instance,
the development of heterogeneous catalytic petrochemical processes dates back to the 1930s. The
more conscious development of such thinking began after several major environmental disasters
and industrial accidents occurred. The aforementioned problems are just a few examples to
demonstrate the potentially harmful nature of chemicals if applied and introduced to the
biosphere without sufficiently careful forward thinking. Rachel Carson’s book, Silent Spring
(1962), which described the destruction of local ecosystems by toxic chemicals, likely was a
wake-up call for the society to address the issues or face grave consequences. As the first impor-
tant step to address these issues the US Congress passed the National Environmental Policy Act in
1969. The US Environmental Protection Agency (US EPA) was established by President Nixon in
1970. Since the 1970s several environmental legislations have been implemented, such as the
Clean Air Act of 1970 and the Safe Drinking Water Act of 1974, that signaled the government’s
intention to solve the problems via regulations. The US Toxic Substances Control Act was passed
in 1976, and now it has over 80,000 chemicals in its listings. Later the more comprehensive Clean
Air Act and the Pollution Prevention Act were enacted, both in 1990. The term Green Chemistry was
coined by the EPA Office of Pollution Prevention and Toxins in the early 1990s. In 1995, the US
EPA established an annual awards program called the Presidential Green Chemistry Awards to
recognize the leaders of innovation from both industry and academia. In 1997, the first PhD
in Green Chemistry program was established at the University of Massachusetts Boston. In the
same year the Green Chemistry Institute was founded, which later became the American Chem-
ical Society Green Chemistry Institute. Starting with the 1990s, several scientific journals devoted
to green chemistry research began publishing original research and review articles in the field.
Today, all major publishers have at least one journal devoted to green or sustainable chemistry
research with several books and textbooks published to aid research and education.

1.1.2 SUSTAINABLE PRODUCTION OF COMMODITIES:

PRINCIPLES AND BASIC CONCEPTS

Several tools and methods that are now considered as part of sustainable synthesis (e.g.,
catalysis) were developed much earlier than the formal green chemistry movement began.
It took concerted and conscious efforts to envision and design a framework that included
the earlier developments and initiated further progress in this field. The basic principle,
benign by design, emphasized that both the product and the process used to produce it should
conform to the basic rules of sustainability. In their seminal book in 1998, Anastas and
Warner established the major principles of green chemistry. Although since then several
“new principles” have been added to the list, the original list is still applicable.

1.1.2.1 Principles of Green Chemistry

1. Prevention: It is better to prevent waste than to treat or clean up waste after it has been
created.
2. Atom economy: Synthetic methods should be designed to maximize the incorporation of
all materials used in the process into the final product.

1. INTRODUCTION
 1.1.2 SUSTAINABLE PRODUCTION OF COMMODITIES: PRINCIPLES AND BASIC CONCEPTS 5
3. Less hazardous chemical syntheses: Wherever practicable, synthetic methods should be
designed to use and generate substances that possess little or no toxicity to human
health and the environment.
4. Designing safer chemicals: Chemical products should be designed to affect their desired
function while minimizing their toxicity.
5. Safer solvents and auxiliaries: The use of auxiliary substances (e.g., solvents, separation
agents, etc.) should be made unnecessary wherever possible and innocuous when
used.
6. Design for energy efficiency: Energy requirements of chemical processes should be recog-
nized for their environmental and economic impacts and should be minimized. If
possible, synthetic methods should be conducted at ambient temperature and pressure.
7. Use of renewable feedstocks: A raw material or feedstock should be renewable rather
than depleting whenever technically and economically practicable.
8. Reduce derivatives: Unnecessary derivatization (use of blocking groups, protection/
deprotection, temporary modification of physical/chemical processes) should be mini-
mized or avoided if possible, because such steps require additional reagents and can
generate waste.
9. Catalysis: Catalytic reagents (as selective as possible) are superior to stoichiometric
reagents
10. Design for degradation: Chemical products should be designed so that at the end of their
function they break down into innocuous degradation products and do not persist in
the environment.
11. Real-time analysis for pollution prevention: Analytical methodologies need to be further
developed to allow for real-time, in-process monitoring and control prior to the forma-
tion of hazardous substances.
12. Inherently safer chemistry for accident prevention: Substances and the form of a substance
used in a chemical process should be chosen to minimize the potential for chemical
accidents, including releases, explosions, and fires.
Since products that involve any chemistry during their preparation are all manufactured
by industry, the aforementioned list had to be amended to include specific issues that
chemical engineers face while transitioning a laboratory process to the industrial setting.
Hence, Anastas and Zimmerman developed a similar set of principles for engineering.

1.1.2.2 Principles of Green Engineering

1. Inherent rather than circumstantial: Designers need to strive to ensure that all materials
and energy inputs and outputs are as inherently nonhazardous as possible.
2. Prevention instead of treatment: It is better to prevent waste than to treat or clean up
waste after it is formed.
3. Design for separation: Separation and purification operations should be designed to
minimize energy consumption and materials use.
4. Maximize efficiency: Products, processes, and systems should be designed to maximize
mass, energy, space, and time efficiency.
5. Output pulled versus input pushed: Products, processes, and systems should be “output
pulled” rather than “input pushed” through the use of energy and materials.

1. INTRODUCTION
6 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

6. Conserve complexity: Embedded entropy and complexity must be viewed as an invest-

ment when making design choices on recycle, reuse, or beneficial disposition.
7. Durability rather than immortality: Targeted durability, not immortality, should be a
design goal.
8. Meet need, minimize excess: Design for unnecessary capacity or capability (e.g., “one size
fits all”) solutions should be considered a design flaw.
9. Minimize material diversity: Material diversity in multicomponent products should be
minimized to promote disassembly and value retention.
10. Integrate material and energy flows: Design of products, processes, and systems must
include integration and interconnectivity with available energy and materials flows.
11. Design for commercial “afterlife”: Products, processes, and systems should be designed
for performance in a commercial “afterlife.”
12. Renewable rather than depleting: Material and energy inputs should be renewable rather
than depleting.
Several other sets of principles have been developed by different groups, for example,
Poliakoff’s mnemonic PRODUCTIVELY, that similarly summarizes the basic concepts
(Prevent waste, Renewable materials, Omit derivatization, Degradable products, Use of safe methods,
Catalysis, Temperature, pressure ambient, In-process monitoring, Very few auxiliaries, E-factor, Low
toxicity, Yes, it is safe). Certainly, the aforementioned principles were not developed overnight.
Several research groups have contributed to the development of the major concepts that
guided the growth of green chemistry. Here, we list these basic concepts and definitions
that will be used in the later chapters of this book.
E-factor: The E (environmental)-factor, developed by Roger Sheldon, is one of the most
practical descriptors of the efficiency; it is the mass ratio of waste to the target product.
For instance, E ¼ 20 means that 20 kg waste is produced to every kilogram of product.
Obviously, the smaller the number, the better; in the best possible circumstances (0 kg
waste is generated with the product), E ¼ 0. The E-factor is a commonly accepted and
applied measure to describe the efficiency of processes in the chemical and pharmaceu-
tical industry for the assessment of the overall environmental impact.
Atom economy (AE): Atom economy (atom efficiency is also used), first described in 1991
by Trost, is defined by the ratio of the molecular weight of the product and the sum
of the molecular weights of all substances consumed in the stoichiometric equation
of a reaction. Commonly it is expressed as a percentage. It is important to highlight
that AE is based on the theoretical reaction (i.e., no unexpected by-products are
factored in) and 100% theoretical yield. Therefore the AE is the best possible scenario
and can be used to assess a reaction at the theoretical level. For example, if a reaction
scheme does not involve the formation of any expected by-product, the AE is 100%
(Scheme 1.1.1).
However, it is worth noting that it cannot be used exclusively to describe the environ-
mental impact of a reaction: it may be that a reaction with 100% AE yields unexpected
by-products (e.g., stereo- or regioisomers) that would decrease the actual AE. Thus a highly
selective reaction with 80% theoretical AE and no unexpected by-products may have less

1. INTRODUCTION
 1.1.2 SUSTAINABLE PRODUCTION OF COMMODITIES: PRINCIPLES AND BASIC CONCEPTS 7

SCHEME 1.1.1 Hydration of cyclohexene to cyclohexanol; a 100% atom economic process.

environmental impact than a 100% AE reaction that is accompanied by extensive unexpected

by-product formation.
Although these are the two most important measures to describe the efficiency of a chem-
ical process, several alternative metrics have been proposed, such as the reaction mass efficiency
(RME) defined as the mass ratio of the obtained product to the total mass of the reactants,
thus incorporating the actual percent yield into traditional AE calculations. Carbon efficiency
is similar to RME, but only considers carbon as a part of the product or starting materials
and reagents. Mass efficiency (total mass of the materials used divided by the mass of product
obtained given as a percentage) and effective mass yield (the ratio of the mass of the desired
product and the total mass of nonbenign reactants) are other available ways to describe
the environmental impact of processes. There is a general agreement in the literature that
the AE and E-factor are the most applicable and widely used measures in many industries.
Although the aforementioned metrics are able to estimate the impact of a process, there are
other considerations to discuss, such as the chemical characteristics of the waste. Obviously,
the ultimate process occurs with 100% AE and 0 E-factor; however, practical processes are
different and mostly produce either expected or unexpected by-products that are considered
waste. The nature of that waste is highly important. It is easy to realize that if the waste is
water (e.g., dehydration reactions) or sodium chloride (nucleophilic substitutions) that are
considered harmless, the process is quite different from, to choose one example from
many, the Jones oxidation of alcohols to ketones that generates a significant amount of chro-
mium salt waste (Scheme 1.1.2).
To consider this highly important aspect, Sheldon introduced the environmental quotient
(EQ), which is calculated by multiplying the E-factor by an arbitrarily assigned environmental
unfriendliness quotient, Q. As an example, one can assign 1 to benign chemicals (such as water
or NaCl) and a large number (e.g., 100 or 1000) to chromium sulfate. Although as of yet a
clear definition or individual assignment of Q values to chemicals is not available, theoreti-
cally it is possible to quantify the environmental impact of chemical waste based on its
amount and toxicity. It is, however, a difficult task as compounds exhibit all sorts of harmful
biological activities, and although it is possible to rank them in terms of one effect (e.g., car-
cinogenicity or mutagenicity), the ranking (and the Q value) could be significantly different if
another type of toxicity is considered. In addition, when a process is generating a compound
that is not yet known, its biological effect only can be estimated, e.g., by quantitative struc-
ture-activity relationship models.
An even more extended approach that embraces the holistic evaluation of a process or
product is the life cycle assessment (LCA). The LCA considers a broad range of issues that

1. INTRODUCTION
8 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

SCHEME 1.1.2 Examples of chemical reactions producing toxic (red) and non-toxic (green) waste.

can be quantified by environmental friendliness metrics. These indicators include energy con-
sumption, carbon footprint and emission of other greenhouse gases, potential contributions
to ozone depletion or smog formation, amount of waste generation, and toxicity of the waste
generated. The application of EQ or LCA, however, requires extended analysis before a pro-
cess can be implemented, and this often contributes to the cost of a product. Nonetheless, as
highlighted by the original 12 principles, it is always better (and likely less expensive) to pre-
vent problems by a thorough analysis than to clean up after an environmental disaster.

1.1.3 GREEN CHEMISTRY AND THE ENVIRONMENT

It is not within the scope of this text to provide a comprehensive examination of environ-
mental chemistry. Indeed, many fine textbooks exist on that subject, and our goal is not to
reduplicate such works. Rather, the goal of the various environmental chemistry chapters in
this text is to put into context the impact of human society on the natural world. While the
precise placement of the dividing line between green chemistry and environmental chem-
istry can be debated, it is clear that the entire purpose of green chemistry is to minimize
that impact. This is most evident in principles 1 and 10: waste prevention and the design
of chemicals such that they degrade harmlessly in the environment. Obviously, then, the
practice of green chemistry requires an understanding of those degradation pathways
and an understanding of what happens to the waste and by-products when they are
emitted. Although various textbooks exist that provide greener pathways for industrial
synthesis, for example, there is an alarming shortage of texts that train green chemists to
think about the chemistry of their products in the wild. With this work, we hope to begin
to bridge that gap.

1. INTRODUCTION
 1.1.3 GREEN CHEMISTRY AND THE ENVIRONMENT 9
It may come as a surprise to some readers that society has long been aware of the impacts
of science and industry on the environment. The Mishnah laws of first- and second-century
Israel specified that threshing floors, leather tanneries, and lime kilns be removed 50 cubits
from the city to reduce exposure to airborne pollutants, and that flax stems be soaked at least
4e5 m from any vegetable fields to prevent water pollution from affecting the neighbor’s
food crops. The impetus for the construction of the Roman aqueducts was to transport clean
drinking water, as the Tiber had become so fouled with human waste. English laws attemp-
ted to curb pollution from the burning of coal as early as 1273, but the wave of the Industrial
Revolution overwhelmed those early efforts.
Even if we as a species were unaware of our effect on the environment, there has been
pollution as long as there has been civilization. There is evidence in ice core data that the
expansion of agriculture by the Romans and the cultivation of rice by the Han dynasty in
China, both in 1st century BCE, led to measurable increases in global methane concentrations.
Looking even further into the past, there is clear evidence of heavy metal pollution of soil and
water arising from metallurgy as long ago as 1500 BCE and continuing for nearly 2000 years.
Indeed, significant levels of these pollutants measured in modern lakes may in fact be
sourced to ancient industry rather than to more modern endeavors.
Ancient impacts aside, it is clear that since the Industrial Revolution the scale and the char-
acter of the pollution has fundamentally changed. Perhaps we can date this to 17th century
England, when John Evelyn wrote of the damage caused by London’s coal smoke in his
pamphlet, Fumifugium, although even this document refers to the history of England’s prob-
lems with coal dating back to the middle ages. Perhaps it dates to the cholera outbreaks
around the world in the 19th century, caused by contaminated drinking water in the growing
cities; or perhaps the burning of the Cuyahoga River, most notably in 1952, a result of the
accumulation of oil slicks on its surface; or the smog incidents of the mid-20th century in Lon-
don, and Pennsylvania and Belgium, in which thousands of people died; or the widespread
use of DDT after World War II, now found in animal tissue samples from the most remote
locations on Earth; or the tragedy of Love Canal, where people living in houses built on a
landfill were exposed to toxic waste as the containers leeched into the soil; or the 1984 Union
Carbide disaster in Bhopal, India, where 4000 people died from exposure to methyl isocya-
nate; or the photochemical smog in Los Angeles during the 1980s, or that of Mexico City,
Delhi, and Beijing today; or Three Mile Island, Chernobyl, and Fukushima, reminding us
that the wonders of the nuclear age bring with them new dangers. It is true that human sci-
ence and technology have combined to produce a society that is awe inspiring. However, it is
also true that this society has wreaked havoc on our natural environment.
According to most geology textbooks, the most recent geological epoch began nearly
12,000 years ago with the dawn of the Holocene. However, the conversation in recent years
has recognized the shift in mankind’s ability to harm our planet on a global scale. In 2000,
Nobel laureate Paul Crutzen argued for the use of the term Anthropocene, referencing that
our current period is defined by our species more than by any other characteristic. Crutzen
did not coin the phrasedit had been used by Soviet scientists as early as the 1960s, and
perhaps even predates them. However, the dawn of the 21st century was also the dawn of
widespread acceptance of the harsh realities of global warming and its associated climate

1. INTRODUCTION
10 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

changes. Already the pH of the oceans is dropping, leading to the distinct possibility of mass
extinction of life in the sea. The ongoing “Holocene extinction” is removing up to 140,000 spe-
cies from our planet each year, a rate that rivals that of the extinction that took the dinosaurs.
Left unchecked, the modern tail of the Industrial Revolution threatens all life on the planet.
Often doomsayers will claim that we are on the verge of destroying the planet itself. This is
presumably hyperboledthe planet has seen mass extinction before, and will again. However,
the same cannot be said of the human race.
To be clear, the authors do not believe that we are witnessing the end of human civiliza-
tion. Because one way or another, our destruction of the environment will be checked. At
some point, the financial arguments against change will fall by the wayside as the need for
change becomes more urgent. Whether driven by government intervention or an industrial
recognition of the bottom line, at some point the solutions to these problems will become
financially competitive with the cost of doing nothing. It falls to practitioners of green chem-
istry to provide the solutions at a cost that obtains that result as soon as possible.

1.1.4 REGULATORY AGENCIES

Environmental regulatory agencies are part of life in most countries. They provide guid-
ance for new developments and oversight for existing industrial technologies as well as com-
mon aspects of life, from the disposal of restaurant waste to application of cosmetics. Since
the detailed discussion of environmental law and regulatory agencies is far beyond the scope
of this introductory chapter, here we describe several of most visible regulatory agencies that
are charged with managing the environmental issues in the largest economies.

1.1.4.1 International: The United Nations

The United Nations (UN) took a leadership role in facilitating discussions, organizing in-
ternational conferences where the member nations could develop strategies to combat envi-
ronmental issues. Per the suggestion of Sweden, the UN organized the United Nations
Conference on Human Environment in Stockholm in 1972. The assembly agreed upon the Stock-
holm Declaration, which put forth 26 principles to guide environmental protection and devel-
opment. The World Commission for Environment and Development, first chaired by Gro Harlem
Brundtland (former Prime Minister of Norway), was established in 1983. It was tasked with
generating a report on the environment and with making recommendations for a worldwide
sustainable and environmentally benign economic development to 2000 and beyond. The
assessment and recommendations of the commission were published in a book entitled
Our Common Future (Oxford University Press) in 1987. Since then, the UN has spearheaded
efforts on various environmental issues.
One enormously successful early agreement was the Montreal Protocol (1987) to combat the
depletion of ozone over the poles in spring, commonly referred to as the “ozone hole.” The
global ban on chlorofluorocarbons and related compounds succeeded in stopping the deterio-
ration, and the atmosphere continues to recover slowly but surely. The success of the Montreal
Protocol was remarkable; former UN Secretary-General Kofi Annan hailed it as “perhaps the

1. INTRODUCTION
 1.1.4 REGULATORY AGENCIES 11
single most successful international agreement to date.” This is in marked contrast to the inter-
national community’s much slower and more contested response to global warming. The most
important and well-known treaties to combat climate change are the Kyoto Protocol (1997) and
the Paris Agreement (2015). The Kyoto Protocol described the commitment of the participating
countries to reduce the emission of greenhouse gases. The Paris Agreement, the result of the UN
Framework Convention on Climate Change, while aiming for a similar goal, made recommenda-
tions on how much to limit the annual temperature increase of the planet. As of today, 131
(out of 197) parties have ratified the Paris Agreement.
This leads us to mention the weaknesses of some of the UN-facilitated agreements. Given
the nature of the UN, these treaties are negotiated by the governments of the participating
countries. However, once the agreement is signed, the law-making bodies of the nations
have to ratify it; thus the countries essentially commit themselves by their own laws to up-
hold the agreement. That has been so far the Achilles’ heel of many such agreements: several
countries ratified it, whereas many others did not. The reasons for not ratifying vary from
country to country and depend on economic development, energy/fuel production and
use, and many other socioeconomic factors. Unfortunately, many of these agreements are
purely political and do not include the development of actual technologies as a response
to global warming.

1.1.4.2 International: International Organization for Standardization

The International Organization for Standardization (ISO) is a nongovernmental interna-
tional organization with 161 members that are commonly the similar standards bodies of
the member countries. In 1946, 25 countries decided to establish the ISO to provide unified
industrial standards. It is a forum to share knowledge and develop consensus-based inter-
national standards that help innovation and offer solutions to global problems. Although
the ISO is not specifically an environmental organization, many of its approximately
21,000 international standards are related to environmental and safety issues. The most
relevant of these are ISO1400-Environmental Management, ISO45001-Occupational Health
and Safety, ISO50001-Energy Management, ISO22000-Food Safety Management, and
ISO31000-Risk Management. However, it is important to note that similar to the above
UN recommendations the ISO standards are applied voluntarily by the individual organi-
zations (e.g., corporations) of the member countries.

1.1.4.3 United States

We have already introduced the US EPA earlier in this chapter, which takes the lead on
many issues from toxic waste cleanup to mitigation of global warming. The EPA fulfills the
roles of a regulatory agency and recommends changes and additions to current environ-
mental laws that Congress considers. The EPA, however, is not just an agency that
regulates and enforces regulations. It has a broad network of research facilities, institutes
in which far-reaching scientific research is conducted in several areas of environment-
related sciences, from sustainable synthesis to atmospheric chemistry. In addition,
all US states have their own EPA-like agencies, sometimes just one umbrellalike

1. INTRODUCTION
12 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

agency; however, in many states, there are separate entities to deal with separate issues
(water, agriculture, etc.).
The National Oceanic and Atmospheric Administration (NOAA) (part of the Department of
Commerce) also concerns itself with environmental issues. It grew out of some of the oldest
government branches dedicated to the environment, including the United States Coast and
Geodetic Survey, which was first established in 1807 by Thomas Jefferson. In 1970, President
Nixon created NOAA from several other agencies, including the Weather Bureau (1870) and
the Bureau of Commercial Fisheries (1871). Its current substructure includes the National
Weather Service, the National Ocean Service, and the Environmental Satellite, Data and In-
formation Service, among others. Through these divisions it contributes by observing and
communicating data related to global warming and atmospheric and water pollution. Similar
to the EPA, the NOAA has facilities that conduct active research on the environment.

1.1.4.4 Canada
The Environment and Climate Change Canada is the major government agency that reg-
ulates and enforces environmental protection in Canada. It was established in 1971 by the
Department of Environment Act to assess, monitor, and protect the environment, including
providing basic weather and meteorological services to the citizens of Canada. The agency’s
responsibilities are those of a typical environmental agency: making environmental deci-
sions/regulations based on available evidence, especially with regard to pollution prevention
and the like. In addition to its support to policy making, the agency is a supporter of a broad
variety of environment-related research through many funding initiatives. Just as in the
United States, the Canadian Provinces have their own environmental agencies.

1.1.4.5 European Union

The European Union established its main environmental agency, the European Environ-
ment Agency (EEA), in 1990, which became operational in 1994. The agency has 33 member
states (28 EU members and Norway, Iceland, Lichtenstein, Switzerland, and Turkey). Six
additional countries from the Balkans work with the Agency as cooperating countries. Given
the nature of the European Union, most member countries had established their own envi-
ronmental agencies long before the EEA, such as the Federal Environmental Agency (and
others) in Germany (1974), the Environment Agency in the United Kingdom (1995), the Min-
istry of Ecology, Sustainable Development and Energy in France (since 1974 under various
names), just to name a few. Thus the EEA’s role is mainly to provide independent informa-
tion on the environment. They are the major EU information source for policy makers as well
as the general public, integrating the principals of sustainability into political and economic
decisions.

1.1.4.6 Russia
The Ministry of Natural Resources and the Environment (MNRE) is the main policy-making
and enforcing body in Russia. Russia has had some sort of natural resources governmental

1. INTRODUCTION
 1.1.4 REGULATORY AGENCIES 13
unit since the 18th century. The MNRE was created in 2008 by merging the former Ministry of
Environment and Ministry of Natural Resources (both founded in 1996, after the collapse of
the Soviet Union). It has several agencies such as the Federal Service for the Supervision
of Natural Resources, the Service for Hydrometeorology and Environmental Monitoring,
and separate agencies for subsoil, water, and forestry management.

1.1.4.7 China
Immediately after the Stockholm Declaration, China created its Environmental Protection
Leadership Group (1974) and environmental protection became a state policy in 1983 with the
Environmental Protection Commission. After several upgrades and name changes, the cur-
rent Ministry of Environmental Protection (MEP) was established in 2008. China, the most
populous country in the world, has seen an unprecedented industrial growth and urbaniza-
tion since the 1980s, which has brought with it significant environmental problems, including
water and air pollution. The major mandates of the MEP include the design, organization,
and implementation of national policies, programs, and plans for environmental protection,
policy making, and regulations and leading the response to major environmental problems.
In addition, it carries out environmental protection science and technological activities
including the organization of projects on engineering, and facilitates the development of envi-
ronmental technology management systems as well as conducts and organizes environ-
mental education.

1.1.4.8 India
India, as the second most populous country in the world, with rapidly growing industrial
activity has its fair share of environmental problems. In addition to industrial accidents, wa-
ter shortages, soil problems (e.g., exhaustion, erosion), deforestation, and, especially in the
major metropolitan areas, air and water pollution affect many areas in the country. To
address these problems, the Central Pollution Control Board (founded in 1974) created the
National Air Quality Monitoring Program. Due to the inspirational power of the Stockholm
Declaration, in 1972, the National Council for Environmental Policy and Planning within the
Department of Science and Technology was established to protect the environment. This
council later became the Ministry of Environment and Forest, which is India’s most important
governmental agency for environmental protection. The Environment Protection Act of 1986
is one of the major early milestones in its actions. The current legislative framework includes
climate change, deforestation management, coastal regulations zones, and pollution control,
among many other tasks.

1.1.4.9 Japan
Many countries started seriously considering environmental protection only after the
Stockholm Declaration (1972), whereas Japan was among the first countries to enact environ-
mental regulations after four major pollution outbreaks occurred in the country in the
1950se60s. In 1958, a water quality conservation law was passed, which was followed in

1. INTRODUCTION
14 1.1 GREEN CHEMISTRY: HISTORICAL PERSPECTIVES AND BASIC CONCEPTS

1962 by a smoke and soot emission control law. In 1971, the first Environmental Agency
was established in Japan. Currently, the Ministry of the Environment is the branch of the
Government of Japan that is responsible for activities related to the environment. This agency
has broad responsibilities, as it is involved in policy making concerning waste management
and recycling, pollution control, nature conservation, wildlife protection, air quality and
transportation, as well as health and chemicals, and is also charged with the care of Japan’s
national parks.

1.1.4.10 Australia
The Department of Environment and Energy (DEE) is the major government agency in
Australia in charge of environmental protection. It designs and implements government pol-
icies and programs to protect and conserve the environment, water, and heritage, and pro-
motes climate action. DEE deals with a broad array of activities, such as far-reaching
environmental protection of Australian air, land, and water; managing the national parks;
conducting research on environmental problems; as well as acting as a funding agency for
environmental research. Similar to the United States and Canada, the Australian states also
have their own individual environmental agencies.

1.1.5 CLOSING THOUGHTS

The nature and scope of the field of chemistry has changed dramatically since the days of
the alchemists. Chemistry impacts nearly every aspect of modern life. The progression has
not always been smooth, and there have been significant missteps along the way. However,
the harnessing of chemistry in the interest of society has brought us to a modern age unimag-
inable by our ancestors. Toward the end of the 20th century, the field of green chemistry was
born from a recognition of those missteps and a desire to minimize the impact of human so-
ciety, and especially of human industry, on our natural environment. The core philosophy
can be expressed in various ways, with lists of principles and metrics. The goal is always
the same: benign by design.
Societal impact on the environment presents us with multiple pressing problems, which
can be addressed by various means. All things considered, it would be preferable if chemical
solutions could be found before political solutions are required. This could entail, for
example, a reimagining of an existing technology (e.g., the electric car, biodegradable plas-
tics), a means to reduce the environmental impact (e.g., solvent-free synthesis, exhaust plume
scrubbers), or a technology to remove existing pollutants (e.g., CO2 sequestration, bioreactor
landfills). By finding a way for companies to profit from the mitigation of pollution, green
chemists can encourage society to adopt these changes much more quickly and completely
than would a reluctant culture enforced by governmental policies. This is not to minimize
the importance of effective policies to control pollution; as we have seen, these efforts are crit-
ical to solving national- and global-scale problems. However, one of the goals of green chem-
istry must be to better facilitate widespread adoption of these new technologies and new
methodologies by making them acceptable for everyone.

1. INTRODUCTION
 PROBLEMS 15

PROBLEMS
1. Calculate the atom economy and E-factor of the following processes:

2. Reactions A and B are two different methods producing the same product P. Reaction
A has a theoretical atom economy of 100% with an actual yield of 65% for the product.
Reaction B only possesses 85% atom economy, with 95% actual yield for the product.
Which reaction is greener, that is, generates less waste considering 100% conversion of
A and B?
3. Research the similarities and differences between environmental quotient and life cycle
assessment.
4. Select any chemical product and design a green pathway for it considering the com-
plete process (all details from finding/manufacturing starting materials, other compo-
nents, minimizing environmental impact, etc.). Show your work in a flowchart from
the beginning of the manufacturing phase to the likely fate of the product/postproduct
in the environment.

1. INTRODUCTION
Another random document with
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 Cold water, taken a swallow at a time at intervals during the day,
has a tonic effect upon the relaxed muscles. It also incites the flow of
gastric juice.

Ulcer of the Stomach. Where this condition is severe,

accompanied with severe pains and vomiting of blood, the dietetic
treatment is to give the nourishment through the rectum for from five
to ten days. Then follows a period of ten days milk diet, with bouillon,
barley water, a beaten egg, and once a day, after the third day,
strained oatmeal gruel.
Limewater is added to the milk to avoid the formation of leathery
curds and to neutralize the acids of the stomach. The patient is given
half a cup of milk every hour for three days, from 7 A. M. to 9 P. M.
From the third to the tenth day increase the quantity to one cupful,
then to a cup and a half and lengthen the periods between feedings
to two hours. If the milk is brought to a boil before the limewater is
added, it digests more readily.
After ten days, for the succeeding ten days the nourishment
should be given every two hours and the diet varied by semi-liquid
foods, such as gruels, toast water, soft boiled egg (once a day) beef
juice, two softened crackers (once a day) gelatin, buttermilk and
strained soups.
After twenty days the patient, if all is well, may very gradually
resume a normal diet, beginning with baked potatoes, softened
toast, lamb chops, a small piece of steak or white meat of chicken. It
is imperative that all food, liquid or solid, be thoroughly mixed with
saliva and that solids be chewed to a pulp.
Liquids must not be swallowed either hot or cold, but about body
temperature. Cold water may be taken into the mouth when more
palatable than warm and held there until about body temperature
before it is swallowed. All liquid should be sipped, not swallowed in
gulps.
 Cancer of the Stomach. Since the growth most often obstructs
the pylorus, the stomach is usually dilated and the general directions
for dilation of the stomach should be followed. If the food will not
digest in the stomach, one must resort to rectal feeding. Where
gastric digestion is near normal, the general principles of diet for
ulceration of the stomach should be followed.

Most cases of intestinal difficulties may traced to

Intestinal a clogged condition, either due to a weakness of
Disorders the nerves and of the intestinal muscles, and a
resultant weak peristalsis, which does not strongly
move the mass along its course, or to a failure of the liver to
discharge sufficient bile to lubricate the mass. If the waste is not
promptly moved through the intestines, irritation may result and the
poisons from bacterial fermentations will be absorbed by the system.
Deranged stomach digestion also interferes with the digestion in
the intestines.

Constipation. The causes of this difficulty are so varied that it can

seldom be regulated by diet alone. It can be helped. A large number
of cases of chronic constipation are due to the failure to respond to
Nature’s call at a regular time each day, thus establishing a regular
habit at a certain hour. Many others are due to the weakness of the
muscular walls of the intestines or to the nerves controlling them. In
this event the intestinal peristalsis is weak. Still another cause is a
failure of the liver to discharge sufficient bile into the intestines to
lubricate the foeces. Many chronic cases are due to the pill and drug
habit. Where one continues to take pills, the condition brings a result
similar to the feeding of “predigested” food,—if the work is done for
the organs they become lazy and rely upon artificial aid. Every part
of the body requires activity for strength.
If the straight front corset cramps the intestines it may cause
constipation by restraining their normal exercise during movements
of the body in walking, etc. Every woman who wears the straight
front corset should take exercises for the intestines morning and
night.
The most natural relief for constipation is exercise,—particularly
exercise directed to the muscles of the intestines and to the nerve
centers controlling them.
Such foods as are laxative in effect, with the free use of water are
helpful. Figs and raisins (due to their seeds), prunes, dates, grapes,
apples, and rhubarb are laxative, due to their acids. These have best
effect when eaten just before retiring.
Oatmeal, or any cereal containing the bran, is laxative,—such as
bran bread or green corn.
As must be inferred from the above statement, the cause of the
difficulty must first be reached.
Children should be trained to attend to Nature’s call regularly
every day. The best time is shortly after breakfast.

Enteritis. (Inflammation or Catarrh of the Intestines) is similar

in its nature to Gastritis or Catarrh of the Stomach and is treated in a
similar manner.
Acute Enteritis, as Acute Gastritis, is usually caused by a strong
irritant,—either by some food which disagrees, or by a mass of
undigested food. A fast of two or three days is the initial dietetic
treatment. A free drinking of water not only soothes the irritated
intestines but it cleanses the intestinal tract and assists the kidneys
in eliminating elements of fermentation; if these are not eliminated,
they will absorb into the blood.
 Physicians usually give a course of calomel and castor oil to
eliminate all intestinal contents.
After the fast, a liquid and semi-liquid diet is followed until
inflammation is relieved. Milk, strained gruels, broths, strained
soups, buttermilk, eggs (soft cooked or raw), beef juice, barley water,
custards, gelatines, soft puddings, etc., are the foods most
nourishing and causing least irritation.
All irritating foods as coarse vegetables, pickles, acid fruits and
fruits with coarse seeds, candies, beer, wines and salads should be
omitted.
Chronic Enteritis has the same general cause as Acute Enteritis,
though its onset is slow and it takes a correspondingly longer time to
correct.

Dysentery, if acute, demands complete rest in bed. The diet in

both Acute and Chronic cases must be confined to easily digested
foods, such as peptonized milk (see page 244), boiled milk, pressed
meat juice, and the white of egg, beaten and served with milk.
Blackberry brandy, and tea made from wild cherry bark, tend to
check the inflammation.
During convalescence, care must be taken not to over-feed. Begin
a more liberal diet with a more liberal allowance of beef juice,
gradually adding tender beef steak, roast beef, fish, white meat of
chicken, eggs, custards, wine jelly, dry toast, blancmange, well
boiled rice and other easily digested food. The beef and egg are
particularly valuable, because of the anaemia occasioned by the loss
of blood.

is sometimes necessary in cases of ulcer,

Rectal Feeding cancer, or tumor, along the digestive tract. Since
food is not absorbed in the large as readily as in the small intestine,
the strength cannot be fully maintained through rectal feeding. In
cases where the stomach is not able to digest the food, it is the best
expedient, however, until the functioning of the stomach is re-
established.
The rectum should be prepared about an hour before the feeding
by a full injection of water, to thoroughly cleanse the intestine. Place
the patient on his side with the hips elevated. If for any reason he
cannot lie on his side, let him lie on his back and elevate the foot of
his bed. After the water cleansing, inject two or three ounces of
water in which a small pinch of salt (6%) has been added and let it
go high up into the rectum.
Two to three ounces four to five hours apart is the desirable
quantity of rectal nutrition for an adult. The white of egg, beef juice,
and milk, all peptonized, are the best foods. The pancreatic trypsin,
sold in preparations of “pancreatin” is best. Unless milk is peptonized
the casein will be difficult to absorb. The food should always be
salted, as salt aids the absorption.
The white of egg should be diluted with four or five times its
volume of water; to beef juice add an equal volume of water. The
yolk of egg contains too much oil to absorb readily. Fats are not
absorbed through the rectum. If egg and beef juice are used without
milk, a little sugar may be added. Milk contains sugar in proportion.
It is not advisable to inject wine as it interferes with absorption of
other foods.
The nutriment should be forced eight to ten inches up into the
rectum to insure absorption. This can be done by using a small
injection point on a rubber tube and gently and patiently turning it as
it is inserted. The tube may be oiled to prevent irritation.

The liver is not, in a strict sense. a digestive organ, but it is very

dependent upon them, as all products of digestion must pass
 through it and the starches, sugars and proteins,
Derangements after they enter the blood, undergo chemical
of the Liver changes here.
For a fuller understanding of the reasons for the following
suggestions regarding diet for the liver, the writer would request a re-
reading, at this point, of the chapter upon the “Work of the Liver”
upon pages 81 to 92.
It will be recalled that the liver acts, not only upon proteins, sugars,
and starches,—the nourishing foods, but it also stands guard over
poisonous ferments, due to putrefactions absorbed from the
intestines, rendering them harmless; to a limited extent it also
oxidizes the poisons of alcohol. The fats also pass through the liver.
Since all products of digestion must pass through this organ, it is
easy to see how it may be overworked, for it is an undisputed fact
that most people eat more food than is required to maintain the body
in nitrogenous equilibrium and to supply the necessary heat and
energy.
After the gorging of a heavy meal, the overloaded blood and liver
express themselves in a sluggish brain and one feels mentally, as
well as physically, logy, or overloaded.
Since both sugar, carbohydrates and protein undergo chemical
changes in the liver, it is evident that a diet consisting of an excess of
either, must overwork the liver, not only through the nutritive food
elements absorbed, but through the toxic substances which must be
absorbed,—due to the excessive amount of food not being digested
as readily as a smaller amount. If the food remains in the intestines
too long, it is attacked by the bacteria always present there,
fermentation results and poisons are absorbed and carried to the
liver, where they must be broken down and rendered harmless, so
as not to affect other parts of the system. If for any reason the liver is
diseased, overloaded, or its action is sluggish, it will not promptly
oxidize these toxins.
One of the most important corrective agencies for an inactive liver
is exercise directed to this organ, to bring a free supply of blood, and
deep breathing of fresh air. It is apparent that the blood must carry its
full quota of oxygen to assist in oxidizing both the nitrogenous waste
and the poisons; and it must be remembered that the liver must
oxidize the waste from its own tissues, as well as from other parts of
the system.
It is apparent, from the above, that the regulation of diet for an
abnormal liver must be more in the quantity than in the quality of
food and in the perfect digestion. It depends also upon the activity of
the intestines, since the poisonous products of imperfectly digested
and fermenting food, not being regularly eliminated, must be
absorbed and carried to the liver. It is to free the intestines of the
waste containing the toxins that physicians give calomel and other
strong cathartics, to work off the toxins. These cathartics also work
off foodstuffs from the intestines before they are absorbed, so that
the liver has more rest.

Torpid Liver or Billiousness. This condition is due to the

sluggish action of this organ and a consequent failure to eliminate
the bile through the bile ducts into the duodenum. It may be caused
by inactivity and a resultant sluggish circulation of blood, to overwork
of the liver, due to overeating, to breathing of impure air, or to
insufficient breathing of pure air. It may also result from constipation
and a resultant absorption of toxic matter as described above.
Many cases of billiousness are occasioned by obstruction of the
opening of the bile ducts into the intestines, which is often
occasioned by an excess of mucus in the duodenum. In such cases
exercise for the intestines is clearly indicated.
In the bending, twisting and squirming movements which the infant
in the cradle makes, the liver is regularly squeezed and relaxed. The
same is true in the free movements of an active child at play. If
during adult life these same free movements of bending and twisting
the trunk were continued daily and correct habits of free breathing of
pure air were established, there would be little call for “liver tonics.”
 The elaboration of carbohydrates in the liver is an important part of
its work and in case of inactive liver the sugars and starches should
be limited, allowing that function to rest. Yet it is a mistake to allow a
diet too rich in protein. The best method is to cut down the quantity
of a mixed diet.
Two glasses of water an hour before breakfast followed by brisk
exercise for the vital organs and deep breathing are important. The
daily action of the bowels is imperative. In extreme cases a fast of
two or three days, with a copious use of water, is recommended.
Following this fast the diet should consist of easily digested foods,
eliminating those containing starch and sugars in too great
proportions, and it should be as limited as possible, consistent with
the actual necessity for rebuilding and for energy.
Some authorities restrict fats in a diet for billiousness but the
presence of fat in the duodenum stimulates the flow of pancreatic
juice, which in turn stimulates the secretion of bile.
Lemon stimulates the action of the hepatic glands and thus tends
to increase the liver activity.
There is a prevalent thought that eggs and milk cause sluggish
liver action. There is no physiological reason for this if too much food
is not eaten. One often loses sight of the fact that milk is a food as
well as a beverage, and that when milk constitutes an appreciable
part of the diet other foods should be limited accordingly.
The DIET may be selected from the following:[10]
Soups.—Light broths and vegetable soup with a little bread toasted
in the oven.
Fish.—Raw oysters, fresh white fish.
Meats.—Mutton, lamb, chicken or game.
Farinaceous.—Whole wheat or graham bread and butter, toast
buttered or dry, toasted crackers, cereals in small portions.
Vegetables.—Fresh vegetables, plain salads of watercress, lettuce,
and celery.
Desserts.—Gelatins, fruits, cornstarch, ice cream, junket, simple
puddings,—all with very little sugar.
 Liquids.—Hot water, lemonade, orangeade, toast water, buttermilk,
loppard milk and unfermented grape juice,—not too sweet.
AVOID.—All rich, highly seasoned foods, candies, cheese, pies,
pastry, pan cakes, or any fried foods, salmon, herring, mackeral,
bluefish, eels, dried fruits, nuts and liquors of all kinds.

The diet for gall stones need have no reduction

Gall Stones in protein nor carbohydrates, since the oxidation,
or the chemical action upon sugars is not
interfered with. The presence of fat in the duodenum increases the
flow of pancreatic juice which, in turn stimulates the flow of bile, so
olive oil is often recommended in case of gall stones.

is a serious disturbance of nutrition. It is known

Diabetes and tested by the appearance of sugar in the urine.
However, the conclusion should not be drawn that
one has diabetes if the urine test for a day shows sugar. This may be
due to an excess of carbohydrates, particularly of sugar in the diet a
day or two previous and all trace of it may disappear in a day. If
continued tests for some period show an excess, nutritional
disturbances are indicated.
The most usual form of diabetes is diabetes mellitus. It is
supposed to be due to a disturbance in the secretions from the
pancreas. Experiments have shown that the general process of
putting the carbohydrates in condition to be absorbed into the blood
is controlled by a secretion from the pancreas.
The difficulty which confronts the dietitian is to prescribe a diet
without carbohydrates which will keep up the body weight and not
disturb the nutritive equilibrium. The diet must consist of protein and
fat and one danger is in the tendency to acetic and other acids in the
blood, which involves the nervous system. The patient has a craving
for sugars and starches, but the system cannot make use of them,
and the heat and energy must be supplied by fats. While, as a rule,
the craving for certain foods is an indication that the system needs
the elements contained in it,—this is true in the craving of the
diabetes patient for carbohydrates,—yet the desire must not be
gratified, because of the inability to digest them.
There is often a distaste for fat, but its use is imperative and in
large quantities, because the weight and general vitality must be
maintained. The effort of the physician is to get the system in
condition to use carbohydrates.
Fats may be supplied in the yolk of egg, cream, butter, cheese,
bacon, nuts, particularly pecans, butternuts, walnuts and Brazil nuts.
In beginning a diet, the change must not be too sudden. At least a
week’s time should be allowed for the elimination of all sugar and
starch. Begin by eliminating sugars and next bread and potatoes.
Van Noorden gives the following diet, free from carbohydrates,
which has been in general use in Europe and America.
BREAKFAST.
Tea or coffee, 6 ounces.
Lean meat (beefsteak, mutton chop, or ham), 4 ounces.
Eggs one or two.
LUNCH.
Cold roast beef, 6 ounces.
Celery, or cucumbers, or tomatoes with salad dressing.
Coffee, without milk or sugar, 2 ounces.
Whisky, drams, diluted with 13 ounces of water.
DINNER.
Bouillon, 6 ounces.
Roast beef, 7½ ounces.
Green salad, 2 ounces.
Vinegar, 2½ drams.
Butter, 2½ drams.
Olive oil, 5 drams, or spinach with mayonnaise, large portion.
Whisky, 5 drams, diluted with 13 ounces water.
SUPPER, 9 P. M.
Two eggs, raw or cooked.

Van Noorden includes alcohol, in whisky, in his diet and most

physicians follow the theory that whisky or brandy aids in the
digestion and absorption of fats; the need is recognized since fats
must be supplied in so large quantities, yet the sweet wines and
beers contain sugar while the sour wines contain acids, which
disturb digestion.
There is a grave question in regard to the advisability of including
alcohol in the diet of a young person afflicted with diabetes and the
greater activity of the young patient will insure more perfect
digestion, so that the physician may not consider alcohol necessary.
Dr. Hall gives the following as a reasonable diet for a diabetic
case, after the first week or two, allowing potatoes.
BREAKFAST.
Tea or coffee, 6 ounces.
Cream, 2 ounces.
Meat, (beefsteak, mutton chops, or ham), 4 ounces.
Bread and butter, 2 slices.
Baked potato, with butter.
LUNCH.
Cold roast beef or cold boiled ham, 6 ounces.
Bread and butter, two slices.
Salad with mayonnaise dressing, egg garniture.
Tea or coffee with cream.
4 P. M.
Egg lemonade or egg orangeade.
DINNER.
Clear soup of any kind.
Roast beef or mutton, or pork.
Potatoes, baked or boiled.
Olives, celery, or radishes.
Side dish of green vegetables.
Bread and butter.
Dessert, milk-egg custard, sweetened with saccharin.
After a week on either of the above diets, in mild cases, sugar will
disappear from the urine. In extreme cases, it may be necessary to
follow this strict regime for two weeks. When the patient begins to
eat a little starch, potatoes and bread are re-instated first. Sugar is
kept out of the diet, except the little in fruit and vegetables, until the
urine shows no trace of it.
The following is a list of foods allowable:
Fresh meat, fish, oysters, clams, lobster, turtle, meat extracts, fats
of all kinds, eggs, such fresh vegetables as peas, beans, lentils,
lettuce, celery, asparagus, cabbage, pickles, clear soups (all kinds),
cheese (all kinds), coffee, tea (without sugar), cream, butter, fruit,
acid drinks and carbonated waters.

In the dietetic treatment of any diseased organ,

Derangements the object must be to give that organ as much rest
of the Kidneys as consistent with keeping up the general nutrition
of the system. The stomach and intestines are so
closely allied that, where one is affected, the other is liable to
affection also, and the dietetic treatment is regulated accordingly. Yet
generally speaking, in stomach disorders the quantity of protein is
limited; in intestinal disorders the starches, sugar and fats are
limited. Since the office of the kidneys is to pass from the system the
soluble salts and the nitrogenous waste, which dissolve in water, the
work of the kidneys in most conditions is aided by a copious drinking
of water. Since uric acid is stimulated by the kidneys, the proteins
should be restricted in the diet, particularly those formed from the
glands of animals,—as liver, sweetbreads, kidneys, also brains.
Potatoes, green vegetables, stone fruits and cranberries aggravate
an acute condition.

Acute Nephritis. In case of inflammation of the kidneys the

excretions are interrupted. In this event the quantity of water should
be limited to three to four glasses a day. In the event that the kidneys
will not excrete the water, the pores of the skin must be kept freely
open by sweat baths to assist in the elimination of waste.
Dr. Hall recommends a milk and cream diet of from three to seven
pints a day, for a few days, according to the case,—two parts of milk
to one of cream. If the urine is scanty, he reduces it to one and one
half pints a day, taken in four or five installments. After the three to
seven days of milk diet he gradually introduces starches and fats.

Brights Disease. This term covers forms of diseases of the

kidneys, associated with albumin in the urine.
Where for any reason the kidneys have difficulty in discharging the
nitrogenous waste of the system, the work of the dietitian must be to
eliminate protein from the diet as closely as may be consistent with
the body necessities. Besides restricting the amount of nitrogenous
foods, the kidneys must be assisted in eliminating the nitrogenous
waste, and the products of the inflammation, by a copious drinking of
water. Hot water and hot diluent drinks are best, such as toast water,
barley water, cream of tartar, lemon and acid drinks. In acute cases
the patient is put on a milk diet of from two to three pints of milk a
day, given one-half pint every three or four hours, diluted with one-
third as much hot water. If the case be a prolonged one, broths may
be included.
Even in cases which are chronic and not acute, it is well to follow a
milk diet for a number of weeks. The quantity of milk, for an
exclusive milk diet, must depend upon the age and size of the
patient as well as upon his ability to exercise. If he is confined to his
room, from five to seven pints of milk a day are sufficient. If he is
taking a great deal of exercise, he may take from eighteen to twenty
glasses of milk a day. If he loses weight on the milk diet, bread and
rice may be added.
It is unwise to begin a milk diet at once, by feeding from eighteen
to twenty glasses of milk a day, but this amount may be
approximated within a week’s time and the change in diet should be
begun by cutting down all meats and legumes and gradually
eliminating starches. In changing from a milk diet to a diet including
more hearty foods, the transition should be gradual.
A. F. Pattee gives the following diet for Brights Disease.
DIET: Soup.—Vegetable or fish soup, broths with rice or barley.
Fish.—Raw oysters or clams, fresh fish broiled or boiled.
Meats.—Eat sparingly, chicken, game, fat bacon, fat ham.
Farinaceous.—Stale bread, whole wheat bread, toast, milk toast,
biscuits, macaroni, rice, cereals of all kinds.
Vegetables.—Onion, cauliflower, mashed potatoes, mushrooms,
lettuce, watercress, spinach, celery, cabbage.
Desserts.—Ripe raw fruits, stewed fruits, rice tapioca, bread and
milk puddings, junkets, cocoa.
Liquids.—Toast water, weak tea, pure water, peptonized milk,
malted milk, fresh buttermilk, milk with hot water, equal parts, whey,
unfermented grape juice.
AVOID.—Fried fish, corned beef, hashes, stews, pork, veal, heavy
bread, batter cakes, lamb, mutton, beef, gravies, beans, peas, malt or
spirituous liquors, tobacco, coffee, ice cream, cake, pastry.
 The condition of the nerves depends upon the
general condition of the system and upon general
Nervous
Disorders nutrition. There is no one food or set of foods
which directly affect any nervous trouble, unless
this trouble be localized by disturbance in some particular organ.
Then the effort must be to correct the difficulty in that organ.
There is no disturbance in any part of the body requiring less
medicine than a disturbance in the nerves. The correction must
come through general hygienic treatment. Regular exercise,
alternated with regular rest periods, the formation of the habit of
complete nerve relaxation, the general regulation of an easily
digested, nutritious diet, with deep breathing exercises, are the best
remedies.
In many cases of nerve debility the nerves seem to be stronger in
the latter part of the day. Where this is the case the hearty meal
should be eaten at this time.

Neurasthenia. In cases of Neurasthenia, or “Tired Nerves,” all

vital organs are more or less affected, because the nerves do not
properly direct digestion, absorption, assimilation or elimination and,
for this reason, the diet should be light and of easily digested foods.
A free, correct breathing of fresh air, day and night, is imperative. It is
important also to thoroughly masticate all food and drink freely of
water. A change of thought, induced by a change of scene or
companions, is helpful.

This difficulty is usually the result of high living. It

Gout most often attacks people past middle age, who
have indulged in rich pastries, puddings, meat
three times a day, or who have frequently indulged in alcohol.
 Being supposedly caused by an excess of uric acid and other
waste deposited in the joints, resulting from too much protein and an
insufficient elimination of the waste of the system, the dietetic
treatment must be a low protein diet. Alcohol is absolutely prohibited
and the quantity of carbohydrates and fats must be cut down as well
as the protein.
In acute cases a diet of bread and milk, or toast and milk, with light
vegetable broths should be followed for one to three days.
In chronic cases the diet may consist of the following:[11]
Soups.—Vegetable broths.
Fish.—Fresh fish, shell fish, raw oysters.
Meats.—It is better to omit all meats. If meat is eaten at all, it should
be confined to game, chicken and fat bacon.
Farinaceous.—Cereals, crackers, dry toast, milk toast, macaroni,
graham or whole wheat bread, rye bread, oatmeal and any of the
breakfast foods.
Nuts.—With salt.
Vegetables.—Celery, lettuce, watercress, all greens, with vinegar,
string beans, green peas, potatoes, carrots and beets.
Fruits.—All fruits, stewed or fresh. Unpeeled apples are especially
recommended. (Greens, with vinegar and unpeeled apples increase
the action of the kidneys.)
Desserts.—Plain puddings, junket, rice, stewed or fresh fruits.
Liquids.—Pure water, toast water, barley water, butter milk, malted
milk, milk.
Eat eggs sparingly and in severe cases, not at all.
AVOID.—Alcohol, coffee, tobacco, dried fruits, nuts, cheese,
candies, pastries, pies, spices, rich puddings, fried foods, vinegar,
pickles, lemons, rhubarb, mushrooms, asparagus, sweet potatoes,
tomatoes, gravies, patties, rich soups, lobster, salmon, crabs,
mackeral, eel, veal, pork, goose, duck, turkey, salted, dried, potted or
preserved fish or meat, (except bacon).
 Since the medical profession is unable to
Rheumatism. determine just what rheumatism is, it is difficult to
prescribe a diet. The theory so long believed that it
is an excess of uric acid in the system is no longer held by most of
the advanced physicians. Some authorities hold that it is a nerve
difficulty; others that it is an excess of lactic acid. Some authorities
put one on an entire meat diet, in case of rheumatism, and others
entirely exclude meat. Uric acid may accompany the disease.
Assuming that it is due to the failure of the system to promptly
eliminate its waste, whether this failure to eliminate be through a
weakened condition of the nerves, and the consequent failure to
properly direct the body activities, the correction of the difficulty must
lie in building up the general vitality and in aiding the system in its
elimination. Hot sweat baths, a free use of water and a free use of
fruits, particularly the citrous fruits, such as lemons, oranges, limes,
etc., are desirable, because they increase the alkalinity of the blood.
The acid unites with other acids of the body acting as a re-agent.
Often when the acids of the stomach are strong, sodium carbonate
(baking soda) produces an alkaline reaction.
The diet should be cut down in quantity. Meat may be eliminated if
an excess of uric acid exists and the above suggestions under the
diet for Gout be followed.
Fruit juices should be used freely because of their alkaline reaction
and because of their diuretic effect. Lemonade, orangeade and all
fresh fruits and vegetables are diuretic.
Regular exercises, until the body is thoroughly heated, deep
breathing of pure air day and night and a copious drinking of water
are necessary.

Interference in the action of the kidneys is apt to

Uremia or result in a retention within the system of the
Uremic elements, which the kidneys, in normal condition,
Poisoning eliminate from the system, such as urea, uric acid,
 urates, sulphuric acid, sulphates, sodium
phosphate, xanthin bodies and conjugated sulphates. These
substances are not thrown off by the skin, or by the lungs, and must
all be eliminated through the kidneys. They are the result of the
oxidation and the breaking down of the proteins of the body. If the
kidneys do not throw these off, the result is Uremic Poisoning, and
the dietetic treatment must be to cause a free action of the kidneys
by the use of diuretics. Of these the citrous fruits, (lemons, oranges,
limes, etc.,) are the best; they neutralize acids and produce an
alkalinity of the blood. They should be used freely.
Meats, eggs and legumes should be eliminated from the diet. A
free drinking of water, milk with limewater, cereals, buttermilk,
kumyss, barley water, toast water, lemonade, orangeade, vegetables
and fruit should constitute the diet. Exercise and free breathing of
fresh air are imperative. All food should be thoroughly masticated.

An excess of uric acid may not always cause

Excess of Uric uremic poisoning, but it indicates an excess of
Acid protein in the system above the amount eliminated
by the kidneys and the skin. This excess is often
the cause of chronic ailments, such as bronchitis, asthma, hay-fever,
severe nerve depression, gout, rheumatism, neuralgia, tonsilitis,
grippe, influenza, colds, etc.
The natural relief is to control the diet, supplying less protein and
to increase the elimination through a free action of the kidneys, of
the pores of the skin, and of the lungs. Systematic exercise, deep
breathing, a copious drinking of water and fresh air day and night,
are the best reliefs.
One may either eliminate the proteins from the diet, or may cut
down the entire quantity of food, and, by exercise, breathing, a
freedom of the pores of the skin and a free drinking of water, so as to
create an activity of the kidneys, may continuously eliminate more
uric acid than is consumed in the food.
 The regulation of the quantity of the food, rather than the cutting
down of the proteins and the feeding of a larger proportion of
starches, is the course pursued where one is inclined to an excess of
uric acid and still has an excess of fat.
In case of an excess of uric acid in thin persons, such proteins
food as meat and eggs may be eliminated and the diet consist
almost wholly of carbohydrates and fats.
The diet is the same as that given above for Gout.

All diets for obesity must be prescribed for the

Obesity individual condition. A large number of the obese
are afflicted with rheumatism, sluggish livers,
sluggish action of the intestines and weak nerves, and the diet must
be governed accordingly.[12]
The regulation of food for reduction of flesh must, also, be
governed by age, sex, by the manner of breathing and by the
amount of daily exercise.
Exercise, breathing and diet are the scientific means of reduction,
the food must be regulated in accordance with the quantity of
carbohydrates and fats daily consumed in heat and energy.

No definite diet can be given for flesh building,

Leanness because a lack of sufficient fat to round out the
figure is due to faulty digestion or assimilation and
the cause must first be eliminated.
It may be that the strength of the muscles and nerves of stomach,
liver and intestines must first be built up by exercises and deep
breathing, and it may be that the habit of nerve relaxation must be
established. Where one’s nerves are tense much nourishment is
consumed in nervous energy and the nerves to digestive organs and
muscles being tense, interfere with digestion and assimilation.
It is apparent that the cause must first be corrected, because to
overload the digestive organs with sugars, starches and fats, further
weakens them.

FOOTNOTES:
[10] Alida Frances Pattee; “Practical Dietetics” Mt. Vernon, N. Y.
[11] A. F. Pattee; “Practical Diatetics,” A. F. Pattee, Publisher,
Mt. Vernon, N. Y.
[12] Editor’s Note: The causes and relief of Obesity are fully
discussed in my book of this series “Poise, Obesity and
Leanness, their Causes and Relief.”