Preview Green Chemistry for Beginners by Anju Srivastava, Rakesh K. Sharma (2021)

Preview Green Chemistry for Beginners by Anju Srivastava, Rakesh K. Sharma (2021) Preview Green Chemistry for Beginners by Anju Srivastava, Rakesh K. Sharma (2021) Preview Green Chemistry for Beginners by Anju Srivastava, Rakesh K. Sharma (2021) Preview Green Chemistry for Beginners by Anju Srivastava, Rakesh K. Sharma (2021) Preview Green Chemistry for Beginners by Anju Srivastava, Rakesh K. Sharma (2021)

Green Chemistry for Beginners

Green Chemistry for Beginners With a Foreword by Paul Anastas

edited by

Rakesh K Sharma | Anju Srivastava

Jenny Stanford Publishing Pte Ltd.

Level 34, Centennial Tower

3 Temasek Avenue

Singapore 039190

Email: editorial@jennystanford.com

Web: www.jennystanford.com

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library

Green Chemistry for Beginners

Copyright © 2021 by Jenny Stanford Publishing Pte Ltd

All rights reserved This book, or parts thereof, may not be reproduced in any form

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ISBN 978-981-4316-96-5 (Hardcover)

ISBN 978-1-003-18042-5 (eBook)

Foreword xv

Anju Srivastava, Reena Jain, Manavi Yadav,

and Rakesh K Sharma

1.5

1.6

Designing of the 12 Principles of Green

Chemistry Green Chemistry and Sustainable Development Parameters to Evaluate Chemical Processes:

1120

1.7 Atom Economy

1.7.1 Atom-Economical Reactions 25271.7.2 Atom-Uneconomical Reactions 271.8

2 Waste: A Misplaced Resource 33

Anju Srivastava, Sriparna Dutta, and

Rakesh K Sharma

2.2 Sources of Waste Generation 37

2.2.1 Chemical Wastes Generated from

Industrial and Academic Sectors 372.2.1.1 Pharmaceutical wastes 372.2.1.2 Wastes from the academic

research sector 43

2.2.3 Electronic Wastes 47

poisoning incident Waste as a Resource

515353532.4.1 Biomass: A Renewable Feedstock 57

2.4.3 Polymers from Renewable Raw Materials: Thinking Green 2.4.3.1 Bioplastics 2.4.3.2 Bioadhesives

5960612.5 Waste Minimization Techniques

2.5.1 Minimizing the Use of Derivatives in

Chemical Processes: A Way toward Improving the Environmental Credentials of Chemical Synthesis 2.5.1.1 Sitagliptin

2.5.2 Recycling Reagents 2.5.2.1 Recycling reagents in

chemical industries and

61

616364

7272742.8

2.9 Learning Outcomes Problems 7475

3 Catalysis: A Promising Green Technology 79

Manavi Yadav, Radhika Gupta, Gunjan Arora,

and Rakesh K Sharma

3.1.1 What Is a Catalyst?

3.1.2 History of Catalysis 8081

3.1.3 Catalytic Route vs Stoichiometric

Route: The Greener Aspect 3.1.4 Nobel Prize Awards in the 823.2

3.3

3.4

3.5

Development of Catalysis Role of Catalysis

88899091919192923.5.4 Reppe Carbonylation Process

3.5.5 Koch Reaction 93943.6 Heterogeneous Catalysis

3.6.1 Haber–Bosch Process 94953.6.2 Ziegler–Natta Polymerization

3.6.3 Ostwald Process 96963.6.4 Contact Process 973.7

Current Challenges and Future Development

in Catalysis

Learning Outcomes

Problems

97100103104104105106106109110112113113114

4 Alternative Reaction Media 119

Radhika Gupta, Reena Jain, and Rakesh K Sharma

4.2 Need for Solvents 1204.3 Problems Related to Traditional Solvent Use 120

4.4 Criteria for the Selection of Green Solvents 1224.5 Green Solvents for Organic Synthesis

4.5.2 Supercritical Fluids 4.5.2.1 Introduction to supercritical

fluids

1291294.5.2.2 Properties of supercritical

4.5.3

4.5.4 4.5.5 4.5.6

4.5.2.3 Supercritical CO2

(Tc = 31.1°C, Pc = 73.8 bar) 4.5.2.4 Supercritical H2O

(Tc = 374.2°C, Pc = 220.5 bar) Ionic Liquids

4.5.3.1 Introduction to ionic liquids 4.5.3.2 Properties of ionic liquids 4.5.3.3 Ionic liquids as solvents Polyethylene Glycols

Organic Carbonates Solvents Obtained from Renewable

132134135135136137139141Resources 1424.5.6.1 Glycerol

4.5.6.2 2-Methyltetrahydrofuran 4.5.6.3 Ethyl lactate

4.5.6.4 γ-Valerolactone

1431451461474.5.7 Fluorous Biphasic Solvents

4.5.7.1 Introduction to fluorous 148

biphasic solvents 4.5.7.2 Advantages of using

fluorous solvents

1481484.5.7.3 Fluorous biphasic system as a

reaction media 1494.6 Solvent-Free Synthesis

4.6.1 When At Least One of the Reactants 151

Is a Liquid 4.6.2 Gas-Phase Catalytic Reactions 4.6.3 Solid–Solid Reaction

1511521524.7 Immobilized Solvents 4.6.4 Benefits of Solvent-Free Synthesis 1531544.8

4.9 Learning Outcomes Problems 155157

5 Greening Energy Sources 161

Gunjan Arora, Pooja Rana, and Rakesh K Sharma

5.2 Microwave as a Greener Energy Source

5.2.1 Mechanism of Microwave Heating

5.2.1.1 What makes microwave

164164technology superior to

conventional heating?

5.2.2 Microwave-Assisted Chemical 165

5.2.2.1 Non-solid-state reactions 1675.2.2.2 Solid-state reactions 1715.3

5.2.3 Challenges Faced by Microwave

Technology Chemistry Using Ultrasonic Energy

5.3.1 How Sonochemistry Works

5.3.2 Factors Affecting the Cavitation Effect

5.3.3 Sonochemistry for Efficient Organic

Synthesis 5.3.4 Applications in Wastewater Treatment

5.3.5 Challenges Faced by Sonochemical

Processes

1731731751761771791805.4 Visible Light–Driven Processes:

5.4.3.2 Photoinduced isomerization 1845.4.3.3 Photodimerization effect

5.4.4 Industrial Applications of

Photochemistry 5.4.4.1 Photonitrosation 1851855.4.4.2 Photo-oxygenation

5.4.5 Advantages of Photochemistry

5.4.6 Photocatalytic Degradation of

Organic Pollutants

185186187

5.4.6.1 Mechanism of photocatalytic

degradation of organic pollutants

5.4.7 Factors Affecting Photocatalytic Degradation

5.4.7.1 Effect of the concentration

188189

of organic pollutants 5.4.7.2 Effect of the catalyst amount 5.4.7.3 Effect of pH

5.4.7.4 Size, structure, and surface

189190190area of the photocatalyst

5.4.7.5 Effect of the reaction 190

temperature 5.4.7.6 Effect of the light intensity

and wavelength of irradiation

1901915.5

5.4.8 Challenges Faced by Photochemical Synthesis Electrochemistry for Clean Synthesis

5.5.1 Basis of Electrochemical Synthesis 5.5.2 Types of Organic Electrochemical Synthesis 5.5.2.1 Anodic oxidative processes 5.5.2.2 Cathodic reductive processes 5.5.2.3 Paired organic

electrosynthesis 5.5.3 Examples of Electrochemical Synthesis 5.5.3.1 Anodic oxidations

1911921931941941941941951955.5.3.2 Cathodic reductions 196

5.6

5.5.3.3 Paired organic

electrosynthesis 5.5.4 Advantages of Electrochemical Synthesis

5.5.5 Challenges Faced by Electrochemical Synthesis Future Outlook

1971981991995.7

5.8 Learning Outcomes Problems 199200

6 Implementation of Green Chemistry: Real-World

6.2.7 Selective Methylation of Active

Methylene Using Dimethyl Carbonate Some Real-World Cases: Green Chemistry

Efforts Honored

207208209210211211212213

6.3.1 Development of NatureWorksTM PLA:

An Efficient, Green Synthesis of a Biodegradable and Widely Applicable Plastic Made from Corn (A Renewable Resource)

6.3.1.1 Greener alternative: 214

Polylactic acid 6.3.1.2 NatureWorks LLC: 215

Synthesizing PLA from corn

6.3.2 Healthier Fats and Oils via a Greener 215

Route: Enzymatic Interesterification for the Production of Trans-Free Fats

6.3.2.1 Green chemistry:

Interesterification of oils 2226.3.2.2 Enzymatic interesterification

6.3.3 Development of Fully Recyclable

Carpet: Cradle-to-Cradle Carpeting 6.3.3.1 Green chemistry: Production

of a cradle-to-cradle carpet 6.3.3.2 Recycling of PO-backed

nylon-faced carpeting

224225226

6.3.4 Design and Development of Environmentally Safe Marine

resolved

2302312316.3.6

6.3.5.3 How the RightfitTM pigments

can be synthesized Design and Application of Surfactants for CO2 Replacing Smog-Producing and Ozone-Depleting Solvents for Precision Cleaning and Service Industry 6.3.6.1 CO2 as a greener alternative 6.3.6.2 Benefits of scCO2

6.3.6.3 How does a surfactant work? 6.3.6.4 Green chemistry innovation 6.3.6.5 Mechanism of action

233

235236

237

2382382396.3.7

6.3.8

Green Synthesis of Ibuprofen by BHC 6.3.7.1 Green chemistry innovation TAML Oxidant Activators: General

239240

6.3.9

Activation of Hydrogen Peroxide for Green Oxidation Technologies 6.3.8.1 Green chemistry innovation Simple and Efficient Recycling of Rare Earth Elements from Consumer

241243

6.3.10

Materials Using Tailored Metal Complexes 6.3.9.1 Green chemistry innovation Using Naturally Occurring Protein to Stimulate Plant Growth, Improve Crop Quality, Increase Yields, and Suppress Disease

6.3.10.1 Green chemistry innovation 6.3.10.2 Mechanism of action

244245

245247248

6.3.10.3 Advantages of harpin 2486.3.11 Environmentally Advanced Wood

Preservatives: Replacing Toxic Chromium and Arsenic with Copper and Quaternary Ammonium Compounds 6.3.11.1 Green chemistry: Removing

arsenic and chromium from

249

6.4 Need for Industry-Academia Collaboration

6.4.1 An Efficient Biocatalytic Process to

Manufacture Simvastatin

2512536.4.2 Green Route for the Manufacture of

6.6

6.7 Learning Outcomes Problems 257257

7 Green Chemistry in Education, Practice, and Teaching 263

Reena Jain, Anju Srivastava, Manavi Yadav,

and Rakesh K Sharma

7.2

7.3

7.4

Green Chemistry in Classroom

Green Chemistry in a Teaching Laboratory

Green Chemistry Institutes and Network

Centers

2652702747.5

8 Green Chemistry: Vision for the Future 283

Pooja Rana, Sriparna Dutta, Anju Srivastava,

and Rakesh K Sharma

8.3.3 Nonpersistent Nature 2908.4 Selective Reagents in Organic Transformations 8.4.1 Green Solvents 290292

8.5

8.4.2 Dry Media Synthesis 8.4.3 Green Catalysis in Organic Synthesis 8.4.4 Catalyst-Free Reactions in Organic Synthesis

8.4.5 Energy-Efficient Synthesis Miniaturization

2922932952952978.5.1 Generic Goals of Miniaturization 297

8.5.2 Miniaturization in Pharmaceutical

8.5.3 Miniaturization in Undergraduate Laboratories 2998.6

3003053083113138.11

8.12 Learning Outcomes Problems 314315

The

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My compliments to Professor R K Sharma for his long-term

Foreword

dedication to advancing green chemistry in service to a sustainable society and in service to students His relentless pursuit of green chemistry distinguishes his work and sets a model for his students

to follow

Paul T Anastas

Yale University

U.S.A

This book has been completed at a time when the novel coronavirus has engulfed the entire planet, killing hundreds of thousands of people and stalling economic activity across the world This unprecedented outbreak can be traced back to the tenuous relationship we humans have had with the biodiversity This generation-defining pandemic crisis compels us to stop and revisit our practices of exploiting nature and disrupting the integrity of the ecosystem to satiate our rapidly increasing appetite for goods and services The planet has been showing signs of distress for a while: extreme weather events, extinction of life forms, fast-depleting fossil fuel resources, and other epidemic-level diseases.

If there is anything to learn from this moment, it is that mere concern for our environment is no longer sufficient The questions that have been raised for decades now need to be answered urgently: how can we transition to low-waste, low-in-toxicity, low-energy practices in order to have tangible positive effects on the environment and society?

In the chemical sciences, green chemistry has developed as a philosophy with a tremendous potential to provide answers to these concerns The principles of green chemistry promise to allow us

to achieve sustainable development goals Thus, it has never been more crucial for up-and-coming chemists (and even nonchemists) to have a grasp of green chemistry concepts and how they can be used

to sustain human life on our fragile planet

The 12 principles of green chemistry are the basic tenets that promote sustainable synthesis and innovations in the form of greener technologies that are broadly applicable to our work as chemists and the wider sciences

This book has been designed to introduce high school and undergraduate students to the beautiful and captivating world

of green chemistry Beginning with what motivates its need and

a discussion of its origins, the book takes the reader through the popular principles that are most commonly used to modify or

Preface

replace reckless polluting methods, eventually discussing the future challenges and the future of this subject The book also provides insights into efforts made by the pioneers in this field in encouraging real-world practitioners to embrace this science.

The book is divided into eight chapters, is written in a simple language for easy understanding, and is relevant for courses in clean technology and green chemistry, environment chemistry, and others Each chapter has been concluded with the expected learning outcomes

Chapter 1 takes us back several decades, to the emergence of this field, with the vision to curb pollution and reduce the environmental impact of chemical industries The 12 principles of green chemistry, postulated by the father of green chemistry, Professor Paul T Anastas, and Dr John C Warner, have brought a paradigm shift in the development of new products and processes that are compatible with human health and environment

Chapter 2 focuses on the serious concerns pertaining to waste generation and attempts toward waste minimization through green chemistry The chapter illustrates how green chemistry can resolve the dual problems of resource deficits and waste surpluses by turning waste into a resource itself Effective projection of the various innovative waste management techniques—such as minimization

of derivatives, recycling of reagents, miniaturization, the “three R” concept of the waste management hierarchy (reduce, recycle, and reuse), and the design for degradation—could drive us toward a zero-waste planet, one which is cleaner, greener, and healthier Catalysis, a key tool of green chemistry that is virtually behind every chemical we use today, is the focus of Chapter 3 Catalysts embody several advantages, with the main aim being moving away from stoichiometric reagents This chapter covers various important transformations with the aid of chemical and biological catalysts Chapter 4 provides a brief overview of some of the most promising alternative solvents, such as water, supercritical fluids, ionic liquids, polyethylene glycols, organic carbonates, biosolvents, and fluorous biphasic solvents Given the lethal effects of conventionally practiced solvents, this chapter presents an effort to educate beginners about the potential benefits that these alternative green solvents offer in the context of sustainability This chapter also discusses the ways

in which organic reactions can be performed under solvent-free conditions

The burning of fossil fuels is one of the key reasons for greenhouse gas emissions, which continues to be a serious threat

to our environment Clean, safe, energy-efficient, and convenient sources of energy are thus being explored vigorously In Chapter

5, some commonly used nonconventional sources of energy are discussed Specific attention has been paid to the introduction, advantages, applications, and limitations of microwave technology, ultrasonic energy, photochemistry, and electrochemistry Shorter reaction times, by-product elimination, better yields, improved selectivity, and homogeneous heating are the major advantages offered by these alternative energy sources

We are beginning to realize the indispensable need to empower our succeeding generations with the right skills as well as the knowledge to practice chemistry in a benign manner This can be accomplished through the effective projection of the implementation

of green chemistry in the real world Chapter 6 showcases green chemistry in action by illustrating some of the most stimulating real-world case studies, broadly based on the US Presidential Green Chemistry Challenge Awards This chapter also sheds light on some

of the most innovative green processes adopted by industries for the synthesis of valuable compounds Each of the examples in this chapter illustrates how the various principles of green chemistry could be put to practice and what would be the underlying advantages of the redesigned greener protocols The need for academic-industrial collaborations in the current global scenario has also been highlighted with the aid of interesting examples

There is a big mismatch between the way chemistry is taught at secondary and senior secondary levels and the global initiatives that guide scientific and public sustainability discourse It is, therefore, pertinent that the worldwide status of green chemistry education be highlighted to chemists, educators, and policy makers

This is the discussion done in Chapter 7, with efforts made by the pioneers in pulling out green chemistry from the side columns and boxes in chapters and integrating it with the mainstream text Ultimately, the mission is to remove the word “green,” that being the only way chemistry is taught and understood It is crucial to understand how to introduce to stakeholders the concept of green chemistry in the classrooms, laboratories, and research so that

it captures their attention and they start thinking of providing solutions to real-world problems

Chapter 8 summarizes the various future directions of research that require an extensive focus while designing and developing any new chemical process or product The significance of this chapter is

to communicate to the readers a brief sense of the various promising innovative techniques, such as biomimetic, continuous flow, combinatorial chemical technology, and miniaturization, that reflect the need of employing traditional science coupled with emerging systems thinking and systems redesigning for accomplishing high performance in terms of both primary functionality as well as sustainability

All the chapters are explained with ample examples and world cases as far as possible We are truly privileged that the father

real-of green chemistry, Prreal-ofessor Anastas, agreed to write the foreword for this book, which is a huge honor but at the same time has raised the bar in terms of our responsibility and public expectations

We hope the readers find the book worth their time and interest

Rakesh K Sharma Anju Srivastava

January 2021

We do not inherit the earth from our fathers, we are borrowing it from our children.

—David Brower

1.1 Introduction

The past few decades of the twentieth century saw chemistry contributing significantly to the advancement of human civilization Chemists, with their magical powers to play with the chemical molecule, have been looked at as the problem solvers of the society They have synthesized crop-enhancing chemical fertilizers and pesticides that enhance crop yields to ensure a constant and

Genesis of Green Chemistry

Green Chemistry for Beginners

Edited by Rakesh K Sharma and Anju Srivastava

Copyright © 2021 Jenny Stanford Publishing Pte Ltd.

ISBN 978-981-4316-96-5 (Hardcover), 978-1-003-18042-5 (eBook)

www.jennystanford.com

Anju Srivastava, a Reena Jain, a Manavi Yadav, a,b

and Rakesh K Sharma b

aDepartment of Chemistry, Hindu College, University of Delhi,

Delhi 110007, India

bGreen Chemistry Network Centre, Department of Chemistry,

University of Delhi, Delhi 110007, India

dr.anjusrivastava@gmail.com

sustainable food supply Modern medicines, health-care products, advanced diagnostic chemical tests, and analysis have played incr

key role in the eradication a The easing innovatithe average life

This ansportation, contribution computing, aerospace, electronics, the

prrole oducts, chemistry in

adhesisuch

plain ys specialty our applications is over and clothes, plastics, ves, aslubricants, our local grpaints, ocery

every, dahary dliwves are, by

detpreroviding and even gents,

Undeniably, ther

standar

and the efore, without the continuous

ds enormoof modern us productisociety vity of the chemical industries,

efforts of chemists

the high these enhancements,

natural resources that the encan be vir

could onment not has been used as a have been attained sourAnd ce of in application

tool called chem

of chemical istry Ho

xploitsciencwev

eer

es , the

ed rapid for the pace society by the scientific the misuse of the otherwise fascinating has come science at a

of headevy velopment has led tprice,o the r welease her

and

e

of

production pollutants of and nonbiodegrtoxic substances adable matinto erials, land, rairesulting , and win ater

impact on the environment and living beings a harmful

and the

products, The scientific until de

on the desired quitmolecules e

velopment recentl of and research on molecules and understanding of the fate and or

discussed t

In fact, eo support this fven the environment act

h levels Numerous examples can be

a negative public image problems for which chemicals have solutions

problems rusing equirthe e chemical solutions.know

can ledge be of mitigchemistryated with As long-tis often erm said, sustainable chemical

In the subsequent sections, the reader will be taken through the

that vhaarious ve over inftime amous led disastto the ers emeraffecting gence the greneen virchemistry onment and and lifits e

trichloroethane (DDT) was developed hydrocarbon dichlor

to be very effective in eradicating not as onla pesticide and

odiphenwas found yl-t

be ors an causing elixir fordiseases both the like agriculturmalaria and e and yello

birnew ds and public other a

ywears ar

living eness beings.

publication, the government banned the use of this pesticide [2, 3].ention Ten after

thatthe naturbook’s

Silent

e

werAre ound selling the a same newly time, synthesized in Europe, pharmaceutical companies tr

the medeating icine prmorning ovsickness ed to be vand

the expecting motherser

nausea thalidomide-based in pregnant women drug for among , y effthe ectichildrve and en born brougto ht these a wavmothers e of jo

While

y w

limbs ere found tThese o hathalidomide ve acute birth defbabies werects with defe born because ormed the or drug missing inad

its enantiomers acting as a teratogen, which was being synthesized had vertently along

with

caused

as the manbirth y as 5000 of

with 10,000 the actual such defdrug The infamous incident was immediately banned such from babies use and in

ormed Germanbabies worldwide, was remoy valone ed from The all drug pharmacists’ outlets [4] the called Invfrenteons, wed in

loer

the 1930s, chlorofluorocarbons (CFCs), popularl their e consider

y due to w toxicity and ednonr a class eactiof wve onder nature, hyfdround ocarnumerbons thatous ,

industrial and consumer applications, including as refrigerants, propellants, hospital sterilant, industrial solvents, and foam-blowing agents Their worldwide market increased multifold in a very short span of time After about 40 years of indiscriminate use

of these so-called benign compounds, it was found in 1974 that these compounds, when released into the atmosphere, diffuse to the stratosphere, where their chlorine component depletes and destroys the ozone layer, which acts as a protective shield against the harmful ultraviolet radiations, which otherwise are dangerous for life on this planet When a definite link was established for this observed relation, CFCs were banned in 1987 under the Montreal Protocol [5]

In the early 1970s, an oil slick and debris within the Cuyahoga

River caught fire in Cleveland, Ohio, US, drawing national attention

to the environmental problems in the United States This was not the first time that the river had caught fire Fires had occurred on the Cuyahoga River several times earlier also In fact, one such fire in

1952 caused damage worth over US$1.5 million Another incident, which in particular brought this problem into spotlight, was the Love Canal site, Niagara Falls, New York, US It was a chemical waste dumpsite constructed in an old abandoned canal where approximately 82 waste chemicals, including a number of suspected carcinogens, such as benzene, chlorinated hydrocarbons, and dioxin, had been dumped Later, the site was sealed and a residential locality was constructed over it However, the chemicals began to ooze out over time and affected people of that area by leading to severe birth defects and miscarriages The entire town had to be evacuated, which led to an expenditure of many millions of US dollars to relocate nearly one thousand households and to remediate the site [6] Times Beach, a small town in in Missouri, USA, used to spray used motor oil on the unpaved streets to settle the rampant dust in the area The hired person started spraying waste oily chemicals along with the oil These chemicals, generated as by-products of the production

of chemical disinfectants, were toxic (dioxins) Oblivious to the toxic nature of the oil spray, the town continued this practice for four years, when widespread unexplained deaths of birds and animals and poisonous effects of dioxin manifesting as acute headaches, diarrhea, and nose bleed among residents were observed In 1982, soil tests showed the alarmingly high levels of dioxin present As if this was not enough, a flash flood in the area worsened the situation,

with more people coming in contact with the hazardous chemicals The site

town w

In 1984, as or

was

derat ed immediatonce declared ely [7].uninhabitable and evacuation of the

an accidental one release of the

the pesticide manufacturing of

whigorst hlindustrial y toxic methcatastryl isocyophes anatoccurre (MIC) ed gwas, hen plant at Union Carbide India in Bhopal, in Madh

3600 ypeople a Pradesin h, their India, sleep, on the 800nig0 ht of December 2–3, killed nearly t

to affe ectto ed this women poisonoThus e plant gas,

the On ChernobApril 26, yl nuclear 1986, the pow

Union This accident was w

orst

er nuclear disaster in history unfolded at

of radioactive mat follo

station wed biny the Ukrraine, elease in the of huge formeramounts Soviet surr

accident was a result of a flawed reactor design

oil spill left a deep ous impactoil

spills, the atMarors [9].

It ch 24, 1989, Exxon Valdez into ExxPrince on Shipping William CompanSound y in spilled

occurred when an oil tanker owned sensitive areas in the world Within Alaska a,

millions one of of gallons of crude oil nearby beaches and killed hundreds of few thousands days,

the this most oil slick ecologicallcov y

of seabirds, seals, ered otters, and w

melt

Since

downs, then,

hales [10]

explosions the world has

sludge flooding towns and at richemical

seen massi

plants, ve oil and spills, vers Figure 1.1 illustratwa

nucleaves of r plant

es a few tsuch oxic envir

Jaipur oil depot fire, 2009

Korba chimney collapse, 2009

Styrene gas release, 2020

Figure 1.1 (a) Bhopal gas tragedy (1984, India), (b) Chernobyl nuclear accident

(1986, Ukraine, erstwhile USSR), (c) Cuyahoga River fire (1969, USA), (d) Los Angeles smog (1943, USA), (e) Love Canal disaster (1984, USA).

These incidents threw light on the dangerous extent to which human acti

environmentvities , which wercompelled e contaminating

pass regulatory laws that would sevrereduce al

the vcountries arious to segments deliber of the and help clean up waste chemical sites On the June release 5, 1972, of pollutants

ate and ever UN conference marked a turning the first ther

natur

eaftal er resourdecidces ed and to celebrmaintatenance e this daof

point

a in the management of Day Additionally, y as

clean the Environmental Protection the

es Agency (EPA) was

o reconcile envir published a report needs

development

of the curr,” for ent generthe

onmental first issues gener ation without

time, as deand velopment defined “sustainable ation This report also highlighted compr

omising the futurthat meets the dangers of ozone e time line of the eand its volution of greffects on global een chemistry [11–13].warming Figure 1.2 provides a

With

egulat

the

ory Agencies in India

of envir rapid pace of industrialization, India has its fair share F

Policy and

the PlannMinistry ing to of prEnotvirect onment the

National environmentCouncil fLator Ener, virthis onmental and Forest, one of the council

occurrRecentled in y, Visa styrakhapatnam, ene gas leakAndhr, reminiscent a Pradesh, of the Bhopal disaster,

ol ved

the that

release mere

of dilution

chemical

in philosoph

would be

y sufficient was soon to alleviate

substance its ultimatin an appropriatfound to be absure impact How

such and

of a

eam substance (air, watthat er, land) could be It uses released

maximum concentr standar

into

concentration level ation guideline levels (MCds

a

is

particular approach

chehas

mical, also thereby GLs) limiting to strictlthe dischary contrge ol resulted in the implementation

of several technologies that deal with pollutants and transform w

substances

considered as an enalready prviresent onmentallin the y benign solution.environment

substances and,

with thus, cannot

the other

be

Act, In stating the 1990that s, the United States passed the Pollution Prevention not

could be be generachieated

wherever possible, in the first ved and viaif segenerveral ated, means, it must ranging be minimized

ht w

chemicals,

as followed giving by the priority expansion to nonpr

olling oduction the riskof s associatthese mated erials with tThis oxic appr

in desirenvire onmental to keep

of

global

the enissues vironmentthat are

ess these With resulting a mission in tthe o find continued strategic det

increrior

easing ation intr

envir

oduced onmental Thiprs toterm ection was and first conservcoined ation, in the greareen ly chemistry

solutions

was to 1990s

t

br

o anch of minimize chemistry reagents, but steps, is rcosts, ather

dous considersubstances ed as a code It is not of a separconduct ate and energy, thereby reducing the

environmental impact of chemical processes More specifically, it focuses on environmental

path

protwection, Thus,

designing

green new prchemical ocesses are benign ays that

not by cleaning waste but by protecting health and environment while by

do design not generate pollutants promoting and innoare vatall

about easing profits [1, 16] It is a rapidly evolving and important arand

of chemical sciences that will e

ea mankind [17–19]

that chemicals are not bad but varentualle needed y bring for back the dethe velopment perspectivof e leaders

esearfrom

ch in grboth academia een chemistry chemistry industry

gained momentum,

working ogr green

A in 1995 [20] This is the only award that is began in gr Shoreen chemistry tly after this,

C Wand

arner safer

with chemistry

the goal In

to the

educatsame

e y

the ear,

new the f

joined or adv

Institute (GCI), a nonprofit the ancement American in Chemical the green Society chemistry to addrdomain

institute, Latweras , the creatGCI ed ess global issues in field of chemistry and en

ChemistrThe gr

vironment

the oundbreaking book

actic on een chemistry entitled

chemistry the field of green chemistry It gives a precise

generally acceptand enumered guidelines ates its 12 for principles, green chemistrywhich

definition have become of green the Since

as translated into numer The ous book languages soon field

resear

As ch of to nogreen w, all chemistry and published

journals plenty have of dedicatarticles ed on their this than

journal

40

e

nations

xclusively on the grmajor een and publishing

and networks from

sustainable houses chemistry have at and least morone all

e

in promoting green chemistry With otime, ver the the wor

community realized the needs and gaps and has thrigr

ld een are chemistry involved ved gradually

1.4 Designing of the 12 Principles of Green

designed process int

to

o

maximize the final

be Wherever practicable, synthetic methodologies should

Principle 4:

toxicity t

designed

o human health and the en

to use and generate substances

vironment

that possess little or no

(e.g., w

solhervents,

environmental Enerand gy economicrequirements impacts should and be should recognized be minimized for their S

reagents (as selective as possible) are superior

end of their function the Chemical pry dooducts not persist should be in the endesigned virso that at the break down into innocuous degradation products onment and

10 Generate

5 Use of safer solvents and auxiliaries

9 Enhancing

catalysis

6 Energy efficiency

8 Reducing derivatives

7 Use of renewable raw materials

Figure 1.3 The 12 principles of green chemistry.

and technologists

y designing

in their appr

quest opriat

traditional and sodium

method hy

to dr

proxide

oduce

as

phenol reactants

invol

in ves multistep reaction Scheme 1.1 depicts the overall reaction a

Analytical methodologies need to be further developed

Scheme 1.1

This chemical

Conventional method of manufacturing phenol.

g) should yield 1 equation mole of shophenol ws that 1 mole of benzene

yield (Eq 1.1) is about 82% (77 g), (94 wg) hich Hois wequitvere , the good, actual

(78

this reaction also generates 1 mole but each mole of phenol produced This side-prof sodium sulfite (126 g) for pr

Scheme 1.2 Alternative method to manufacture phenol.

chemical

ts in (Ethe

r1.2) desir

eaction

q The ed

and product is expressed as

100, the lesser will be the w

er its to valthe ue tis otal to

the desired product

100% For ateom xample, economphenol

Relativve molecular mass

In comparison, the y atsince

produced the

of

copr

all r

froduct

eactant

om benzene has

s

is only an appr

and eciable propene

om economy 37% when phenol value

economy is the Diels–Alder reaction (Scheme 1.3), where all the atoms of reactants are involved in the final product.

Scheme 1.3 Diels–Alder reaction.

poisonous (Scheme gas and 1.4) hence Ho

of bisphenol A (Fig 1.4) with carbonyl carbonate, which is produced has

Scheme 1.4 Formation of carbonyl chloride.

Scheme 1.5 Formation of diphenyl carbonate.

by using tant to produce two chiral forms separ

produce catalone ysts of that the can twenhance o chiral molecules the rate of

atthe ely This desircan ed rbe eaction done the synthesis of polymers Another example is ha

the ve popular high tougones hness Poltypheno be

thatable not to one absor

only ylsulf is b

armore less e seflammable vere impacts but than also formula depicted in Fig 1.5 one such polymer, with the

such as

Table 1.1 Greener alternatives to toxic solvents

Safer green solvents Properties

Ionic liquids (ILs) ILs are liquids at room temperature and below

They are nonvolatile, have no vapor pressure, can provide nonaqueous reaction media of varying polarities, do not require any special apparatus

or methods to carry out reactions in them, and can be reused These properties make ILs a suitable green alternative to toxic solvents

(Continued)

Pharmaceutical products are usually chiral

∑ dry-cleaning equipment. Supercritical water: Organic substances are insoluble in water, but most of them become soluble in water when it becomes supercritical

at 374°C and 218 atm Hence, this can be used as a green solvent for many organic transformations

Solvent free No solvent is the best solvent Some chemical

reactions run under neat conditions

∑  Reactions in solid

phase ∑  Numerous reactions take place in the solid

state that are simple to operate and economical and prevent solvent-based issues

∑  Reactions in

gaseous phase ∑  Examples of reaction in the gas phase include

synthesis of ammonia, methanol, and ethene Water Due to limited chemical compatibility, use of

water as a solvent was not known until it found success in accelerating rates of some reactions due to its high polarity Reactions carried out

in an aqueous medium include the Diels–Alder reaction, oxidations, reductions, epoxidations, and polymerizations (with or without catalysts) Water-borne paints have substituted volatile organic compounds, such as the hydrocarbons Immobilized solvents Solvents immobilized on polymer beads minimize

the volatility associated with organic solvents and offer efficiency in separation through simple filtration, in comparison to tedious procedures like rotary evaporation and distillation.

Design f or energy efficiency:

oximes product

is one yields

of the

examples in

Beckmann the use

the

of solid

is an excellent example that

temper

gy souratur

takhen

es carried

place at out

of renewand

able nontfeedstocks is n

for

ylon, synthesizingplasticizers, adipic and lubricaacid, wnts, hich and is required in the pr

othe reaction is carried oduction

xic glucose out in of aqueous media Some other examples are as follows:

e readily biodegradable and are derived

deri

on pr

v

from bioethanol and used to make biobased

ot

ati

ection ves: A typical example of use of a

part of the molecule, leaunderving going

of an o

alcohol xidation

by the alcohol unaffoxidizes

converting it into the alcohol is regenerated through benzyl ether

ected

Aftthe erwother vage This ard,

fine cheof micals, derivatization pharmaceuticals, is extremel

handling reagents like benzy

dyy es, important and pesticides for synthesizing However, danger

y ection are not l chloride only being (a used known but arhazare regenerd) can ated be step Another problem lies with the

temporary modifications in properties like viscosity, vapor pressure, dispersibility

certain compounds , and water These solubility

ed their

e much be recymorcled and reused, such as zeolite and silica groups can catalyze a number their

e benign, prand further modifications on converting benzene and propene of rteactions

operties

One A solid example zeolitis e with

o cumene during the manufits

of

acturuse

acid

in phenol (Scheme

e acid

nyast

lon

e of

6, sulfuric

a polymer acid

used

in the

in

Scheme 1.6 A solid zeolite with acid groups as a catalyst for the conversion of

benzene and propene into cumene.

Scheme 1.7 Isomerization of oxime into caprolactum by a solid acid zeolite

e as the by-product from effluents in the