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Green Chemistry for Beginners Green Chemistry for Beginners With a Foreword by Paul Anastas edited by Rakesh K Sharma | Anju Srivastava Published by Jenny Stanford Publishing Pte Ltd Level 34, Centennial Tower 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 or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the publisher For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA In this case permission to photocopy is not required from the publisher ISBN 978-981-4316-96-5 (Hardcover) ISBN 978-1-003-18042-5 (eBook) Contents Foreword Preface Genesis of Green Chemistry Anju Srivastava, Reena Jain, Manavi Yadav, and Rakesh K Sharma 1.1 Introduction 1.2 Early History 1.3 Need for Green Chemistry: The Whys and Wherefores 1.4 Designing of the 12 Principles of Green Chemistry 1.5 Green Chemistry and Sustainable Development 1.6 Parameters to Evaluate Chemical Processes: E-Factor and LCA 1.7 Atom Economy 1.7.1 Atom-Economical Reactions 1.7.2 Atom-Uneconomical Reactions 1.8 Hazards and Risks in Chemistry 1.9 Learning Outcomes 1.10 Problems Waste: A Misplaced Resource Anju Srivastava, Sriparna Dutta, and Rakesh K Sharma 2.1 Introduction 2.2 Sources of Waste Generation 2.2.1 Chemical Wastes Generated from Industrial and Academic Sectors 2.2.1.1 Pharmaceutical wastes 2.2.1.2 Wastes from the academic research sector 2.2.2 Plastic Wastes 2.2.3 Electronic Wastes xv xvii 1 11 20 22 25 27 27 28 29 29 33 33 37 37 37 43 44 47 vi Contents 2.2.4 Paper Wastes 2.3 Problems Associated with the Generation and Mismanagement of Waste 2.3.1 Global Case Studies Reflecting Mismanagement of Waste 2.3.1.1 Minamata mercury poisoning incident 2.4 Waste as a Resource 2.4.1 Biomass: A Renewable Feedstock 2.4.2 Biodiesel 2.4.3 Polymers from Renewable Raw Materials: Thinking Green 2.4.3.1 Bioplastics 2.4.3.2 Bioadhesives 2.5 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 laboratories 2.5.3 Miniaturization 2.5.4 Reduce, Reuse, and Recycle 2.5.4.1 Reduce 2.5.4.2 Reuse 2.5.4.3 Recycle Design for Degradation 2.6 Conclusion 2.7 2.8 Learning Outcomes 2.9 Problems Catalysis: A Promising Green Technology Manavi Yadav, Radhika Gupta, Gunjan Arora, and Rakesh K Sharma 3.1 Introduction 3.1.1 What Is a Catalyst? 3.1.2 History of Catalysis 50 51 53 53 53 57 58 59 60 61 61 61 63 64 65 68 70 71 71 72 72 74 74 75 79 79 80 81 Contents 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 3.11 3.12 3.13 3.1.3 Catalytic Route vs Stoichiometric Route: The Greener Aspect 3.1.4 Nobel Prize Awards in the Development of Catalysis Role of Catalysis Next-Generation Catalysts Classification of Catalysts Homogeneous Catalysis 3.5.1 Hydroformylation Reaction 3.5.2 Olefin Hydrogenation Using Wilkinson’s Catalyst 3.5.3 Monsanto and Cativa Process 3.5.4 Reppe Carbonylation Process 3.5.5 Koch Reaction Heterogeneous Catalysis 3.6.1 Haber–Bosch Process 3.6.2 Ziegler–Natta Polymerization 3.6.3 Ostwald Process 3.6.4 Contact Process 3.6.5 Catalytic Converters Phase Transfer Catalysts Asymmetric Catalysis Nanocatalysis: Emerging Hybrid Catalysis 3.9.1 What Is Nanocatalysis? 3.9.2 Synthetic Approaches 3.9.3 Catalytic Applications 3.9.3.1 Metal nanoparticles 3.9.3.2 Metal oxide nanoparticles 3.9.3.3 Magnetic nanoparticles Biocatalysis Current Challenges and Future Development in Catalysis Learning Outcomes Problems Alternative Reaction Media Radhika Gupta, Reena Jain, and Rakesh K Sharma 4.1 Introduction 4.2 Need for Solvents 4.3 Problems Related to Traditional Solvent Use 82 88 89 90 91 91 91 92 92 93 94 94 95 96 96 97 97 100 103 104 104 105 106 106 109 110 112 113 113 114 119 119 120 120 vii viii Contents 4.4 4.5 4.6 4.7 4.8 4.9 Criteria for the Selection of Green Solvents Green Solvents for Organic Synthesis 4.5.1 Water 4.5.2 Supercritical Fluids 4.5.2.1 Introduction to supercritical fluids 4.5.2.2 Properties of supercritical fluids 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) 4.5.3 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 4.5.4 Polyethylene Glycols 4.5.5 Organic Carbonates 4.5.6 Solvents Obtained from Renewable Resources 4.5.6.1 Glycerol 4.5.6.2 2-Methyltetrahydrofuran 4.5.6.3 Ethyl lactate 4.5.6.4 γ-Valerolactone 4.5.7 Fluorous Biphasic Solvents 4.5.7.1 Introduction to fluorous biphasic solvents 4.5.7.2 Advantages of using fluorous solvents 4.5.7.3 Fluorous biphasic system as a reaction media Solvent-Free Synthesis 4.6.1 When At Least One of the Reactants Is a Liquid 4.6.2 Gas-Phase Catalytic Reactions 4.6.3 Solid–Solid Reaction 4.6.4 Benefits of Solvent-Free Synthesis Immobilized Solvents Learning Outcomes Problems 122 124 124 129 129 131 132 134 135 135 136 137 139 141 142 143 145 146 147 148 148 148 149 151 151 152 152 153 154 155 157 ... Green Chemistry for Beginners Green Chemistry for Beginners With a Foreword by Paul Anastas edited by Rakesh K Sharma | Anju Srivastava Published by Jenny Stanford Publishing... Foreword Preface Genesis of Green Chemistry Anju Srivastava, Reena Jain, Manavi Yadav, and Rakesh K Sharma 1.1 Introduction 1.2 Early History 1.3 Need for Green Chemistry: The Whys and Wherefores... Problems Green Chemistry in Education, Practice, and Teaching Reena Jain, Anju Srivastava, Manavi Yadav, and Rakesh K Sharma 7.1 Introduction 7.2 Green Chemistry in Classroom 7.3 Green Chemistry