Catalisis

Gadi Rothenberg Catalysis

Gadi Rothenberg

Catalysis
Concepts and Green Applications

The Author Dr. Gadi Rothenberg Van‘t Hoff Institute for Molecular Sciences, University of Amsterdam, The Netherlands www.science.uva.nl/~gadi

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in thesebooks, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for

Cover picture Ada Rothenberg, Tel Aviv, Israel, http://www.adarothenberg.com

British Library Cataloguing-in-Publication Data A catalogue record for this book isavailable from the British Library. Bibliographic information published by the Deutsche Nationalbibliothek Die Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available in the Internet at . # 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of thisbook may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Typesetting Thomson Digital, Noida, India Printing Strauss GmbH,Mörlenbach Binding Litges & Dopf Buchbinderei GmbH, Heppenheim

Printed in the Federal Republic of Germany Printed on acid-free paper ISBN: 978-3-527-31824-7

I never write metropolis for seven cents, because I can get the same price for city. Mark Twain

VII

Contents
Preface XIII

1 1.1 1.1.1 1.1.2 1.1.3 1.1.4 1.2 1.2.1 1.2.2 1.2.3 1.3 1.3.1 1.3.2 1.3.3 1.4 1.5

Introduction 1 GreenChemistry and Sustainable Development 1 What is ‘‘Green Chemistry’’? 2 Quantifying Environmental Impact: Efficiency, E-factors, and Atom Economy 4 Just How ‘‘Green’’ is this Process? 6 Product and Process Life-Cycle Assessment (LCA) 9 What is Catalysis and Why is it Important? 10 Homogeneous Catalysis, Heterogeneous Catalysis, and Biocatalysis 12 Replacing Stoichiometric Reactions with CatalyticCycles 19 Industrial Example: The BHC Ibuprofen Process 22 Tools in Catalysis Research 23 Catalyst Synthesis and Testing Tools 24 Catalyst Characterization Tools 26 Tools for Modeling/Mechanistic Studies 28 Further Reading 29 Exercises 31 References 35 The Basics of Catalysis 39 Catalysis is a Kinetic Phenomenon 39 Reaction Rates, Reaction Orders, Rate Equations, and Rate-Determining Steps 40 TheReaction Order 42 The Rate-Determining Step 43 The Reaction Profile and the Reaction Coordinate 44 Zero-Order, First-Order, and Second-Order Kinetics 46

2 2.1 2.1.1 2.1.1.1 2.1.1.2 2.1.2 2.1.3

Catalysis: Concepts and Green Applications. Gadi Rothenberg Copyright # 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-31824-7

VIII

Contents

2.1.3.1 2.1.3.2 2.1.3.3 2.1.4 2.1.52.1.6 2.1.7 2.1.8 2.2 2.2.1 2.2.1.1 2.2.2 2.2.3 2.2.4 2.3 2.3.1 2.3.2 2.3.2.1 2.3.2.2 2.3.3 2.3.3.1 2.4

Zero-Order Rate Equations 46 First-Order Rate Equations 47 Second-Order Rate Equations 48 Langmuir–Hinshelwood Kinetics 49 The Steady-State Approximation 52 Michaelis–Menten Kinetics 54 Consecutive and Parallel First-Order Reactions 56 Pre-Equilibrium, ‘‘Catalyst Reservoirs,’’ and CatalystPrecursors 58 Practical Approaches in Kinetic Studies 60 Initial Reaction Rates and Concentration Effects 61 Concentration Effects 62 Creating Pseudo Order Conditions 62 What You See versus What You Get 63 Learning from Stoichiometric Experiments 64 An Overview of Some Basic Concepts in Catalysis 64 Catalyst/Substrate Interactions and Sabatier’s Principle 65 Catalyst Deactivation, Sintering, and...