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Inorganic Chemistry for Geochemistry and Environmental Sciences k Trim Size: 189mm x 246mm Luther ffirs.tex V3 - 04/22/2016 7:32 A.M. Page i Inorganic Chemistry for Geochemistry and Environmental Sciences k k k k Trim Size: 189mm x 246mm Luther ffirs.tex V3 - 04/22/2016 7:32 A.M. Page ii k k k k Trim Size: 189mm x 246mm Luther ffirs.tex V3 - 04/22/2016 7:32 A.M. Page iii Inorganic Chemistry for Geochemistry and Environmental Sciences Fundamentals and Applications GEORGE W. LUTHER, III k School of Marine Science & Policy, k University of Delaware, USA k k Trim Size: 189mm x 246mm Luther ffirs.tex V3 - 04/22/2016 7:32 A.M. Page iv This edition first published 2016 © 2016 John Wiley & Sons Ltd Registered office John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reusethe copyright material in this book please see our website at www.wiley.com. The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designsand Patents Act 1988. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books. Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendor mentioned in this book. Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. It is sold on the understanding that the publisher isnot engaged in rendering professional services and neither the publisher nor the author shall be liable for damages arising herefrom. If professional advice or other expert assistance is required, the services of a competent professional should be sought. k k The advice and strategies contained herein may not be suitable for every situation. In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. No warranty may be created or extended by any promotional statements for this work. Neither the publisher nor the author shall be liable for any damages arising herefrom. Library of Congress Cataloging-in-Publication Data Names: Luther III, George W. Title: Inorganic chemistry for geochemistry and environmental sciences : fundamentals and applications / George W. Luther, III. Description: Chichester, West Sussex : John Wiley & Sons, Inc., 2016. | Includes bibliographical references and index. Identifiers: LCCN 2015047266 | ISBN 9781118851371 (cloth) | ISBN 9781118851401 (epdf) | ISBN 9781118851418 (epub) Subjects: LCSH: Chemistry, Inorganic. | Geochemistry. | Bioinorganic chemistry. | Transition metals–Environmental aspects. | Sulfides–Environmental aspects. | Chemical ecology. Classification: LCC QH541.15.C44 L88 2016 | DDC 577/.14–dc23 LC record available at http://lccn.loc.gov/2015047266 A catalogue record for this book is available from the British Library. Set in 9/11pt, TimesLTStd by SPi Global, Chennai, India. 1 2016 k k Trim Size: 189mm x 246mm Luther ffirs.tex V3 - 04/22/2016 7:32 A.M. Page v To B.J., Gregory and Stephanie k k k k Trim Size: 189mm x 246mm Luther ffirs.tex V3 - 04/22/2016 7:32 A.M. Page vi k k k k Trim Size: 189mm x 246mm Luther ftoc.tex V3 - 04/22/2016 2:03 P.M. Page vii Contents About the Author xv Preface xvii Companion Website xix 1. Inorganic Chemistry and the Environment 1 1.1 Introduction 1 1.1.1 Energetics of Processes 1 1.2 Neutron–Proton Conversion 3 1.3 Element Burning Reactions – Buildup of Larger Elements 4 1.4 Nuclear Stability and Binding Energy 5 1.4.1 The “r” and “s” Processes 6 1.5 Nuclear Stability (Radioactive Decay) 8 1.6 Atmospheric Synthesis of Elements 8 1.7 Abundance of the Elements 8 1.7.1 The Cosmos and the Earth’s Lithosphere 8 k 1.7.2 Elemental Abundance (Atmosphere, Oceans, and Human Body) 10 k 1.8 Scope of Inorganic Chemistry in Geochemistry and the Environment 17 1.8.1 Elemental Distribution Based on Photosynthesis and Chemosynthesis 17 1.8.2 Stratified Waters and Sediments – the Degradation of Organic Matter by Alternate Electron Acceptors 19 1.9 Summary 21 1.9.1 Environmental Inorganic Chemistry 22 References 22 2. Oxidation–Reduction Reactions (Redox) 24 2.1 Introduction 24 2.1.1 Energetics of Half Reactions 24 2.1.2 Standard Potential and the Stability of a Chemical Species of an Element 26 2.2 Variation of Standard Potential with pH (the Nernst Equation) 29 2.3 Thermodynamic Calculations and pH Dependence 29 2.4 Stability Field of Aqueous Chemical Species 31 2.5 Natural Environments 32 2.6 Calculations to Predict Favorable Chemical Reactions 32 2.6.1 Coupling Half-Reactions 34 2 + 2 + − 2.6.2 One-Electron Oxygen Transformations with Fe and Mn to Form O2 35 k k Trim Size: 189mm x 246mm Luther ftoc.tex V3 - 04/22/2016 2:03 P.M. Page viii viii Contents 2.7 Highly Oxidizing Conditions 38 2.7.1 Ozonolysis Reactions 38 2.7.2 Atmospheric Redox Reactions 39 Appendix 2.1 Gibbs Free Energies of Formation 43 References 43 3. Atomic Structure 45 3.1 History 45 3.2 The Bohr Atom 46 3.3 The Schrodinger Wave Equation 47 3.4 Components of the Wave Function 50 3.4.1 Radial Part of the Wave Function, R(r)50 3.4.2 Angular Part of the Wavefunction Ylml( , ) and Atomic Orbitals 54 3.5 The Four Quantum Numbers 56 3.6 The Polyelectronic Atoms and the Filling of Orbitals for the Atoms of the Elements 58 3.7 Aufbau Principle 61 3.8 Atomic Properties 62 3.8.1 Orbitals Energies and Shielding 62 3.8.2 Term Symbols: Coupling of Spin and Orbital Angular Momentum 63 3.8.3 Periodic Properties – Atomic Radius 67 3.8.4 Periodic Properties – Ionization Potential (IP) 67 3.8.5 Periodic Properties – Electron Affinity (EA) 71 k k 3.8.6 Periodic Properties – Electronegativity ()74 3.8.7 Periodic Properties – Hardness ()75 References 77 4. Symmetry 79 4.1 Introduction 79 4.2 Symmetry Concepts 79 4.2.1 Symmetry Operation 79 4.2.2 Symmetry Element 79 4.2.3 Symmetry Elements and Operations 80 4.3 Point Groups 84 4.3.1 Special Groups and Platonic Solids/Polyhedra 85 4.3.2 Examples of the Use of the Scheme for Determining Point Groups 88 4.4 Optical Isomerism and Symmetry 92 4.4.1 Dichloro-Allene Derivatives (C3H2Cl2)92 4.4.2 Tartaric Acid 93 4.4.3 Cylindrical Helix Molecules 93 4.5 Fundamentals of Group Theory 93 4.5.1 C2v Point Group 95 4.5.2 Explanation of the Character Table 96 4.5.3 Generation of the Irreducible Representations (C2v Case) 97 4.5.4 Notation for Irreducible Representations 97 k k Trim Size: 189mm x 246mm Luther ftoc.tex V3 - 04/22/2016 2:03 P.M. Page ix Contents ix 4.5.5 Some Important Properties of the Characters and their Irreducible Representations 98 4.5.6 Nonindependence of x and y Transformations (Higher Order Rotations) 98 4.6 Selected Applications of Group Theory 101 4.6.1 Generation of a Reducible Representation to Describe a Molecule 101 4.6.2 Determining the IR and Raman Activity of Vibrations in Molecules 104 4.6.3 Determining the Vibrational Modes of Methane, CH4 105 4.6.4 Determining the Irreducible Representations and Symmetry of the Central Atom’s Atomic Orbitals that Form Bonds 107 4.7 Symmetry Adapted Linear Combination (SALC) of Orbitals 111 4.7.1 Sigma Bonding with Hydrogen as Terminal Atom 111 4.7.2 Sigma and Pi Bonding with Atoms Other than Hydrogen as Terminal Atom 114 Appendix 4.1 Some Additional useful Character Tables 120 References 122 5. Covalent Bonding 123 5.1 Introduction 123 5.1.1 Lewis Structures and the Octet Rule 123 5.1.2 Valence Shell Electron Pair Repulsion Theory (VSEPR) 126 5.2 Valence Bond Theory (VBT) 127 5.2.1 H2 and Valence Bond Theory 129 5.2.2 Ionic Contributions to Covalent Bonding 130 k k 5.2.3 Polyatomic Molecules and Valence Bond Theory 131 5.3 Molecular Orbital Theory (MOT) 132 5.3.1 H2 132 5.3.2 Types of Orbital Overlap 137 5.3.3 Writing Generalized Wave Functions 138 5.3.4 Brief Comments on Computational Methods and Computer Modeling 139 5.3.5 Homonuclear Diatomic Molecules (A2) 140 5.3.6 Heteronuclear Diatomic Molecules and Ions (AB; HX) – Sigma Bonds Only 144 5.3.7 Heteronuclear Diatomic Molecules and Ions (AB) – Sigma and Pi Bonds 147 5.4 Understanding Reactions and Electron Transfer (Frontier Molecular Orbital Theory) 150 5.4.1 Angular Overlap 151 5.4.2 H+ +OH− 151 5.4.3 H2 +D2 152 5.4.4 H2 +F2 153 5.4.5 H2 +C2 154 5.4.6 H2 +N2 (also CO + H2) 154 5.4.7 Dihalogens as Oxidants 156 − 5.4.8 O2 as an Oxidant and its Reaction with H2S and HS 157 5.5 Polyatomic Molecules and Ions 161 + 5.5.1 H3 Molecular Cation 161 5.5.2 BeH2 – Linear Molecule with Sigma Bonds Only 163 5.5.3 H2O – Angular Molecule with Sigma Bonds Only 165 k k Trim Size: 189mm x 246mm Luther ftoc.tex V3 - 04/22/2016 2:03 P.M.
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