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Industrial Inorganic Chemistry iranchembook.ir/edu iranchembook.ir/edu iranchembook.ir/edu Theopen University RSaC U ROYAL SOCIETY OF CHEMISTRY The Molecular World Elements of the p Block iranchembook.ir/edu This publication forms part of an Open University course, S205 The Molecular World. Most of the texts which make up this course are shown opposite. Details of this and other Open University courses can be obtained from the Call Centre, PO Box 724, The Open University, Milton Keynes MK7 6ZS, United Kingdom: tel. +44 (0) 1908 653231, e-mail [email protected] Alternatively, you may visit the Open University website at http://www.open.ac.uk where you can learn more about the wide range of courses and packs offered at all levels by The Open University. The Open University, Walton Hall, Milton Keynes, MK7 6AA First published 2002 Copyright 0 2002 The Open University All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, transmitted or utilized in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without written permission from the publisher or a licence from the Copyright Licensing Agency Ltd. Details of such licences (for reprographic reproduction) may be obtained from the Copyright Licensing Agency Ltd of 90 Tottenham Court Road, London W 1T 4LP. Edited, designed and typeset by The Open University. Published by the Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 OWF, UK. Printed in the United Kingdom by Bath Press Colourbooks, Glasgow. ISBN 0 85404 690 9 A catalogue record for this book is available from the British Library. 1.1 s205book 9 i 1.1 iranchembook.ir/edu This series provides a broad foundation in chemistry, The series has been devised as the course material for introducing its fundamental ideas, principles and the Open University Course S205 The Molecular World. techniques, and also demonstrating the central role of Details of this and other Open University courses can be chemistry in science and the importance of a molecular obtained from the Course Information and Advice Centre, approach in biology and the Earth sciences. Each title is PO Box 724, The Open University, Milton Keynes attractively presented and illustrated in full colour. MK7 6ZS, UK; Tel+44 (0)1908 653231; e-mail: ces-gen @ open.ac.uk. Alternatively, the website at The Molecular World aims to develop an integrated www.open.ac.uk gives more information about the approach, with major themes and concepts in organic, wide range of courses and packs offered at all levels inorganic and physical chemistry, set in the context of by The Open University. chemistry as a whole. The examples given illustrate both the application of chemistry in the natural world and its Further information about this series is available at importance in industry. Case studies, written by w w w. rsc. o rghole cu lanvorld. acknowledged experts in the field, are used to show how Orders and enquiries should be sent to: chemistry impinges on topics of social and scientific interest, such as polymers, batteries, catalysis, liquid Sales and Customer Care Department, Royal Society of crystals and forensic science. 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The titles in The Molecular World series are: edited by Lesley Smart and Michael Gagan edited by David Johnson edited by Michael Mortimer and Peter Taylor edited by Elaine Moore edited by Peter Taylor and Michael Gagan edited by Lesley Smart edited by Charles Harding, David Johnson and Rob Janes edited by Peter Taylor iranchembook.ir/edu Course Team Chair Course Reader Lesley Smart Cliff Ludman Open University Authors Course Assessor Eleanor Crabb (Book 8) Professor Eddie Abel, University of Exeter Michael Gagan (Book 3 and Book 7) Audio and Audiovisual recording Charles Harding (Book 9) Kirsten Hintner Rob Janes (Book 9) Andrew Rix David Johnson (Book 2, Book 4 and Book 9) Elaine Moore (Book 6) Design Michael Mortimer (Book 5) Steve Best Lesley Smart (Book 1, Book 3 and Book 8) Carl Gibbard Peter Taylor (Book 5, Book 7 and Book 10) Sarah Hack Judy Thomas (Study File) Lee Johnson Ruth Williams (skdls, assessment questions) Mike Levers Other authors whose previous contributions to the earlier Sian Lewis courses S246 and S247 have been invaluable in the Jenny Nockles preparation of this course: Tim Allott, Alan Bassindale, Stuart Jon Owen Bennett, Keith Bolton, John Coyle, John Emsley, Jim Iley, Ray John Taylor Jones, Joan Mason, Peter Morrod, Jane Nelson, Malcolm Howie Twiner Rose, Richard Taylor, Kilu Warr. Liz Yeomans Course Manager Library Mike Bullivant Judy Thomas Course Team Assistant Picture Researchers Debbie Gingell Lydia Eaton Course Editors Deana Plummer Pat Forster Technical Assistance Ian Nuttall Brandon Cook Bina Sharma Pravin Pate1 Dick Sharp Peter Twomey Consultant Authors Pamela Wardell Ronald Dell (Case Study: Batteries and Fuel Cells) Adrian Dobbs (Book 8 and Book 10) CD-ROM Production Clms Falshaw (Book 10) Andrew Bertie Andrew Galwey (Case Study: Acid Rain) Greg Black Guy Grant (Case Study: Molecular Modelling) Matthew Brown Alan Heaton (Case Study: Industrial Organic Chemistry, Philip Butcher Case Study: Industrial Inorganic Chemistry) Chris Denham Bob Hill (Case Study: Polymers and Gels) Spencer Harben Roger Hill (Book 10) Peter Mitton Anya Hunt (Case Study: Forensic Science) David Palmer Corrie Imrie (Case Study: Liquid Crystals) BBC Clive McKee (Book 5) Rosalind Bain Bob Murray (Study File, Book 11) Stephen Haggard Andrew Platt (Case Study: Forensic Science) Melanie Heath Ray Wallace (Study File, Book 11) Darren Wycherley Craig Williams (Case Study: Zeolites) Tim Martin Jessica Barrington iranchembook.ir/edu ELEMENTS OF THE p BLOCK Charlie Harding, Rob Janes and David Johnson 1.1 Group numbers and the Periodic Table 15 2.1 Oxidation numbers or oxidation states 17 2.2 Balancing redox equations 19 2.3 Summary of Section 2 21 3.1 Strengths of acid and bases 22 3.2 The Bronsted-Lowry theory 22 3.3 The pH scale and acid strength 25 3.4 Summary of Section 3 27 4.1 Lewis acids and bases 29 4.2 The strengths of chemical bonds 30 4.3 Bond enthalpy terms and electronegativities 32 4.4 Dipole moments 33 4.5 Intermolecular forces 36 4.6 Summary of Section 4 39 5.1 Preparation and properties of hydrogen 42 5.2 Industrial uses of hydrogen 43 5.3 Hydrogen as a fuel 44 5.4 Atomic and ionic properties of hydrogen 46 5.5 The aqueous hydrogen ion 49 5.6 Summary of Sections 5.1-5.5 50 iranchembook.ir/edu 5.7 The hydrides of the typical elements 50 5.7.1 Salt-like hydrides 51 5.7.2 Macromolecular hydrides 51 5.7.3 Molecular hydrides 52 5.7.4 Trends in structure 52 5.8 Hydrogen-bonding 52 5.9 Summary of Sections 5.7 and 5.8 59 6.1 Industrial uses of the halogens 63 6.2 Properties of halogen atoms 64 6.3 Oxidation number -1: halides 65 6.3.1 The hydrogen halides 66 6.4 Thermodynamics of the halogen-halide relationship 68 6.4.1 Halides and oxidation numbers 70 6.4.2 Oxidizing strength of the halogens in aqueous solution 71 6.5 Summary of Sections 6.1-6.4 72 6.6 Higher oxidation states of the halogens 74 6.6.1 Halogen oxides and oxoacids 77 6.6.2 Interhalogen compounds 80 6.6.3 Polyhalogen ions 81 6.6.4 Summary of Section 6.6 83 7.1 The discovery of the noble gases 85 7.2 The manufacture and properties of the noble gases 87 7.3 Uses of the noble gases 89 7.4 Summary of Sections 7.1-7.3 90 7.5 Noble gas compounds 91 7.5.1 The fluorides and oxides of xenon and krypton 91 7.5.2 Other xenon compounds 94 7.5.3 Helium, neon and argon chemistry 94 7.5.4 The structure of noble gas compounds 95 7.5.5 The bonding in noble gas compounds 96 7.5.6 Summary of Section 7.5 98 iranchembook.ir/edu 8.1 Single and multiple bonds 101 8.2 Third-row elements: a case for expansion of the octet? 102 8.3 Trends in the Periodic Table 104 8.3.1 Trends across the Periods 104 8.3.2 Trends down the Groups 105 8.4 Summary of Section 8 107 9.1 Boron: occurrence and extraction 109 9.1.1 The boron atom 109 9.1.2 Lewis acidity in the boron halides 109 9.1.3 Boron and the borides 111 9.1.4 The boron hydrides 113 9.1.5 Boron-oxygen compounds 114 9.1.6 Summary of Section 9. I 116 9.2 Aluminium 117 9.2.1 Aqueous chemistry 118 9.2.2 Aluminium sulfate and water treatment 118 9.2.3 Aluminium toxicity 120 9.2.4 Aluminium halides 122 9.2.5 Two observations about aluminium chemistry 123 9.3 Gallium, indium and thallium 123 9.3.1 The inert pair effect 126 9.3.2 Summary of Sections 9.2 and 9.3 127 10.1 Structures and properties of the elements 129 10.2 Carbon 132 10.2.1 Carbides - molecular, salt-like and interstitial 137 10.2.2 Oxides of carbon 138 10.2.3 Summary of Section 10.2 141 10.3 Silicon 142 10.3.1 Bonding in silicon compounds 143 10.3.2 Silicon-oxygen compounds 145 10.3.3 Halosilanes 149 10.3.4 Compounds of silicon with hydrogen and alkyl groups 150 10.4 Germanium, tin and lead 153 10.5 Summary of Sections 10.3 and 10.4 154 iranchembook.ir/edu 11.1 Structures and properties of the elements 156 11.2 Nitrogen 158 11.2.1 Nitrogen hydrides 161 11.2.2 Nitrogen halides 162 11.2.3 Azides 163 11.2.4 Nitrogen-oxygen compounds 163 11.2.5 Summary of Sections 11.1 and 11.2 169 11.3 Phosphorus 170 11.3.1 The chemistry of phosphorus 171 11.3.2
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