Mercury Handbook Chemistry, Applications and Environmental Impact . Published on 11 October 2013 http://pubs.rsc.org | doi:10.1039/9781849735155-FP001 View Online . Published on 11 October 2013 http://pubs.rsc.org | doi:10.1039/9781849735155-FP001 View Online Mercury Handbook Chemistry, Applications and Environmental Impact Leonid F Kozin and Steve Hansen Email: [email protected], [email protected] . Published on 11 October 2013 http://pubs.rsc.org | doi:10.1039/9781849735155-FP001 View Online Technical Editor: Cezary Guminski Translated by Mark Kit ISBN: 978-1-84973-409-7 A catalogue record for this book is available from the British Library . r L F Kozin and S C Hansen 2013 All rights reserved Published on 11 October 2013 http://pubs.rsc.org | doi:10.1039/9781849735155-FP001 Apart from fair dealing for the purposes of research for non-commercial purposes or for private study, criticism or review, as permitted under the Copyright, Designs and Patents Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry or the copyright owner, or in the case of reproduction in accordance with the terms of licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK. Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page. The RSC is not responsible for individual opinions expressed in this work. Published by The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 0WF, UK Registered Charity Number 207890 Visit our website at www.rsc.org/books Preface The Mercury Handbook attempts to cover all of the basic subject matter related to the condensed phase physics, chemistry, metallurgy, application and environmental aspects of mercury. The present book is derived from Leonid F. Kozin’s book on the physical chemistry and metallurgy of high- purity mercury (Fizikokhimiia i Metallurgiia Vysokochistoi Rtuti i ee Splavov). The original Russian text was translated by Mark Kit of Language Interface in New York. Unfortunately a large percentage of the original work remains in Russian at the present time. Dr. Cezary Guminski assisted in the translation and technical editing of the book and also wrote a chapter on the use of mercury in small-scale gold mining. Numerous important contributions were made to the book by others. Jason Gray of Nippon Instruments North America explained the practical . operation of atomic fluorescence spectroscopy. A thorough discussion of the medical symptoms of mercury intoxication was generously providead by Bethlehem Apparatus, Inc. of Hellertown, Pennsylvania. The University of Illinois at Urbana-Champaign has provided invaluable access to its vast Published on 11 October 2013 http://pubs.rsc.org | doi:10.1039/9781849735155-FP005 collection of online and print journals. Dr. Tim Brumleve of APL Engineered Materials, Inc. has assisted in the proof reading of key chapters of the present book. The authors wish to thank their families for their extraordinary patience during the writing and editing of the manuscript. The staff of the Royal Society of Chemistry has endured more than necessary and is complimented for their professionalism and for their patience. Special mention should be given to Mrs. Janet Freshwater, Mrs. Alice Toby-Brant, Ms. Sarah Salter, Mrs. Katrina Harding, Mrs Rosalind Searle and others. They were exceptionally polite and patient throughout the entire writing process. Lastly, the staff of Strawberry Mercury Handbook: Chemistry, Applications and Environmental Impact By Leonid F Kozin and Steve Hansen r L F Kozin and S C Hansen 2013 Published by the Royal Society of Chemistry, www.rsc.org v View Online vi Preface Fields in Urbana has provided encouragement and refreshment throughout the arduous task of writing this monograph. Additional information and updates to the Mercury Handbook can be found at www.mercuryhandbook.com. Leonid F. Kozin Kyiv, Ukraine Steve C. Hansen Urbana, Illinois . Published on 11 October 2013 http://pubs.rsc.org | doi:10.1039/9781849735155-FP005 Contents Chapter 1 Physicochemical Properties of Metallic Mercury 1 1.1 Atomic Properties 1 1.2 Crystallography 3 1.2.1 P–T Diagram 3 1.3 Melting Point 4 1.4 Heat of Fusion 4 1.5 Heat Capacity 4 1.6 Thermal Conductivity 6 1.7 Emissivity 9 1.8 Boiling Point, Heat and Entropy of Vaporization 9 1.9 Vapor Pressure 10 . 1.9.1 Solid Mercury 10 1.9.2 Liquid Mercury 12 1.9.3 Triple Point 12 1.9.4 Critical Temperature and Pressure 13 Published on 11 October 2013 http://pubs.rsc.org | doi:10.1039/9781849735155-FP007 1.10 Density 14 1.11 Surface Tension 17 1.12 Viscosity 18 1.13 Isothermal Compressibility 19 1.14 Thermal Expansion Coefficient 20 1.15 Self-diffusion 21 1.16 Electrical and Magnetic Properties 24 1.17 Hall Coefficient 26 1.18 Superconductivity 27 1.19 Excited-state Properties 27 References 28 Mercury Handbook: Chemistry, Applications and Environmental Impact By Leonid F Kozin and Steve Hansen r L F Kozin and S C Hansen 2013 Published by the Royal Society of Chemistry, www.rsc.org vii View Online viii Contents Chapter 2 Amalgam Solubility 36 2.1 Solubility of Metals in Mercury 36 2.2 Amalgams with Compounds Formed in the Solid Phase 40 References 46 Chapter 3 Diffusion of Metals in Mercury 50 3.1 Effect of Atomic Size on Diffusion 50 3.1.1 Effect of Atomic Radius 51 3.2 Temperature Dependence of Diffusion in Amalgams 54 3.3 Concentration Effects on Diffusion 55 3.4 Diffusion of Mercury in Solid Metals 57 References 58 Chapter 4 Purification of Mercury Using Chemical and Electrochemical Methods 61 4.1 Technical Requirements for Mercury 61 4.2 Chemical Methods for Mercury Treatment 62 4.3 Single-stage Electrochemical Methods for Obtaining High-purity Mercury 75 . References 77 Published on 11 October 2013 http://pubs.rsc.org | doi:10.1039/9781849735155-FP007 Chapter 5 Chemical Properties of Mercury 80 5.1 Inorganic Mercury Compounds 80 2þ 21 5.1.1 Disproportionation in Hg2 and Hg 80 5.1.2 Solubility of Metallic Mercury in Water 81 5.1.3 Solubility of Mercury in Ionic Solutions 84 5.2 Mercury(I) and Mercury(II) Halides and Pseudohalides 86 5.2.1 Mercury(I) Fluoride – Hg2F2 87 5.2.2 Mercury(II) Fluoride – HgF2 87 5.2.3 Mercury(I) Chloride (Calomel) – Hg2Cl2 89 5.2.4 Mercury(II) Chloride (Corrosive Sublimate) – HgCl2 90 5.2.5 Mercury(I) Bromide – Hg2Br2 96 5.2.6 Mercury(II) Bromide – HgBr2 97 5.2.7 Mercury(I) Iodide – Hg2I2 101 5.2.8 Mercury(II) Iodide – HgI2 103 5.2.9 Mixed Mercury(II) Halides 106 View Online Contents ix 5.2.10 Mercury(II) Cyanide – Hg(CN)2 106 5.2.11 Mercury(I) Dithiocyanate – Hg2(SCN)2 108 5.2.12 Mercury(II) Dithiocyanate – Hg(SCN)2 108 5.3 Oxygen Compounds of Mercury(I) and Mercury(II) 109 5.3.1 Mercury(I) Oxide – Hg2O 109 5.3.2 Mercury(II) Oxide – HgO 110 5.3.3 Mercury(I) Nitrate Dihydrate – Hg2(NO3)2 Á 2H2O 114 5.3.4 Mercury(II) Nitrate – Hg(NO3)2 115 5.3.5 Mercury(I) Perchlorate – Hg2(ClO4)2 116 5.3.6 Mercury(II) perchlorate – Hg(ClO4)2 116 5.4 Organometallic Mercury Compounds 116 5.4.1 Organometallic Mercury(I) Compounds 116 5.4.2 Organometallic Mercury(II) Compounds 117 References 120 Chapter 6 Electrochemical Properties of Mercury 128 6.1 Kinetics and Mechanism of Discharge and Ionization of Mercury in Simple Electrolytes 128 6.2 Kinetics and Mechanism of Discharge and Ionization of Mercury in Complex-forming Media 138 References 140 . Chapter 7 Lighting 143 Published on 11 October 2013 http://pubs.rsc.org | doi:10.1039/9781849735155-FP007 7.1 Introduction 143 7.1.1 Lamp Color and Quality Measurements 144 7.2 Fluorescent Lighting 144 7.2.1 Mercury Content in Fluorescent Lamps 146 7.2.2 Amalgam-controlled Mercury Vapor Pressure 146 7.2.3 Temperature-controlled Amalgams 147 7.2.4 Mercury Dispensers 149 7.3 Measurement of Mercury Vapor Pressure of Fluorescent Lamp Amalgams 151 7.3.1 Vapor Pressure Measurement System 151 7.3.2 Atomic Absorption Spectrometry 152 7.3.3 Knudsen Effusion Mass Spectrometry 152 7.4 High-pressure Mercury Lamp 152 7.5 Ultra-high-performance Lamps 153 7.6 High-pressure Sodium Lamps 154 7.7 Metal Halide Lamps 157 References 159 View Online x Contents Chapter 8 Synthesis of Semiconducting Compounds 163 8.1 Synthesis of Semiconducting Mercury Compounds 163 8.1.1 Sublimation and Resublimation Methods 170 8.1.2 Methods Used to Grow Single Crystals 170 8.2 Indirect Synthesis of Mercury Chalcogenides 171 8.2.1 Transport Reactions Method 172 8.2.2 Epitaxial Layer Growth 174 References 176 Chapter 9 Chlor-Alkali Process 180 9.1 Introduction 180 9.2 Electrochemistry of the Mercury Cathode Process 180 9.3 Sodium–Mercury Phase Diagram 181 9.4 Production of Chlorine 185 References 191 Chapter 10 Use of Mercury in Small-scale Gold Mining 193 Cezary Guminski 10.1 Introduction 193 10.1.1 Reasons for Artisanal Gold Mining 194 10.1.2 Mercury Pollution 194 10.2 Method of Artisanal Gold Mining 194 . 10.3 Environmental Degradation Caused by Small-scale Gold Mining 196 10.4 Remedies or Improvements to Small-scale Published on 11 October 2013 http://pubs.rsc.org | doi:10.1039/9781849735155-FP007 Gold Mining 197 References 198 General References 198 Chapter 11 Mercury Legislation in the United States 199 11.1 Introduction 199 11.2 Mercury Legislation 199 11.2.1 Mercury Export Ban Act 200 11.2.2 Mercury-containing and Rechargeable Battery Management Act 201 11.2.3 Legislation Controlling Mercury Release 201 11.2.4 Food and Drug Administration 204 11.3 Mercury Regulations and Standards 204 11.3.1 Measurement of Mercury in Water 205 11.3.2 Land Disposal Restrictions 205 11.3.3 Mercury in Air 205 11.4 Occupational Safety and Health Administration 207 View Online Contents xi 11.5 Department of Transportation and International Air Transport Association 207 References 208 Chapter 12 Environmental Aspects of the Industrial Application of Mercury 209 Leonid F.