IODINE CHEMISTRY AND APPLICATIONS IODINE CHEMISTRY and APPLICATIONS Edited by TATSUO KAIHO Copyright © 2015 by John Wiley & Sons, Inc. All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada 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, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com. 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I. Title. TP245.I6K35 2014 661′.1–dc23 2014017643 Cover Image: Courtesy of Tatsuo Kaiho Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 CONTENTS LIST OF CONTRIBUTORS ix PREFACE xiii 1 Overview 1 Tatsuo Kaiho PArt I CHARACTERISTICS, ELEMENTAL OF IODINE 7 2 Physical Properties of Iodine 9 Tatsuo Kaiho 3 Analytical Methods for Iodine and Iodides 15 Hirofumi Kanoh and Takehisa Konishi 4 Ion Chromatography 25 Anna Błażewicz 5 Inorganic Iodides 55 Tatsuo Kaiho 6 Organic Iodides 75 Tsugio Kitamura v vi CONTENTS 7 Hypervalent Iodine 103 Toshifumi Dohi and Yasuyuki Kita 8 Iodine and Halogen Bonding 159 Giancarlo Terraneo, Giuseppe Resnati, and Pierangelo Metrangolo PArt II ProDUCTION OF IODINE 195 9 History of Iodine 197 James L. Marshall and Virginia R. Marshall 10 Production Process in the Past 207 Tatsuo Kaiho 11 Iodine Production from Caliche 213 Armin Lauterbach 12 Iodine Production from Oilfield Brine 221 Stanley T. Krukowski 13 Iodine Production from Natural Gas Brine 231 Nobuyuki Kaneko and Tatsuo Kaiho 14 Recycling of Iodine 243 Tatsuo Kaiho PArt III SYNTHESIS OF IODINE COMPOUNDS 249 15 Iodinating Reagents 251 Haruhiko Taguchi 16 Oxidizing Agents 277 Toshifumi Dohi and Yasuyuki Kita 17 Reaction of Iodo Compounds 303 Toshifumi Dohi and Yasuyuki Kita 18 Metal Iodides–Mediated Reaction 329 Makoto Shimizu, Iwao Hachiya, and Junji Inanaga CONTENTS vii PArt IV BIOLOGICAL APPLICATION OF IODINE 353 19 Iodinated X-Ray Contrast Agents 355 Werner Krause 20 Iodine as Disinfectant 375 Waldemar Gottardi 21 Synthetic Thyroid Hormone 411 Steven E. Rokita 22 Iodine Deficiency Disorders and Their Correction Using Iodized Salt and/or Iodine Supplements 421 Michael B. Zimmermann 23 Pharmaceuticals: Therapeutic Agents 433 Tatsuo Kaiho 24 Agrochemicals and Anthelmintics 439 Peter Jeschke and Tatsuo Kaiho PArt V INDUSTRIAL APPLICATION OF IODINE 457 25 Diaryliodonium Salt Photoacid Generators 459 James V. Crivello 26 Polarizing Films 479 Bart Kahr and Kevin M. Knowles 27 Iodine in Polymer Synthesis: An Important Element for Precision Polymerizations 489 Mitsuo Sawamoto 28 Iodine in Dye-Sensitized Solar Cells 501 Lars Kloo 29 Fluorinated Repellents 513 Toyomichi Shimada 30 Etching Gas 523 Seiji Samukawa 31 Other Industrial Applications 547 Tatsuo Kaiho viii CONTENTS PArt VI BIOINORGANIC CHEMISTRY AND EnvironMENTAL CHEMISTRY OF IODINE 555 32 Iodine Bioinorganic Chemistry: Physiology, Structures, and Mechanisms 557 Frithjof C. Küpper and Peter M.H. Kroneck 33 Atmospheric Chemistry of Iodine 591 Lucy J. Carpenter PArt VII RADioisotope OF IODINE 603 34 Radioactive Iodine 605 Yoshifumi Shirakami INDEX 625 LIST OF CONTRIBUTORS Anna BłażewiczDepartment of Analytical Chemistry, Medical University of Lublin, Lublin, Poland Lucy J. Carpenter Wolfson Atmospheric Chemistry Laboratories, University of York, Heslington, York, UK James V. Crivello Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, Troy, New York, NY, USA Toshifumi Dohi College of Pharmaceutial Sciences, Ritsumeikan University, Kusatsu, Shiga, Japan Waldemar Gottardi Department of Hygiene, Microbiology and Social Medicine, Division of Hygiene and Medical Microbiology, Innsbruck Medical University, Innsbruck, Austria Iwao Hachiya Department of Chemistry for Materials, Mie University, Tsu, Mie, Japan Junji Inanaga Institute for Molecular Chemistry and Engineering, Kyushu University, Fukuoka, Japan Peter Jeschke Bayer CropScience AG, Monheim am Rhein, Germany Bart Kahr Department of Chemistry and Molecular Design Institute, New York University, New York, NY, USA Tatsuo Kaiho Nihon Tennen Gas Co., Ltd., Chiba, Japan ix x LIST OF CONTRIBUTORS Nobuyuki Kaneko Institute for Geo-Resources and Environment, Geological Survey of Japan, AIST, Tsukuba, Ibaraki, Japan Hirofumi Kanoh Chiba University, Chiba, Japan Yasuyuki Kita Emeritus Professor of Osaka University, Ritsumeikan University, Kusatsu, Shiga, Japan Tsugio Kitamura Department of Chemistry and Applied Chemistry, Graduate School of Science and Engineering, Saga University, Saga, Japan Lars Kloo KTH Royal Institute of Technology, Stockholm, Sweden Kevin M. Knowles Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UK Takehisa Konishi Chiba University, Chiba, Japan Werner Krause Bayer Healthcare Pharmaceuticals, Berlin, Germany Peter M.H. Kroneck Department of Biology, University of Konstanz, Konstanz, Germany Stanley T. Krukowski Oklahoma Geological Survey, Mewbourne College of Earth and Energy, The University of Oklahoma, Norman, OK, USA Frithjof C. Küpper Oceanlab, University of Aberdeen, Newburgh, UK Armin Lauterbach SQM, Santiago, Chile James L. Marshall Department of Chemistry, University of North Texas, Denton, TX, USA Virginia R. Marshall Department of Chemistry, University of North Texas, Denton, TX, USA Pierangelo Metrangolo Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Milan, Italy Giuseppe Resnati Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Milan, Italy Steven E. Rokita Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA Seiji Samukawa Tohoku University, Sendai, Japan Mitsuo Sawamoto Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto, Japan Toyomichi Shimada Asahi Glass Co., Ltd., Tokyo, Japan LIST OF CONTRIBUTORS xi Makoto Shimizu Department of Chemistry for Materials, Mie University, Tsu, Mie, Japan Yoshifumi Shirakami Research Centre Nihon Medi-Physics, Co., Ltd., Sodegaura, Chiba, Japan Haruhiko Taguchi Tokyo Chemical Industry Co., Ltd., Tokyo, Japan Giancarlo Terraneo Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Milan, Italy Michael B. Zimmermann Laboratory for Human Nutrition, Department of Health Science and Technology, Swiss Federal Institute of Technology (ETH) Zürich, Zurich, Switzerland PREFACE A member of the halogen group on the periodic table, iodine is found in seaweeds, the brine extracted along with natural gas, and Chilean caliche deposits. Iodine is a micronutrient element that is fundamental to a living body and is essential for the subsistence and growth of humans and animals. The goiter-preventing effects of iodine in seaweeds were known to the legendary Chinese emperor Shen-Nung as early as around 3000 BC, and the knowledge of this treatment was available in Greece by the time of Hippocrates. Nevertheless, iodine was not isolated and recog- nized as an element until the early nineteenth century. In 1811, Barnard Courtois of France found that violet vapor with a strong smell was generated while producing niter from seaweed ashes, and that when the vapor was cooled down,