MOLTEN SALTS AND IONIC LIQUIDS MOLTEN SALTS AND IONIC LIQUIDS Never the Twain? Edited by Marcelle Gaune-Escard Ecole Polytechnique Marseille, France Kenneth R. Seddon QUILL, The Queen's University of Belfast Belfast, United Kingdom WILEY A JOHN WILEY & SONS, INC., PUBLICATION Copyright © 2010 by John Wiley & Sons, Inc. 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, 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. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, 201-748-6011, fax 201-748-6008, or online at http://www.wiley.com/go/permission. 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. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at 877-762-2974, outside the United States at 317-572- 3993 or fax 317-572-4002. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com. Library of Congress Cataloging-in-Publication Data: Molten salts and ionic liquids : never the Twain? / edited by Marcelle Gaune-Escard, Kenneth R. Seddon. p. cm. Includes bibliographical references and index. ISBN 978-0-471-77392-4 (cloth) 1. Fused salts. 2. Ionic solutions. 3. Coulomb potential. I. Gaune-Escard, Marcelle. II. Seddon, Kenneth R., 1950- QD189.M596 2009 546' .34-dc22 2008047048 Printed in the United States of America 10 9 8 7 6 5 4 3 21 CONTENTS Acknowledgements ix Preface xi Editorial xiii Contributors xvii 1 Ionic Liquids in the Temperature Range 150-1500 K: Patterns and Problems 1 C. Austen Angelí 2 Conductivities of Ionic Liquid Mixtures with Organic Electrolyte Solutions 25 D. Bansal, F. Croce, J. Swank, and M. Salomon 3 How Hydrophilic Ionic Liquids Behave in Aqueous Solutions 37 Marijana Blesic, Kenneth R. Seddon, Natalia V. Plechkova, Nimal Gunaratne, Antonio Lopes, and Luis Paulo N Rebelo 4 Mass Spectrometric Studies on Ionic Liquid Aggregates 49 R. Lopes da Silva, I. M. Marrucho, J. A. P. Coutinho, and Ana M. Fernandes 5 Study of Sm-Al Alloy Formation in the Molten LiCl-KCl Eutectic 63 G. De Córdoba and C. Caravaca 6 Alumina Solubility and Electrical Conductivity in Potassium Cryolites with Low Cryolite Ratio 75 Alexander Dedyukhin, Alexei Apisarov, Olga Tkatcheva, Yurii Zaikov, and Alexander Redkin 7 Ionic Liquids as Solvents for the Variable Temperature Electrodeposition of Metals and Semiconductors: A Short Introduction 85 S. Zein El Abedin and F. Endres v vi CONTENTS 8 Predicting the Thermodynamic Behaviour of Water + Ionic Liquids Systems Using COSMO-RS 101 M. G. Freiré, L. M. N. B. F. Santos, I. M. Marrucho, and J. A. P. Coutinho 9 Metallic Inert Anodes for Aluminium Electrolysis 123 /. Galasiu, R. Galasiu, and C. Nicolescu 10 The Behaviour of Phosphorus and Sulfur in Cryolite-Alumina Melts: Thermodynamic Considerations 133 /. Galasiu, R. Galasiu, C. Nicolescu, J. Thonstad, and G. M. Haarberg 11 Ionic Liquid-Ionic Liquid Biphasic Systems 143 Dirk Gerhard, Friedrich Fick, and Peter Wasserscheid 12 Recent Developments in the Reprocessing of Spent Fuel by Catalyst Enhanced Molten Salt Oxidation (CEMSO) 151 Trevor R. Griffiths, Vladimir A. Volkovich, and W. Robert Carper 13 Plasma-Induced Molten Salt Electrolysis to Form Functional Fine Particles 169 Yasuhiko ho, Tokujiro Nishikiori, and Takuya Goto 14 Liquid Electrolytes: Their Characterisation, Investigation, and Diverse Applications 181 Keith E. Johnson 15 Protection of a Microstructured Molybdenum Reactor from High Temperature Oxidation by Electrochemical Deposition Coatings in Molten Salts 193 S. A. Kuznetsov, A. R. Dubrovskiy, S. V. Kuznetsova, E. V. Rebrov, M. J. M. Mies, M. H. J. M. de Croon, and J. C. Schouten 16 Molten Salt Synthesis of LaA10 Powder at Low Temperatures 219 3 Zushu Li, Shaowei Zhang, and William Edward Lee 17 Accurate Measurement of Physicochemical Properties on Ionic Liquids and Molten Salts 229 V. M. B. Nunes, M. J. V. Lourenqo, F. J. V. Santos, M. L. S. M. Lopes, and C. A. Nieto de Castro 18 Molten Salt Physics and Chemistry in the Current Development of Spent Nuclear Fuel Management 265 Toru Ogawa, Kazuo Minato, and Yasuo Arai CONTENTS vii 19 An Organic Chemist's Perspective on High Temperature Molten Salts and Room Temperature Ionic Liquids 279 Richard M. Pagni 20 Raman Spectroscopy of High Temperature Melts 301 G. N. Papatheodorou, A. G. Kalampounias, and S. N. Yannopoulos 21 Thermodynamic Properties of LnI-MI Binary Systems 3 (Ln = La or Nd; M = K, Rb, or Cs) 341 Leszek Rycerz, M. F. Butman, and Marcelle Gaune-Escard 22 Materials Informatics for Molten Salts Chemistry 355 Changwon Suh, Slobodan Gadzuric, Marcelle Gaune-Escard, and Krishna Rajan 23 A Novel Ionic Liquid-Polymer Electrolyte for the Advanced Lithium Ion Polymer Battery 367 Daisuke Teramoto, Ryo Yokoyama, Hiroshi Kagawa, Tsutomu Sada, and Naoya Ogata 24 Solubility of A10 in NaCl-KCl Based Molten Salt System 389 2 3 Y. Xiao, C. R. Mambote, G. A. Wierink, and A. van Sandwijk 25 Molten Salt Synthesis of Ceramic Materials 397 Shaowei Zhang, D. D. Jayaseelan, Zushu Li, and William Edward Lee 26 Fuel Cell and Electrolysis Studies with Dual Phase Proton and Oxide Ion Conduction 407 Bin Zhu, S. Li, X. L. Sun, and J. C. Sun Index 419 ACKNOWLEDGEMENTS Although our names appear on the title page as editors, the production of this volume would not have been possible without the superlative support we received. In particular, Joyce Bartolini was the conference secretary for the Tunisia meeting, and Deborah Poland was the editorial assistant for this volume. The energy, and meticulous attention to detail, of Joyce and Deborah, and their willingness to go that extra mile, have been invaluable, and are fully appreciated. Also without the financial support of the conference sponsors, the original meeting would not have happened, and so we gratefully acknowledge the generosity of: The European Association for Chemical and Molecular Sciences; The Electrochemical Society; US Army— Communications-Electronics Research Development and Engineering Center; US Army—International Technology Center Atlantic; The European Office of Aerospace Research and Development, Air Force Office of Scientific Research, United States Air Force Research Laboratory; US Navy—Office of Naval Research Global; and the International Council for Science: Committee on Data for Science and Technology. MARCELLE GAUNE-ESCARD KENNETH R. SEDDON ix x ACKNOWLEDGEMENTS EUCHEM CONFERENCES ON MOLTEN SALTS 1966 Norway, Trondheim Tormod F0rland 1968 Italy, Pavia Mario Rolla 1970 France, Trois Epis Jean Brenet 1972 UK (England), Cirencester Douglas Inman 1974 Germany, Freising Alfred Klemm 1976 The Netherlands, Leiden Jan A. A. Ketelaar 1978 Sweden, Lysekill Arnold Lunden 1980 Israel, Dead Sea Yizhak Markus 1982 France, La Gaillarde Marcelle Gaune-Escard 1984 Denmark, Helsing0r Niels J. Bjerrum 1986 Norway, Geiranger Harald 0ye 1988 UK (Scotland), St. Andrews John Duffy 1990 Greece, Patras George Papatheodorou 1992 Belgium, De Haan Bernard Gilbert 1994 Germany, Bad Herrenalb Werner Freyland 1996 Slovakia, Smolenice Vladimir Danek 1998 France, Porquerolles Marcelle Gaune-Escard 2000 Denmark, Karrebaeksminde Niels J. Bjerrum 2002 UK (England), Oxford Paul Madden 2004 Poland, Piechowice Adolf Kisza EUCHEM CONFERENCES ON MOLTEN SALTS AND IONIC LIQUIDS 2006 Tunisia, Hammamet Marcelle Gaune-Escard Kenneth R. Seddon 2008 Denmark, Copenhagen Rasmus Fehrmann 2010 Germany, Bamberg Peter Wasserscheid 2012 UK (Wales), Newport Kenneth R. Seddon 2014 Greece Soghomon Boghosian PREFACE Between Sunday 17th September 2006 and Friday 22nd September 2006, a meeting of major significance occurred in Hammamet, Tunisia: the 21st meeting of a series of EuChem Conferences on Molten Salts (for a comprehensive list, see preceding page). Not only did the 21st meeting have a metaphorical significance—a coming of age— but it marked a change in focus and title for the meetings. No longer the EuChem Conferences on Molten Salts, they were relaunched, phoenix-like, as the EuChem Conferences on Molten Salts and Ionic Liquids. This was a result of a long series of private conversations with many key figures, which culminated in an editorial (reproduced on the following pages) in Molten Salts Bulletin (2005, 85, 1-3). A gauntlet had been thrown down. To condense the arguments: Molten salts and ionic liquids are both liquid salts containing only ions—they are thus the same subject. All that is different is the temperature! Both fields involve the study of Coulombic fluids for academic and industrial purposes, both employ the same principles, both require skilled practitioners (but high temperature systems require greater skills), both speak the same language; all that is different is image, and how superficial is that? There is so much knowledge, both empirical and theoretical, which can be passed from the molten salt community to the ionic liquid community, and vice versa. The gauntlet was picked up, and the result was the Hammamet meeting, and this book. We believe this meeting has catalysed a rapprochement between the two communities: East has met West, the peaches have touched, the brooklets have mingled, and the Montagues and the Capulets are reunited. Both fields are now stronger for this, and the future meetings are assured to be the prime focus for renewing these exchanges. Whilst representing some of the key talks at the meeting, this book also provides discussion on the transfer of experimental methods and techniques between the differing temperature regimes. While it is conventionally invidious to highlight specific chapters, the reviews from Austen Angelí, Keith Johnson, Richard Pagni, and George Papatheodorou are remarkable for their depth of insight and breadth of pedagogic experience, while the chapter from Tsutomu Sada shows the way forward to the industrialisation of products based on this new technology. We believe this book will also act as a line in the sand—the contents are a snapshot of a strengthened field. The tears of the phoenix are said to contain the healing abilities of purity, and its cry is said to be a beautiful song. May it long continue to sing, and may we be aware enough to listen. MARCELLE GAUNE-ESCARD KENNETH R. SEDDON xi EDITORIAL NEVER THE TWAIN ? Oh, East is East, and West is West, and never the twain shall meet, Till Earth and Sky stand presently at God's great Judgment Seat; But there is neither East nor West, Border, nor Breed, nor Birth; When two strong men stand face to face, tho' they come from the ends of the earth! —Rudyard Kipling, The Ballad of East and West (1889) Marcelle has asked me to write a personal editorial for Molten Salts Bulletin, and so I am taking her at her word. It will be personal, and hence it will be polemical. And I take as my subject the unfortunate, nay potentially disastrous, split which has emerged between the (high temperature) molten salt community (East) and the (low tempera- ture) ionic liquid community (West). I will argue that this is destructive, cliquish, petty, and (if continuing) will result in the loss of key skills to the whole community. I do not want to wait until Judgement Day for the strong men (and women) of both camps to stand face to face! I had the honour and privilege of being introduced to low-temperature molten salts, henceforth referred to as ionic liquids, by the fathers of the field-Chuck Hussey and John Wilkes. I was able to learn at the feet of the experts, in depth, the practical and theoretical aspects of ionic liquids, including much unpublished information. In other words, they taught me the tricks of the trade, with enthusiasm and generosity. It led to years of fruitful collaboration with Chuck, and my introduction into the molten salts community. This was dominated by the grandfathers of the field, Bob Osteryoung and Gleb Mamantov. Now, from my experience in the field of second-harmonic genera- tion, whose practitioners were (by and large, but not universally) mean-minded, self- obsessed prima donnas, who treated newcomers as potential threats. I had steeled myself for a similar response from the molten salt community. Never had I been more wrong. I was immediately drawn to the core of the subject, and Bob and Gleb (intellectual giants) could not have been more welcoming to a tyro, and immensely generous with both their time and advice. And then there were the conferences: the Gordon Conferences, the Molten Salt Sessions at the Electrochemical Society meetings, the EUCHEM meetings, the Molten Salt series, and the Molten Salts Discussion Group (MSDG). And, as a zenith, the NATO ASI meeting in Camerino, 'From Molten Salts Bulletin, 85 1-3 (2005). xiii