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Inorganic Ion Exchangers in Chemical Analysis Editors Mohsin Qureshi, Ph.D. (Deceased) Emeritus Scientist Council of Scientific and Industrial Research Retired Dean Faculty of Engineering and Technology Aligarh Muslim University Aligarh, India K. G. Varshney, Ph.D. Department of Applied Chemistry Faculty of Engineering and Technology Aligarh Muslim University Aligarh, India CRC Press Boca Raton Ann Arbor Boston Library of Congress Cataloging-in-Publication Data Inorganic ion exchangers in chemical analysis / editors, Mohsin Qureshi, K. G. Varshney. p. cm. Includes bibliographical references and index. ISBN 0-8493-5526-5 1. Inorganic ion exchange materials. 2. Ion exchange. I. Qureshi, Mohsin. II.Varshney, K. G. QD562.I63I56 1990 543'.0893—dc20 90-39194 CIP This book represents information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Every reasonable effort has been made to give reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. All rights reserved. This book, or any parts thereof, may not be reproduced in any form without written consent from the publisher. Direct all inquiries to CRC Press, Inc., 2000 Corporate Blvd., N.W., Boca Raton, Florida 33431. © 1991 by CRC Press, Inc. 1991 by CRC Press, Inc. International Standard Book Number 0-8493-5526-5 Library of Congress Card Number 90-39194 Printed in the United States DEDICATION To all friends and colleagues in the international community of chem- ists who have made 3 decades of inorganic ion exchangers such a pleasure. K. G. Varshney, Ph.D. PREFACE Since the publication of C. Β. Amphlett's monograph Inorganic Ion Exchangers in 1964, these materials have gained renewed interest and a well defined position in analytical chem- istry. As a result, in 1982 A. Clearfield edited a CRC Press publication entitled Inorganic Ion Exchange Materials which gave an excellent description of these various types of materials as elucidated by authorities in the field. The main emphasis of these publications has, however, been on physical chemistry, particularly of the crystalline materials. The amorphous or poorly crystalline inorganic ion exchangers were not properly dealt with and their analytical aspects were not fully explored. In view of this, the present project was undertaken in order to give a comprehensive overview of the diverse studies done so far on inorganic ion exchangers and their analytical applications. An attempt has been made to highlight the various aspects of these studies with the help of a renowned group of scientists working in the field of chemical analysis. It is hoped that the information presented in this publication will benefit analytical chemists seeking some simple and novel means of separations with the help of the easy-to-prepare chromatographic materials. K. G. Varshney, Ph.D. THE EDITORS Professor Mohsin Qureshi, Ph.D., was an Emeritus Scientist of the Council of Sci- entific and Industrial Research of India. He retired as the Head of the Chemistry Section and Dean of the Faculty of Engineering and Technology, Aligarh Muslim University on March 31, 1984. He was appointed as a Lecturer of Chemistry in the Chemistry Department of Aligarh Muslim University in 1944, joined the Louisiana State University, Baton Rouge as a graduate student in 1955, and received his Ph.D. degree in 1958 from that University under Professor P. W. West. On his return to India in 1959, Dr. Qureshi started a new course in Analytical Chemistry leading to the M.S. degree in Aligarh Muslim University. In 1963 he was appointed Reader in Analytical Chemistry and in 1968 Professor in the Chemistry Section, Ζ. H. College of Engineering and Technology, Aligarh Muslim Uni- versity, Aligarh. Professor Qureshi died on July 17, 1988 in a road accident. Until his death, Professor Qureshi had been an active worker and was engaged in three research projects sponsored by the Council of Scientific and Industrial Research (CSIR), the University Grants Commission (UGC), and the Department of Science and Technology (DST). His research interests included chromatography, ion exchange, synthetic inorganic ion exchangers, detection and determination of organic functional groups, solid state chem- istry, and environmental chemistry. Professor Qureshi published more than 130 research papers in leading international journals and guided about 30 students for the Ph.D. degree. He was a Fellow of the Chemical Society of England, chaired numerous sessions in national and international conferences, and was invited to deliver talks by various Indian and foreign universities and research organizations. Krishna Gopal Varshney, Ph.D., at present, a Reader in the Department of Applied Chemistry, Faculty of Engineering and Technology, Aligarh Muslim University, did his M.Sc. in 1963 and Ph.D. in 1968 specializing in Analytical Chemistry from Aligarh Muslim University, Aligarh (India) under the supervision of Professor Mohsin Qureshi. He was engaged in the various assignments of teaching and research before his placement as Lecturer in 1971 in his present department, where he started guiding research independently. In 1983 he went to Rome as a Visiting Professor to do postdoctoral research with Professor Aldo LaGinestra at the University of Rome on thermal and catalytic behavior of inorganic ion exchangers. Thus far, Dr. Varshney has guided 13 students for their Ph.D. degree and 18 students for their M.Phil, degree, and has about 100 research publications to his credit all in journals of international repute. He has attended more than 20 conferences/seminars/workshops both of national and international character and has lectured/presided in some of them. His fields of main interest have been chromatography, ion exchange, electrophoresis, spectrophoto- metry, synthetic inorganic ion exchangers and environmental chemistry. Dr. Varshney has been a member of the Advisory Board of CRC's Handbook of Chro- matography (Inorganics) with Drs. Gunter Zweig and Joseph Sherma as its Chief Editors and Dr. Mohsin Qureshi as the Section Editor. He has also been a co-author in a chapter entitled ' Thin Layer Chromatography of Inorganics and Organometallics" in the Handbook of Thin Layer Chromatography, edited by Drs. J. Sherma and B. Fried, a Marcel Dekker publication. Dr. Varshney is a life member of the various learned scientific societies of India, such as the Indian Science Congress, Indian Chemical Society, Indian Council of Chemists, and the Indian Society of Analytical Scientists. He also particpates in panels of experts for various leading research journals of India. The current research interest of Dr. K. G. Varshney lies in the area of environmental studies. He has been conducting research projects funded by the Council of Scientific and Industrial Research (CSIR), the University Grants Commission (UGC), and the U. P. Council of Science and Technology (UPCST) to explore the various applications of inorganic ion exchangers, such as the industrial effluent treatments, catalysis, and the analysis of alloys, minerals and pharmaceutical products. CONTRIBUTORS Cornells J. Coetzee, D.Sc. Mohsin Qureshi, Ph.D. Professor (Deceased) Department of Chemistry Emeritus Scientist University of the Western Cape Council of Scientific and Industrial Bellville, South Africa Research Retired Dean Alan Dyer, Ph.D., D.Sc. Faculty of Engineering and Technology Reader Aligarh Muslim University Department of Chemistry Aligarh, India University of Salford Salford, England J. van R. Smit, D.Phil. Hahn & Hahn Mukhtar A. Khan, Ph.D. Hatfield, Pretoria Reader Republic of South Africa Department of Chemistry Jamia Millia Islamia New Delhi, India Laszlo Szirtes, Ph.D. Institute of Isotopes Milan Marhol, Ph.D. Hungarian Academy of Sciences Nuclear Research Institute Budapest, Hungary Rez u Prahy, Czechoslovakia Vladimir Pekarek, C.Sc. Department of Crystallization and Krishna Gopal Varshney, Ph.D. Calorimetry Department of Applied Chemistry Institute of Inorganic Chemistry Faculty of Engineering and Technology Czechoslovak Academy of Sciences Aligarh Muslim University Prague, Czechoslovakia Aligarh, India ACKNOWLEDGMENTS I am grateful to my friend Dr. J. P. Rawat, Reader, Department of Chemistry, Aligarh Muslim University, Aligarh, for his valuable suggestions and critical evaluation of the manuscript despite his very busy schedules. My thanks are also due to the publishers who granted permission to reproduce information from the sources noted in the text, and to Mr. H. C. Saxena for his excellent typing skills. In conclusion, my sincere thanks to my family members for their great sacrifices and moral support during the preparation of this manuscript. K. G. Varshney, Ph.D. TABLE OF CONTENTS Chapter 1 Historical Background of Inorganic Ion Exchangers, Their Classification, and Present Status 1 Vladimir Pekarek and Milan Marhol Chapter 2 Modern Theories of Ion Exchange and Ion Exchange Selectivity with Particular Reference to Zeolites 33 A. Dyer Chapter 3 Insoluble Heteropolyacid Salts 57 J. van R. Smit Chapter 4 Inorganic Ion Exchangers in Radio Chemical Analysis 91 Laszlo Szirtes Chapter 5 Inorganic Ion Exchangers for Ion Selective Electrodes 143 C. J. Coetzee Chapter 6 Amorphous Inorganic Ion Exchangers 177 K. G. Varshney and Mukhtar A. Khan Index 271

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