Fundamentals and Applications of Anion Separations

360 Pages·2004·9.96 MB·English

by  Bruce A. Moyer

FUNDAMENTALS AND
APPLICATIONS OF
ANION SEPARATIONS
FUNDAMENTALS AND
APPLICATIONS OF
ANION SEPARATIONS
Edited by
Bruce A. Moyer
Oak Ridge National Laboratory
Oak Ridge, Tennessee
and
Raj P. Singh
Osram Sylvania
Towanda. Pennsylvania
Kluwer Academic / Plenum Publishers
New York, Boston, Dordrecht, London, Moscow
Library of Congress Cataloging-in-Publication Data
Fundamentals and applicat ions of anion separations/[ed ited by] Bruce A. Moyer and Raj
P. Singh.
p. em.
Includes bibliographical references and index.
ISBN 0-306-47911-7
I. Anion separation-Congresses. 2. Anions-Analysis-Congresses. I. Moyer, Bruce A.
II. Singh, Raj Pal. III. American Chemical Society Meeting (2001: Chicago, Ill.)
QD562 .A54F86 2003
541' .3722-dc22
2003068654
Proceedings of an American Chemical Society (ACS) Symposium, held August 26-31, 2001, in Chicago , IL.
ISBN 0-306-47911-7
©2004 Kluwer Academic/Plenum Publishers, New York
233 Spring Street, New York, New York 10013
http://www.kluweronline .com
1098765432
A C.I.P. record for this book is available from the Library of Congress
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Preface
This book documents the proceedings of the symposium "Fundamentals and
Applications of Anion Separations" held during American Chemical Society National
Meeting in Chicago, Illinois, August 25-30 , 200 I. Nearly 40 papers devoted to
discussions on anion separation related to fundamental research and applications were
presented. The symposium, sponsored by Osram Sylvania, BetzDearbom, and the
Separation Science & Technology Subdivision of the Industrial & Engineering
Chemistry Division of the American Chemical Society was organized by Bruce A.
Moyer, Chemical Sciences Division , Oak Ridge National Laboratory, P.O. Box 2008 ,
Building. 4500S , Oak Ridge , TN 37831-6119, and Raj P. Singh , Chemicals and
Powders R&D, Osram Sylvania, Chemical and Metallurgical Products Division,
Towanda, PA 18848. It drew presenters from Australia, the Czech Republic, France,
Germany, Japan , South Africa , Thailand, the United Kingdom, and the United States .
Separations constitute an integral part of chemical industry. Chemical products
typically originate in resources that must be concentrated and purified, chemically
transformed, and subjected to fmal purification . Effluent streams from the processes
must be treated to recycle reusable components and to remove environmentally harmful
species. Some industrial processes are devoted to environmental cleanup after pollution
has occurred. In addition, many analytical methods require a separation for
preconcentration, or a separation may be an inherent part of the analysis itself. Micro-
separations occurring at membranes or interfaces are also related phenomena employed for
ion sensing. Many species targeted for separation are naturally anionic. Although the
standard separations techniques of extraction, ion exchange, adsorption, precipitation, etc.
apply, the chemical approaches required must be tailored specifically to accommodate the
negative charge and electron-rich nature of anionic species. Hence, the topic of anion
separations occupies an important area of interest within the broader scope of separation
science and technology.
The subject of anion recognition and separation has in fact been growing rapidly in
recent years, with exciting discoveries at the fundamental level and economically
significant applications at the industrial level. This book, the first of its kind, covers the
breadth of knowledge being pursued at both ends of the basic-applied spectrum of anion
separation research and development. The need for the symposium and corresponding
book was anticipated in that basic discoveries in chemistry often encounter delay in
reaching the application stage, basic researchers are often unaware of practical
v
vi PREFACE
applications, and applied chemists are often unaware of basic advances. Thus, reflecting
the objectives of the symposium, the main objectives of the book are (I) to disseminate
the high-impact opportunities for practical applications that can motivate basic research in
anion separations , (2) to identify applications for exciting discoveries being made at basic
research level toward developing innovative products and processes, and (3) to target
fundamental research for understanding and improving selective separation of anions.
Chapters presented in the book focus primarily on chemical approaches for
manipulating selectivity in anion separations. In so doing, the chapters deal with the
following subtopics: design and synthesis of novel anion receptors, selective separation
and recovery of anions by ion exchange, selective separation and recovery of anions by
liquid-liquid extraction, anion-selective sorbents and inorganic ion exchangers,
environmental remediation and waste treatment, and separation and purification of anions
via precipitation and crystallization. The subject matter of the various chapters pertains
to applications in nuclear-waste remediation, hydrometallurgy, ion sensing,
separation/preparation, and new anion sieves for environmental and other applications.
By way of presentation, more fundamental papers are collected at the front of the book,
becoming more applied and technique-oriented in later chapters. Approximately a third
of the chapters deal with the design and use of anion receptors, compounds that display a
special affinity for anions and function by multi-point interactions. A basic
understanding of such compounds is only now emerging, and they are gradually
beginning to find their way into applications. Eventually, specific anion receptors have
the potential to enhance standard separation techniques such as liquid-liquid extraction,
and several chapters in fact deal with such enhancements. The lead chapter summarizes
progress in the design and synthesis of anion receptors for separations and sensing.
Following are two chapters discussing respectively physical and theoretical aspects of
anion binding. Three subsequent chapters describe different families of anion receptors
and their chemical behavior. To begin to shift the focus of the book toward applications
and methods, specific needs for development of methods for anion separations in the
U.S. Department of Energy complex are then described in Chapter 7. Chapters 8-10
present specific approaches to anion extraction using receptors to enhance affinity and
selectivity. Anion exchange, a work-horse separation technique for half a century, still
represents vastly fertile ground for selectivity enhancements, improvements, and novel
applications, as discussed in Chapters 11-13. Materials derived from biological sources
represent an attractive area of development from the "green" perspective. Biosorbents in
particular are the topic of the next three chapters. A subsequent chapter deals with a
novel concept in activated-carbon materials, one of the most versatile chemical platforms
for sorbtion of many types of chemical species. Finally, the book is capped off by two
chapters on progress in inorganic sorbents and a chapter on a problem in anion
crystallization.
Although a large number of reviews and books are published every year on
separations of cationic species, a book on anion separation containing chapters from the
leaders in the field is welcome. This collection of chapters can be used as a guide for
graduate students who desire exposure to recent research results in anion binding and
separation . The book will also be a useful tool to scientists and engineers involved in
research and development in both academic and industrial settings.
Bruce A. Moyer
Raj P. Singh
August 2003
Acknowledgments
We express our appreciation to the participants in the Chicago symposium. Our
special thanks are extended to the tutorial speakers, Spiro Alexandratos and Jonathan
Sessler, and to the many session chairs . We thank the authors for their hard work in
preparing the respective chapters of the book. Financial support for the symposium was
provided by Osram Sylvania, BetzDearbom, and the Separation Science & Technology
Subdivision of the Industrial & Engineering Chemistry Division of the American
Chemical Society and is gratefully acknowledged. Thanks are also due to Kathy
Hammerly (Osram Sylvania, Towanda), Deborah A. Smith , Judith H. Moyer, Becky
Maggard, and Deborah L. Goddard (Oak Ridge National Laboratory) for editorial and
secretarial assistance. Bruce A. Moyer was supported by the Division of Chemical
Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S .
Department of Energy , under contract DE-AC05-000R22725 with Oak Ridge National
Laboratory, managed and operated by UT-Battelle, LLC.
vll
CONTENTS
1. ANIONS IN SUPRAMOLECULAR CHEMISTRY
Binding, sensing, and assembly .
Philip A. Gale
I. INTRODUCTION I
2. BINDING 1
3. SENSING 14
4. ASSEMBLy ............ 21
5. CONCLUSIONS 27
6. ACKNOWLEDGMENTS 27
7. REFERENCES 28
2. MECHANISMS OF ANION RECOGNITION
From halides to nucleotides 31
Hans-Jorg Schneider
1. INTRODUCTION 31
2. ANION COMPLEXATION IN WATER 31
2.1. Ion Pairing 31
2.2. Salt Effects on Ion Pairing 34
2.3. Ion Pairing and Additional Lipophilic Effects 35
2.4. Hydrogen Bond-Based Anion Receptors 38
2.5. Simple or Highly Preorganized Receptors? 40
3. ACKNOWLEDGMENTS 41
4. REFERENCES AND NOTES 41
ix
x CONTENTS
3. STRUCTURAL ASPECTS OF HYDROGEN BONDING
WITH NITRATE AND SULFATE
Design criteria for polyalcohol hosts 43
Benjamin P. Hay, David A. Dixon, Gregg 1. Lumett a, Rubiceli a Vargas, and
Jorge Garza
1. INTRODUCTION 43
2. METHODOLOGY 44
3. RESULTS AND DISCUSSION 45
3.1. N0 - Complexes 45
3
3.2. S042- Complexes 50
4. SUMMARY 55
5. ACKNOWLEDGMENTS 56
6. REFERENCES 56
4. SYNTHETIC RECEPTORS FOR ANION RECOGNITION 59
Suzanne L. Tobey and Eric V. Anslyn
1. INTRODUCTION 59
2. PHOSPHATE RECOGNITION WITH THE INTENT OF RNA
HYDOLYSIS 60
3. SENSING FOR CARBOXYLATE-CONTAINING NATURAL
PRODUCTS AND PHOSPHATE-CONTAINING COMPOUNDS ....... 61
4. RECOGNITION OF ACTIVE METHYLENE COMPOUNDS AND
pKA DETERMINATIONS 65
5. RECOGNITION OF INORGANIC ANIONS 66
6. SUMMARY 67
7. ACKNOWLEDGMENTS 67
8. REFERENCES 67
5. 2,3-DIPYRROLYLQUINOXALINE-BASED ANION SENSORS 71
Jonathan L. Sessler, Bruno Andrioletti, Pavel Anzenbacher, Jr., Chris Black,
Leah Eller, Hiroyuki Furuta , Karolina Jurs lkova, Hiromit su Maeda ,
Manuel Marquez, Toshihisa Mizuno , and Andrew Try
1. INTRODUCTION 71
2. SYNTHESIS AND INITIAL STUDIES 72
3. ' MET AL-CONT AINING SYSTEMS 76
4. QUINOXALINE SYSTEMS BEARING MULTIPLE PYRROLES 76
5. MACROCYCLIC SYSTEMS INCORPORATING QUINOXALINES 79
5.1. Quinoxpyrroles.......................................... ..................................... 80
CONTENTS xi
5.2. Quinoxphyrins................................................... ............................. 79
5.3. Quinoxaline-Br idged Schiff-Base Porphyrinoids........................... 81
6. CONCLUSION 83
7. ACKNOWLEDGMENT 83
8, REFERENCES 83
6. METALLA TED CALIXARENES AND
CYCLOTRIVERATRYLENES AS ANION HOSTS 87
K. Travis Holman and Jerry L. Atwood
1. INTRODUCTION 87
2. rr -METALLATED CALIX[4jARENES 91
3. A rr-METALLATED CALIX[5jARENE 94
4. rr-METALLATED CYCLOTRIVERATRYLENES 95
5. CONCLUSIONS 103
6. REFERENCES 103
7. THE PROBLEM WITH ANIONS IN THE DOE COMPLEX 107
Gregg J. Lumetta
1. INTRODUCTION 107
2. LITANY OF OFFENDING ANIONS 108
2.1. Tank Wastes 108
2.2. The Environment .... 109
3. APPROACHES TO MITIGATING DOE ANION PROBLEMS 110
3.1. Removing Problematic Anions from Tank Wastes 110
3.2. Removing Problematic Anions from Groundwater 112
4. CONCLUSIONS 113
5. ACKNOWLEDGMENTS 113
6. REFERENCES 113
8. DlTOPIC SALT-BINDING RECEPTORS FOR POTENTIAL USE IN
ANION SEPARATION PROCESSES 115
Joseph M. Mahoney, John P. Davis, and Bradley D. Smith
1. INTRODUCTION 115
2. DITOPIC SALT-BINDING RECEPTORS 118
3. LIQUID EXTRACTION OR MEMBRANE TRANSPORT USING
DITOPIC SALT RECEPTORS 120
4. SUMMAR Y 122
5. ACKNOWLEDGMENTS 122
6. REFERENCES 122
xii CONTENTS
9. DUAL·HOST COMBINATIONS: USING TRIPODAL AMIDES TO
ENHANCE CESIUM NITRATE EXTRACTION BY
CROWN ETHERS 125
Konstantinos Kavallieratos, Jeffrey C. Bryan, Richard A. Sachleben,
Gary J. Van Berkel, Oscar D. Espetia, Melissa A. Kelly, Andrew Danby,
Kristin Bowman-James, and Bruce A. Moyer
1. INTRODUCTION 125
2. DESIGN CONSIDERATIONS FOR DUAL-HOST SYSTEMS FOR
CESIUM NITRATE EXTRACTION 128
2.1 . Cesium Hosts 128
2.2. Nitrate Hosts 129
3. THERMOCHEMICAL MODEL FOR DUAL-HOST
EXTRACTION: BINDING CONSTANTS AND EXTRACTION
ENHANCEMENTS 131
4. DUAL-HOST EXTRACTION: AMIDE ANION HOSTS DERIVED
FROM 1,3,5-BENZENETRICARBOXYLIC (TRIMESIC) ACID ........ 135
5. NITRATE BINDING AND DUAL-HOST EXTRACTION USING
AMIDE-TYPE ANION HOSTS DERIVED FROM
TRIS-(2-AMINOETHYL) AMINE (TREN) 139
6. 1,3,5-TRIS(AMINOMETHYL) BENZENE DERIVATIVES 144
7. CONCLUSIONS 145
8. ACKNOWLEDGMENTS 146
9. REFERENCES AND NOTES 146
10. BINDING AND EXTRACTION OF PERTECHNETATE AND
PERRHENATE BY AZACAGES 151
Holger Stephan, Karsten Gloe , Werner Kraus, Hartmut Spies, Bernd Johannsen.
Kathrin Wichmann, GUnter Reck, Dillip K. Chand, Parimal K. Bharadwa] .
Ute MUller, Walter M. MUller, and Fritz Vogtle
1. INTRODUCTION 151
2. RESULTS AND DISCUSSION 153
2.1. Liquid-Liquid Extraction Experiments 153
2.2. Structural Considerations 158
3. CONCLUSIONS 164
4. EXPERIMENTAL SECTION 164
4.1. Synthesis 164
4.2. Liquid-Liquid Extraction Procedure 165
4.3. X-ray Crystallography............................................................ ....... 165
5. ACKNOWLEDGMENTS 166
6. REFERENCES 166