The Heaviest Metals E-Book
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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Serie: EIC Books
- Sprache: Englisch
An authoritative survey of the science and advanced technological uses of the actinide and transactinide metals The Heaviest Metals offers an essential resource that covers the fundamentals of the chemical and physical properties of the heaviest metals as well as the most recent advances in their science and technology. The authors - noted experts in the field - offer an authoritative review of the actinide and transactinide elements, i.e., the elements from actinium to lawrencium as well as rutherfordium through organesson, the current end of the periodic table, element 118. The text explores the history of the metals, their occurrence and issues of production, and covers a broad range of chemical subjects including environmental concerns and remediation approaches. The authors also offer information on the most recent and emerging applications of the metals, such as in superconducting materials, catalysis, and research into medical diagnostics. This important resource: * Provides an overview of the science and advanced technological uses of the actinide and transactinide metals * Describes the basic chemical and physical properties of the heaviest metals, and discusses the challenges and opportunities for their technological applications * Contains accessible information on the fundamental features of the heaviest metals, special requirements for their experimental study, and the critical role of computational characterization of their compounds * Highlights the most current and emerging applications in areas such as superconducting materials, catalysis, nuclear forensics, and medicine * Presents vital contemporary issues of the heaviest metals Written for graduate students and researchers working with the actinide and transactinide elements, industrial and academic inorganic and nuclear chemists, and engineers, The Heaviest Metals is a comprehensive volume that explores the fundamental chemistry and properties of the heaviest metals, and the challenges and opportunities associated with their present and emerging technological uses.
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Table of Contents
Cover
Contributors
Series Preface
Volume Preface
Part 1: Background
1 Discovery of the Actinide and Transactinide Elements
1 Introduction
2 What Are the Actinides and the Transactinides?
3 The Place of the Actinides and Transactinides in the Periodic Table
4 The Pre‐uranium Actinides: Actinium, Protactinium, and Thorium
5 Discovery of Uranium Fission
6 The Berkeley Hegemony
7 The First Transuranides: Neptunium, Plutonium, Americium, Curium, Berkelium, and Californium
8 Einsteinium and Fermium: Children of a Blast
9 The First Transfermium Elements or the Last of the Actinides: Mendelevium, Nobelium, and Lawrencium
10 The First Transactinides
11 The Uncontested GSI Elemental Discoveries
12 The Last Tenants in the Periodic Table
13 Period 8: The Superactinides and Beyond
14 Conclusion
15 Acknowledgments
16 Endnotes
17 Related Articles
18 Abbreviations and Acronyms
19 Further Reading
20 References
2 Production of Plutonium
1 Introduction
2 Separation of Plutonium from Irradiated Fuel and Targets
3 Conversion Chemistry
4 Metal Preparation and Purification
5 High‐Purity Metal Preparation
6 Acknowledgments
7 Related Articles
8 Abbreviations and Acronyms
References
3 Controlling Actinide Extraction Chemistry (Separation of Actinides from Lanthanides as Part of Nuclear Fuel Recycling)
1 Introduction
2 Spent Nuclear Fuel
3 Actinide and Lanthanide Chemistry
4 Extraction Processes
5 Ligand Design and Methodology
6 Sanex Process Ligands
7 Conclusions
Related Articles
9 Abbreviations and Acronyms
References
Part 2: Fundamentals
4 Electronic Structure of the Actinide Elements
1 Introduction
2 Valence Orbitals and Relativistic Effects
3 Ligand–Field and Spin–Orbit Interactions
4 Magnetic Properties as Probes for the Electronic Structure
5 Concluding Remarks and Outlook
6 Acknowledgments
7 Related Articles
8 Abbreviations and Acronyms
References
5 Electronic Structure of the Transactinide Atoms
1 Introduction
2 Methodology
3 Applications
4 Beginning of the Eighth Period—Relativistic Effects Increase
5 Summary and Conclusion
Related Articles
7 Abbreviations and Acronyms
References
6 Chemical Properties of the Transactinide Elements
1 Introduction
2 Methods Used in the Study of the Transactinide Elements
3 Chemical Properties of the Transactinide Elements
4 Conclusion
5 Related Articles
6 Abbreviations and Acronyms
7 References
7 Multiple Bonding in Actinide Chemistry
1 Introduction
2 Synthesis, Structure, and Reactivity
3 Computational Studies
4 Conclusions
5 Acknowledgments
6 Related Articles
7 Abbreviations and Acronyms
8 References
8 Electronic Structure of Actinide Oxides
1 Introduction
2 Actinide Dioxides
3 Actinide Sesquioxides
4 Other Actinide Oxides
5 Concluding Remarks
Related Articles
7 Abbreviations and Acronyms
8 References
Part 3: Characterization Methods
9 Crystallography of Actinide Complexes
1 Introduction
2 Actinide Crystal Structures
3 Isotopes for Structural Chemistry Studies
4 Crystal Structures of Thorium Complexes
5 Crystal Structures of Uranium Complexes
6 Crystal Structures of Neptunium and Plutonium Complexes
7 Crystal Structures of Rare Actinide Complexes: Ac, Pa, Am, Cm, Bk
8 Challenges of Data Collection and Refinement of Actinide‐Containing Structures
9 Conclusions
10 Acknowledgments
11 Related Articles
12 Abbreviations and Acronyms
13 References
10 Solid State NMR of Actinide-Containing Compounds
1 Introduction
2 NMR in a Nutshell
3 NMR on Nuclei of Actinide Atoms
4 NMR on Nuclei of Ligand Atoms: O NMR in the Actinide Oxides AO
2
5 Conclusion
6 Related Articles
7 Abbreviations and Acronyms
8 References
11 Mössbauer Spectroscopy of Actinide Compounds
1 Introduction
2 The Mössbauer Effect
3 Experimental Techniques
4 Hyperfine Interactions
5 NpFeAsO
6 NpTGa
5
7 Summary
8 Related Articles
9 Abbreviations and Acronyms
10 References
12 Photoelectron Spectroscopy of Actinide Materials
1 Introduction
2 Photoemission from Reduced Actinide Systems and Compounds
3 Photoemission of Oxidized Actinide Systems
4 Actinides Oxides—Surface Reduction
Related Articles
6 Abbreviations and Acronyms
7 References
13 Laser-Based Spectroscopic Studies of Actinide Complexes
1 Introduction
2 Experimental Considerations
3 Time‐Resolved Laser Fluorescence Spectroscopy of U(VI)
4 Spectrophotometry Coupled with LWCC of U(IV)
5 Laser‐Induced Photoacoustic Spectroscopy of P(VI)
6 Spectrophotometry and TRLFS of A(III)
7 Conclusions
8 Acknowledgments
9 Endnote
10 Related Articles
11 Abbreviations and Acronyms
12 References
14 Ab Initio Electronic Structure Calculations for Actinide and Transactinide Atoms and Molecules
1 Introduction
2 General Considerations
3 Relativistic Hamiltonians
4 Basis Sets
5 Computational Methods
6 Program Systems
7 Range of Applications
8 Conclusions
Acknowledgment
10 Related Articles
11 Abbreviations and Acronyms
12 References
Part 4: Distinctive Chemistry
15 Divalent Actinides and Transactinides: Inorganic and Organometallic Complexes
1 Introduction
2 Divalent Actinide Molecular Species in the Gas Phase
3 Divalent Actinide Molecular Species in Cryogenic Noble Gas Matrices
4 Divalent Actinide Molecular Complexes in Condensed Phases (Solution and Solid)
5 Divalent Transactinide Molecular Species
6 Conclusion
7 Acknowledgments
8 Related Articles
9 Abbreviations and Acronyms
10 References
16 Organometallic Chemistry of Pentavalent Uranium
1 Introduction
2 Complexes of Uranium(V) with Aromatic Substituents: Metallocenes and Arenes
3 U(V) Hydrocarbyls: Alkyls and Carbenes
4 Miscellaneous U(V)–CO Interactions
5 Acknowledgments
6 Related Articles
7 Abbreviations and Acronyms
8 References
17 Amido Complexes of the Actinides
1 Introduction
2 Amido Complexes
3 Conclusion
4 Related Articles
5 Abbreviations and Acronyms
6 References
18 Actinide Pnictogen Complexes
1 Introduction
2 Neutral Coordinating Ligands
3 Monoanionic Ligands
4 Dianionic Ligands
5 Trianionic Ligands
6 Elemental Cyclic Bridging Ligands
7 Conclusion
8 Related Articles
References
19 Actinide Borohydrides
1 Introduction
2 Homoleptic Tetrahydroborate Complexes
3 Homoleptic Methyltrihydroborate Complexes
4 Lewis Base Adducts of BH
4
and BH
3
Me Complexes
5 Aminodiboranate Complexes
6 Other Actinide Borohydride Complexes
7 Conclusion
8 Related Articles
9 Abbreviations and Acronyms
10 References
20 Supramolecular and Macrocyclic Chemistry of the Actinides
1 Introduction
2 Supramolecular Assemblies Involving Actinides
3 Actinide‐Related Macrocyclic Systems
4 Related Articles
5 Abbreviations and Acronyms
6 References
21 Actinide Polyoxometalates
1 Introduction
2 Structures of Uranyl Peroxide POMs
3 General Features of Uranyl Peroxide POMs
4 Formation and Dynamics of Uranyl Peroxide POMs
5 Uranyl Peroxide Clusters in Solution
6 Applications of Uranyl Peroxide Clusters
7 Nonperoxide Actinide POMs
8 Conclusion
9 Related Articles
10 Abbreviations and Acronyms
11 References
Part 5: Environmental and Health Issues
22 Actinide Speciation and Bioavailability in Fresh and Marine Surface Waters
1 Introduction
2 Metal Speciation
3 Chemical Trends and Features of the Actinides
4 Actinide Speciation in Natural Surface Waters
5 Actinium
6 Thorium
7 Protactinium
8 Uranium
9 Neptunium
10 Plutonium
11 Americium
12 Curium
13 Berkelium
14 Californium
15 Global Trends in Surface Water Chemistry and Influence on Actinide Speciation And Bioavailability
16 Water Quality Guidelines for Protecting Freshwater and Marine Ecosystems
17 Actinide Bioaccumulation
18 Recommendations for Further Work
19 Acknowledgments
20 Glossary
21 Related Articles
22 Abbreviations and Acronyms
23 References
23 Transuranic Biogeochemistry
1 Introduction
2 Aqueous Chemical Speciation of Transuranic Elements under Environmental Conditions in the Absence of Microbial Interactions
3 Transuranic Element Association and Transformation by Microorganisms
4 Concluding Remarks and Future Work
5 Related Articles
6 Abbreviations and Acronyms
7 References
24 Sustainable Remediation in Complex Geologic Systems
1 Introduction
2 Site Characterization
3 Hydrological Model Development
4 Geochemical Model Development
5 Case Study in Remediation
Related Articles
7 Abbreviations and Acronyms
8 References
25 Nuclear Forensics
1 Introduction
2 Nuclear Forensic Signatures
3 Summary
4 Related Articles
5 Abbreviations and Acronyms
6 References
26 Actinides in Medicine
1 Introduction
2 Actinides in Medicine
3 Outlook and Conclusion
4 Related Articles
5 Abbreviations and Acronyms
6 References
Part 6: Special Applications
27 Actinide Elements in Catalysis
1 Introduction
2 Catalytic Transformations of Alkynes
3 Catalytic Coupling of Aldehydes
4 Catalytic Addition of Protic Nucleophiles (E–H) to Heterocumulenes
5 Dehydrocoupling of Amines and Silanes
6 Catalytic Reduction of Azides and Hydrazines
7 Polymerization Reactions Mediated by Organoactinide Complexes
8 Ring‐Opening Polymerization of Epoxides
9 Uranium in the Electro Catalytic Production of H
2
from Water and Coupling of Carbon Monoxide
10 Reductive Homologation and Functionalization of Carbon Monoxide
11 Conclusion
12 Acknowledgments
13 Related Articles
14 Abbreviations and Acronyms
15 References
28 Superconductivity of the Heaviest Metals and Their Compounds
1 Introduction
2 5f‐Electrons and Their Influence on Superconductivity and Magnetic Order in Trans‐actiniums up to Pu
3 Actinides beyond Pu
4 Concluding Remarks
5 Related Articles
6 Abbreviations and Acronyms
7 References
Index
End User License Agreement
List of Tables
2525
Table 1 Discovery of the actinides and transactinides
Table 2 Critical energies of some representative nuclei
Table 3 Summary of various proposals for elements 104–112 and the final IUPAC...
Table 4 Isotope and half‐life data of the transfermium elements
2528
Table 1 Common plutonium isotopes, half‐lives, and typical compositions for t...
2529
Table 1 Approximate mass and
t
1/2
of U and Pu radioisotopes found in SNF
12
Table 2 Approximate mass and
t
1/2
of the minor actinides Np, Am, and Cm radioi...
2530
Table 1 Spin and angular momentum expectation values for the ground‐state dou...
2632
Table 2 CC transition energies in Au (eV)
Table 1 Transition energies in Rf
and Rf (eV)
Table 3 CC excitation energies, electron affinity, and ionization potentials ...
Table 4 Ionization potentials and excitation energies of Cn(E112) and its ion...
Table 5 Ionization potential (IP) and excitation energies (EE) of neutral lea...
Table 6 Ionization potentials of group‐14 elements (eV)
Table 7 Electron affinities of the alkali atoms (meV)
Table 8 Ionization potential (IP) and excitation energies (EE) of Ac and eka‐...
Table 9 Fock‐space and intermediate Hamiltonian transition energies of thoriu...
Table 10 Fock‐space and intermediate Hamiltonian transition energies of eka‐t...
2637
Table 1 Isotopes typically used for chemical studies of transactinides
2535
Table 1 Sums of the single, double, and triple bond covalent radii for select...
Table 2 Uranium‐terminal imido bond lengths in different oxidation states and...
Table 3 U–N
nitrido
bond lengths and stretch frequencies for uranium terminal ...
Table 4 U(V) terminal mono‐oxo complexes synthesized by oxygen atom transfer ...
Table 5 U(VI) terminal mono‐oxo complexes synthesized by oxygen atom transfer...
Table 6 Uranium terminal mono‐oxo bond lengths in different oxidation states ...
Table 7 Comparison of uranium terminal heavier chalcogenide bond lengths to c...
Table 8 Ranges for U–E (E = P, As) bond lengths in phosphinidene, phosphide, ...
2532
Table 1 Comparison with experiment of optimized lattice constants for actinid...
Table 2 Optimized Coulombic (
U
) and exchange (
j
) values in eV for AnO
2
using ...
Table 3 Crystallographic information for An
2
O
3
Table 4 Calculated properties of β‐ and
α
‐Pu
2
O
3
: equilibrium lattice cons...
Table 5 Calculated properties of A‐ and C‐type An
2
O
3
: band gap for the lowest...
Table 6 Crystallographic information for uranium oxides
Table 7 Predicted properties of U
2
O
5
: equilibrium lattice constants, the bulk...
Table 8 Calculated properties of U
3
O
8
: equilibrium lattice constants, the bul...
Table 9 Calculated properties of UO
3
: equilibrium lattice constants, the bulk...
2536
Table 1 List of chemical structure entries for actinides in both the Cambridg...
Table 2 Comparisons of the average bond lengths of An(HDPA)
3
· (H
2
O) for both...
2538
Table 1 The magnetic transition temperature and hyperfine parameters referred...
2539
Table 1 Transition metals incorporated into U‐based films
2557
Table 1 Luminescence characteristics of U(VI)‐hydroxo species measured in thi...
Table 2 Luminescence characteristics of U(VI)‐carbonate species measured in t...
2544
Table 1 Calculated Nalewajski–Mrozek bond indices, empirical bond lengths and...
2551
Table 1 Summary of
31
P NMR resonances (ppm) as well as actinide–phosphorus bon...
2552
Table 1 Distances (Å) and angles (°) of halogen–halogen interactions observed...
2559
Table 1 Physicochemical forms of metals in natural waters
Table 2 Formal and effective cationic charge for each actinide (An) oxidation...
Table 4 Analytical techniques used to determine actinide speciation in natura...
Table 3 Stable oxidation state(s) for selected actinides in oxic natural surf...
Table 5 Surface water chemistry for model fresh‐, estuarine and coastal seawa...
Table 6 Predicted change in actinide speciation and bioavailability in the di...
Table 7 Predicted change in actinide speciation and bioavailability in the di...
Table 8 Uranium guideline values (or quality standards) for protecting freshw...
Table 9 The range of concentration factors (CFs) for actinides in freshwater ...
2562
Table 1 Development of the non‐electrostatic SCM with minimum number of fitte...
2566
Table 1 Analytical techniques used in the fourth analytical exercise organize...
Table 2 The most common nuclear forensic signatures and the type of informati...
Table 3 Categories of U and Pu
Table 4 Examples of dimensions of fuel pellets used in different reactor type...
2563
Table 1 Common radionuclides for PET and SPECT imaging along with their imagi...
Table 2 Decay characteristics of therapeutic radionuclides
1
,
25
,
26
Table 3 Comparison of targeting vectors used in targeted radionuclide therapy
Table 4 Radionuclides currently used for clinical and preclinical radiotherap...
Table 5 Different routes explored to produce
225
Ac
11
,
42
,
43
,
47
,
48
,
49
,
50
,
Table 6 Preclinical studies with
225
Ac
Table 7 Clinical studies with
225
Ac
Table 8 Preclinical studies with
227
Th
2558
Table 1 Superconductivity of f‐electron elements at ambient pressure and by a...
Table 2 Critical temperatures
T
c
for superconductivity of Th and Th‐based comp...
Table 3 Ambient‐pressure transition temperatures of conventional U‐based supe...
Table 4 Transition temperatures of unconventional U‐based superconductors
Table 5 Normal‐state electronic specific heat parameters
γ
of superconduc...
List of Illustrations
Guide
Cover
Table of Contents
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THE HEAVIEST METALS: Science and Technology of the Actinides and Beyond
Editors
William J. Evans
University of California, Irvine, CA, USA
Timothy P. Hanusa
Vanderbilt University, Nashville, TN, USA
Copyright
This edition first published 2019
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Yale University, New Haven, CT, USA
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CA, USA
Karl E. Wieghardt
Mülheim an der Ruhr, Germany
Vivian Yam
Hong Kong
Contributors
John Arnold
University of California, Berkeley, CA, USA;
Lawrence Berkeley Laboratory, Berkeley, CA, USA
Multiple Bonding in Actinide Chemistry
Bhavna Arora
Lawrence Berkeley National Laboratory, Berkeley, CA, USA
Sustainable Remediation in Complex Geologic Systems
Jochen Autschbach
University at Buffalo, State University of New York, Buffalo, NY, USA
Electronic Structure of the Actinide Elements
Rami J. Batrice
Technion—Israel Institute of Technology, Haifa, Israel
Actinide Elements in Catalysis
Eva R. Birnbaum
Los Alamos National Laboratory, Los Alamos, NM, USA
Actinides in Medicine
Anastasia Borschevsky
Van Swinderen Institute for Particle Physics and Gravity;
University of Groningen, Groningen, The Netherlands
Electronic Structure of the Transactinide Atoms
Hakim Boukhalfa
Los Alamos National Laboratory, Los Alamos, NM, USA
Transuranic Biogeochemistry
Paul L. Brown
Geochem Australia, Kiama, NSW, Australia
Actinide Speciation and Bioavailability in Fresh and Marine Surface Waters
Michael A. Boreen
University of California, Berkeley, CA, USA
Multiple Bonding in Actinide Chemistry
Peter C. Burns
University of Notre Dame, Notre Dame, IN, USA
Actinide Polyoxometalates
Xiaoyan Cao
University of Cologne, Cologne, Germany
Ab Initio Electronic Structure Calculations for Actinide and Transactinide Atoms and Molecules
Samantha K. Cary
Los Alamos National Laboratory, Los Alamos, NM, USA
Crystallography of Actinide Complexes
Wansik Cha
Korea Atomic Energy Research Institute, Daejeon, Republic of Korea
Laser‐Based Spectroscopic Studies of Actinide Complexes
Hye‐Ryun Cho
Korea Atomic Energy Research Institute, Daejeon, Republic of Korea
Laser‐Based Spectroscopic Studies of Actinide Complexes
David L. Clark
Los Alamos National Laboratory, Los Alamos, NM, USA
Production of Plutonium
Justin N. Cross
Los Alamos National Laboratory, Los Alamos, NM, USA
Crystallography of Actinide Complexes
Scott R. Daly
University of Iowa, Iowa City, IA, USA
Actinide Borohydrides
Miles Denham
Savannah River National Laboratory, Aiken, SC, USA
Sustainable Remediation in Complex Geologic Systems
Michael Dolg
University of Cologne, Cologne, Germany
Ab Initio Electronic Structure Calculations for Actinide and Transactinide Atoms and Molecules
Christoph E. Düllmann
Johannes Gutenberg University Mainz, Mainz, Germany;
GSI Helmholtzzentrum für Schwerionenforschung GmbH, Darmstadt, Germany;
Helmholtz Institute Mainz, Mainz, Germany
Chemical Properties of the Transactinide Elements
Carol Eddy‐Dilek
Savannah River National Laboratory, Aiken, SC, USA
Sustainable Remediation in Complex Geologic Systems
Moris S. Eisen
Technion—Israel Institute of Technology, Haifa, Israel
Actinide Elements in Catalysis
Ephraim Eliav
Tel Aviv University, Tel Aviv, Israel
Electronic Structure of the Transactinide Atoms
Rachel Eloirdi
European Commission, Joint Research Centre, Directorate G, Nuclear Safety & Security, Karlsruhe, Germany
Photoelectron Spectroscopy of Actinide Materials
David J.H. Emslie
McMaster University, Hamilton, ON, Canada
Amido Complexes of the Actinides
Michael E. Fassbender
Los Alamos National Laboratory, Los Alamos, NM, USA
Actinides in Medicine
Maryline G. Ferrier
Los Alamos National Laboratory, Los Alamos, NM, USA
Actinides in Medicine
Greg Flach
Savannah River National Laboratory, Aiken, SC, USA
Sustainable Remediation in Complex Geologic Systems
Zachary Fisk
University of California, Irvine, CA, USA
Superconductivity of the Heaviest Metals and Their Compounds
Franz J. Freibert
Los Alamos National Laboratory, Los Alamos, NM, USA
Production of Plutonium
Marco Fontani
Università degli Studi di Firenze, Sesto Fiorentino, Italy
Discovery of the Actinide and Transactinide Elements
Skye Fortier
University of Texas, El Paso, TX, USA
Organometallic Chemistry of Pentavalent Uranium
Piotr Gaczyński
Institut für Physikalische und Theoretische Chemie, Braunschweig, Germany
Mössbauer Spectroscopy of Actinide Compounds
Frédéric Gendron
University at Buffalo, State University of New York, Buffalo, NY, USA
Electronic Structure of the Actinide Elements
John K. Gibson
Lawrence Berkeley National Laboratory, Berkeley, CA, USA
Divalent Actinides and Transactinides: Inorganic and Organometallic Complexes
Thomas Gouder
European Commission, Joint Research Centre, Directorate G, Nuclear Safety & Security, Karlsruhe, Germany
Photoelectron Spectroscopy of Actinide Materials
Laurence M. Harwood
University of Reading, Reading, UK
Controlling Actinide Extraction Chemistry (Separation of Actinides from Lanthanides as Part of Nuclear Fuel Recycling)
Kongqiu Hu
Chinese Academy of Sciences, Beijing, China
Supramolecular and Macrocyclic Chemistry of the Actinides
Susan Hubbard
Lawrence Berkeley National Laboratory, Berkeley, CA, USA
Sustainable Remediation in Complex Geologic Systems
Kevin D. John
Los Alamos National Laboratory, Los Alamos, NM, USA
Actinides in Medicine
Euo C. Jung
Korea Atomic Energy Research Institute, Daejeon, Republic of Korea
Laser‐Based Spectroscopic Studies of Actinide Complexes
Uzi Kaldor
Tel Aviv University, Tel Aviv, Israel
Electronic Structure of the Transactinide Atoms
Isabell S.R. Karmel
Technion—Israel Institute of Technology, Haifa, Israel
Actinide Elements in Catalysis
Hee‐Kyung Kim
Korea Atomic Energy Research Institute, Daejeon, Republic of Korea
Laser‐Based Spectroscopic Studies of Actinide Complexes
G. Koutroulakis
University of California, Santa Barbara, Santa Barbara, CA, USA
Solid State NMR of Actinide‐Containing Compounds
Jianhui Lan
Chinese Academy of Sciences, Beijing, China
Supramolecular and Macrocyclic Chemistry of the Actinides
Konstantin Lipnikov
Los Alamos National Laboratory, Los Alamos, NM, USA
Sustainable Remediation in Complex Geologic Systems
Klaus Lützenkirchen
European Commission, Joint Research Centre, Karlsruhe, Germany
Nuclear Forensics
Joaquim Marçalo
Universidade de Lisboa, Bobadela, Portugal
Divalent Actinides and Transactinides: Inorganic and Organometallic Complexes
Leonor Maria
Universidade de Lisboa, Bobadela, Portugal
Divalent Actinides and Transactinides: Inorganic and Organometallic Complexes
Scott J. Markich
Aquatic Solutions International, Collaroy, NSW, Australia
Actinide Speciation and Bioavailability in Fresh and Marine Surface Waters
Klaus Mayer
European Commission, Joint Research Centre, Karlsruhe, Germany
Nuclear Forensics
Tara Mastren
Los Alamos National Laboratory, Los Alamos, NM, USA
Actinides in Medicine
Lei Mei
Chinese Academy of Sciences, Beijing, China
Supramolecular and Macrocyclic Chemistry of the Actinides
Jesse Murillo
University of Texas, El Paso, TX, USA
Organometallic Chemistry of Pentavalent Uranium
David Moulton
Los Alamos National Laboratory, Los Alamos, NM, USA
Sustainable Remediation in Complex Geologic Systems
Mary Neu
Los Alamos National Laboratory, Los Alamos, NM, USA
Transuranic Biogeochemistry
Mary V. Orna
The College of New Rochelle, New Rochelle, NY, USA
Discovery of the Actinide and Transactinide Elements
Hans R. Ott
ETH Zürich, Hönggerberg, Zürich, Switzerland
Superconductivity of the Heaviest Metals and Their Compounds
Lindsay E. Roy
Savannah River National Laboratory, Aiken, SC, USA
Electronic Structure of Actinide Oxides
Brian L. Scott
Los Alamos National Laboratory, Los Alamos, NM, USA
Crystallography of Actinide Complexes
Weiqun Shi
Chinese Academy of Sciences, Beijing, China
Supramolecular and Macrocyclic Chemistry of the Actinides
Zsolt Varga
European Commission, Joint Research Centre, Karlsruhe, Germany
Nuclear Forensics
Sean P. Vilanova
University of Missouri, Columbia, MO, USA
Actinide Pnictogen Complexes
Justin R. Walensky
University of Missouri, Columbia, MO, USA
Actinide Pnictogen Complexes
Haruko Wainwright
Lawrence Berkeley National Laboratory, Berkeley, CA, USA
Sustainable Remediation in Complex Geologic Systems
Maria Wallenius
European Commission, Joint Research Centre, Karlsruhe, Germany
Nuclear Forensics
James Westwood
University of Reading, Reading, UK
Controlling Actinide Extraction Chemistry (Separation of Actinides from Lanthanides as Part of Nuclear Fuel Recycling)
Guy Yardeni
Nuclear Research Centre Negev, Beer Sheva, Israel
Actinide Elements in Catalysis
H. Yasuoka
Max Planck Institute for Chemical Physics of Solids, Dresden, Germany
Solid State NMR of Actinide‐Containing Compounds
Series Preface
The success of the Encyclopedia of Inorganic Chemistry (EIC), pioneered by Bruce King, the founding Editor in Chief, led to the 2012 integration of articles from the Handbook of Metalloproteins to create the newly launched Encyclopedia of Inorganic and Bioinorganic Chemistry (EIBC). This has been accompanied by a significant expansion of our Editorial Advisory Board with international representation in all areas of inorganic chemistry. It was under Bruce's successor, Bob Crabtree, that it was recognized that not everyone would necessarily need access to the full extent of EIBC. All EIBC articles are online and are searchable, but we still recognized value in more concise thematic volumes targeted to a specific area of interest. This idea encouraged us to produce a series of EIC (now EIBC) Books, focusing on topics of current interest. These will continue to appear on an approximately annual basis and will feature the leading scholars in their fields, often being guest coedited by one of these leaders. Like the Encyclopedia, we hope that EIBC Books continue to provide both the starting research student and the confirmed research worker a critical distillation of the leading concepts and provide a structured entry into the fields covered.
The EIBC Books are referred to as spin‐on books, recognizing that all the articles in these thematic volumes are destined to become part of the online content of EIBC, usually forming a new category of articles in the EIBC topical structure. We find that this provides multiple routes to find the latest summaries of current research.
I fully recognize that this latest transformation of EIBC is built on the efforts of my predecessors, Bruce King and Bob Crabtree, my fellow editors, as well as the Wiley personnel, and, most particularly, the numerous authors of EIBC articles. It is the dedication and commitment of all these people that are responsible for the creation and production of this series and the “parent” EIBC.
Robert A. Scott
University of Georgia
Department of Chemistry
January 2019
Volume Preface
The Heaviest Metals: Science and Technology of the Actinides and Beyond is focused on the elements of highest atomic number—the actinides (Ac–Lr) and transactinides (Rf–Og). Their history spans virtually the entire era of modern chemistry, from the discovery of uranium by Klaproth in 1789 to the confirmation of the names of nihonium, moscovium, tennessine, and oganesson in 2016. Their importance is hard to overstate: collectively, they comprise a quarter of all known elements, and the names of several of them (uranium and plutonium) are widely known to the general public owing to the centrality of their roles in nuclear power generation and weaponry. Radioactivity and nuclear fission were first recognized in an actinide metal (uranium), key discoveries that altered our understanding of the very nature of a chemical element. Of course, many of these metals, including the late actinides and all of the transactinides, are charitably classified as exotics, unlikely ever to appear outside a research laboratory. Nevertheless, their study has refined our knowledge of the effects of relativity on chemical properties in general, and stimulated the development of methods for conducting experiments on an ultratrace scale, with elements that are produced only a few atoms at a time.
An area as extensive as this cannot be covered with justice in a single volume, so we have attempted to strike a balance between broad overviews and more focused topics. The Heaviest Metals begins with a counting of the fascinating (and convoluted) discovery of the actinides and transactinides, and then moves on to describe issues with the production of plutonium, the actinide synthesized in greatest quantity, and the complex problems involved in extracting and separating individual actinides. The next section looks at the electronic structure of the actinides and transactinides, chemical properties of the transactinides, and then the question of multiple bonding with these metals. Following this, the challenges in actinide crystallography are detailed, and the application of various spectroscopic techniques (solid‐state NMR, Mössbauer,photoelectron, and laser‐based spectroscopies) and computational investigations to characterize compounds of these elements are reviewed. The next section examines compounds with metals in the divalent (Th, U, Np, Pu) and pentavalent (U) oxidation states, areas of intense current research activity. The distinctive chemistries of actinide/group 15 complexes, metal borohydrides, supramolecular complexes, and polyoxometalates are also examined. Environmental and health issues are the focus of the next section, where questions of actinide speciation in freshwater and oceans, the biological transformations of actinide ions, and the movement of actinides in subsurface plumes are addressed. Separate chapters describe the emerging field of nuclear forensics, which tracks actinides to prevent theft or illegal disposal, and the multiple benefits provided by actinide radiotherapy. The volume closes with a look at two novel applications: actinide‐based catalysis and the superconducting properties of actinide materials.
The Heaviest Metals was intended not only to inform, but also to inspire the reader to imagine new ways in which the elements at the frontier of the periodic table can advance multiple areas of chemistry. If it accomplishes that, our goal for the volume will have been reached.
Finally, we wish to thank the editorial staff at Wiley for their expert shepherding of the project from its earliest conception. Without their steadfast help, it could not have been completed.
Bill Evans
University of California,
Irvine, CA, USA
Tim Hanusa
Vanderbilt University,
Nashville, TN, USA
January 2019
Part 1Background
1Discovery of the Actinide and Transactinide Elements
Mary V. Orna
The College of New Rochelle, New Rochelle, NY, USA
and
Marco Fontani
Università degli Studi di Firenze, Sesto Fiorentino, Italy
1 Introduction
2 What Are the Actinides and the Transactinides?
3 The Place of the Actinides and Transactinides in the Periodic Table
4 The Pre‐uranium Actinides: Actinium, Protactinium, and Thorium
5 Discovery of Uranium Fission
6 The Berkeley Hegemony
7 The First Transuranides: Neptunium, Plutonium, Americium, Curium, Berkelium, and Californium
8 Einsteinium and Fermium: Children of a Blast
9 The First Transfermium Elements or the Last of the Actinides: Mendelevium, Nobelium, and Lawrencium
10 The First Transactinides
11 The Uncontested GSI Elemental Discoveries
12 The Last Tenants in the Periodic Table
13 Period 8: The Superactinides and Beyond
14 Conclusion
15 Acknowledgments
16 Endnotes
17 Related Articles
18 Abbreviations and Acronyms
19 Further Reading
20 References
1 Introduction
“Discovery is new beginning. It is the origin of new rules that supplement, or even supplant, the old…Were there rules for discovery, then discoveries would be mere conclusions.”1 The history of the discovery of the actinides and the transactinides, the 30 elements that comprise the very last part of the present periodic table of the elements, is peppered with rules: new rules, old rules transformed, new rules broken and remade—not necessarily by those doing the research, but often by Nature itself. Furthermore, if we consider the ways in which discoveries are made, they often fall into the categories of planned research, trial and error, or accidental discovery. Add to this a creative and observing mind2 and you can encompass virtually all of the discoveries, and the methods used to further understand and gain more information about how the discovery can be exploited. It would be useful to analyze the following story for these characteristics, for this is the discovery that set in motion the train of events that would expand and change the periodic table forever.
In 1896, Henri Becquerel (1852–1908) reported that the double sulfate of potassium and uranium, formulated by him as [SO4(UO)K·H2O] using the superscript notation common at the time, emitted radiation capable of penetrating light‐opaque paper to expose silver salts. He realized that the so‐called phosphorescent material was emitting this radiation by its very nature and not by becoming phosphorescent owing to exposure to light.3 Subsequent work showed that the radiation could also penetrate thin sheets of aluminum and copper. Becquerel realized at this stage that the radiation was analogous to the newly discovered Roentgen rays.4 Five additional notes in the same volume of the journal follow the course of his further experiments to show, beyond a doubt, that the radiation was spontaneous and owing to the uranium component of the salt. It was Marie Curie (1867–1934) who eventually named the new phenomenon “radioactivity.”
Radioactivity, as evinced by the first actinide to be discovered, was to dominate the scientific, political, economic, and social scenes of the first half of the twentieth century. And during that century, all the rest of the actinides, and most of the transactinides, were to be discovered.
Using radioactivity as the signature by which radioactive atoms could be detected, scientists began to bombard targets with particles such as α‐particles and neutrons as they became available, and then to identify the products of these reactions. They gradually surpassed the known limit of atomic number 92 to venture onto an unknown sea, not knowing where it would lead. So far, the journey has led to the discovery of 26 elements beyond uranium, completing the seventh row of the periodic table. This has involved massive amounts of funding, dedicated and persevering work on the part of genius‐level individuals, and a surprising degree of international cooperation even during the Cold War. It has led to spectacular discoveries, overturned assumptions and theories, and glimpses of a Nature full of unexpected surprises.
2 What Are the Actinides and the Transactinides?
A simple definition of the groups in question is: the elements beginning with actinium, with atomic number 89, and ending with the last element to be discovered and that completes period 7 of the periodic table, oganesson, with atomic number 118. None of these elements possesses a stable isotope; every actinide and transactinide is radioactive with half‐lives that vary from billions of years, such as thorium, 232Th, with a half‐life of 1.41 × 1010 years, to µs, such as darmstadtium, 267Ds, with a half‐life of 3 × 10−6 s. Table 1 lists these 30 elements (occupying about 25% of the periodic table) in order of the atomic number. However, discovery chronology does not follow from this order.
Table 1 Discovery of the actinides and transactinides
Atomic number
Symbol
Name/symbol
Discoverer
Date of discovery
Place of discovery
89
Ac
Actinium
Debierne
1899
Paris, France
90
Th
Thorium
J. J. Berzelius
1829
Stockholm, Sweden
91
Pa
Protactinium
Hahn, Meitner
1917
Berlin, Germany
Fajans
Karlsruhe
Soddy, Cranston, Fleck
Glasgow, Scotland
92
U
Uranium
Martin Klaproth
1789
Berlin, Germany
93
Np
Neptunium
McMillan, Abelson
1940
LBNL, USA
94
Pu
Plutonium
Seaborg, Wahl, Kennedy
1940
LBNL, USA
95
Am
Americium
Seaborg, Morgan, James, Ghiorso
1944
LBNL, USA
96
Cm
Curium
Seaborg, James, Ghiorso
1944
LBNL, USA
97
Bk
Berkelium
Thompson, Ghiorso, Seaborg
1949
LBNL, USA
98
Cf
Californium
Thompson, Street, Ghiorso, Seaborg
1950
LBNL, USA
99
Es
Einsteinium
Choppin, Thompson, Ghiorso, Harvey
1952
LBNL, USA
100
Fm
Fermium
Choppin, Thompson, Ghiorso, Harvey
1952
LBNL, USA
101
Md
Mendelevium
Choppin, Thompson, Ghiorso, Harvey, Seaborg
1955
LBNL, USA
102
No
Nobelium
Flerov and others
1958
JINR, Russia
103
Lr
Lawrencium
Ghiorso, Larsh, Sikkeland, Latimer
1961
LBNL, USA; JINR, Russia
104
Rf
Rutherfordium
Ghiorso, Flerov
1964
LBNL, USA; JINR, Russia
105
Db
Dubnium
Various
1968
LBNL, USA; JINR, Russia
106
Sg
Seaborgium
Ghiorso and others
1974
LBNL, USA
107
Bh
Bohrium
Armbruster, Münzenberg, Hofmann, others
1981
GSI, Germany
108
Hs
Hassium
Armbruster, Münzenberg, Hofmann, others
1984
GSI, Germany
109
Mt
Meitnerium
Armbruster, Hofmann, Münzenberg, others
1982
GSI, Germany
110
Ds
Darmstadtium
Armbruster, Hofmann, others
1994
GSI, Germany
111
Rg
Roentgenium
Armbruster, Hofmann, others
1994
GSI, Germany
112
Cn
Copernicium
Hofmann, others
1996
GSI, Germany
113
Nh
Nihonium
Various
2004
RIKEN, Japan
114
Fl
Flerovium
Various
1999
LLNL, USA; JINR, Russia
115
Mc
Moscovium
Various
2010
LLNL, ORNL, USA; JINR, Russia
116
Lv
Livermorium
Various
2000
LLNL, USA; JINR, Russia
117
Ts
Tennessine
Various
2010
LLNL, ORNL, USA; JINR, Russia
118
Og
Oganesson
Various
2006
LLNL, USA; JINR, Russia
The first actinide to be discovered, in 1789 by Martin Heinrich Klaproth (1743–1817), was uranium; a century later it was, as well, the first element recognized to be radioactive. Klaproth's alertness to detail accompanied by his pure love of science5 no doubt prepared him to recognize a new substance when he dissolved the mineral pitchblende in nitric acid, and then neutralized the solution with strong base and observed the formation of a yellow precipitate. Using the tried and true method of heating the precipitate in the presence of a reducing agent, he obtained a black powder that he took for the element, which he named uranium in honor of the newly discovered planet, Uranus.6
A glance at Table 1 is quite informative regarding discovery. The first three actinides to be discovered were “lone wolf” affairs: a single discoverer is named, and that brings us to the end of the nineteenth century. It is an entirely different matter for the entire twentieth century: discovery is a team affair, often with long lists of multiple authors: we have entered the age of “big chemistry,” characterized by specialized and expensive equipment in a national laboratory. It is easy to see that the Lawrence Berkeley National Laboratory, California, USA (LBNL) exercised a monopoly on actinide discoveries, completing the list with element number 103, lawrencium. Discoveries of the transactinides exhibit more international collaboration but, as we shall see, cooperation during the Cold War was never all sweetness and light.
3 The Place of the Actinides and Transactinides in the Periodic Table
The modern periodic table is a grid consisting of 7 rows (periods) and 18 columns (groups). Periods 6 and 7 exceed the 18‐column model with 32 groups each in the long form, and two offset rows of 15 elements each in the traditional, or medium‐long, configuration, used for convenience so that the table will fit on a normal printed page, as shown in Figure 1.
Figure 1 The standard medium‐long form of the periodic table
The grid, originally arranged in order of increasing atomic weights of the elements, is now arranged in order of increasing atomic number (the number of protons in the nucleus of an atom, often abbreviated Z) in one dimension, and in order of similar chemical properties in the second dimension to form the groups. This grid actually defines the way electrons arrange themselves in atoms in terms of principal energy levels and sublevels that they occupy, the so‐called s, p, d, and f blocks. Not only has it brought order out of the chaos of so many elements with so many different properties, but it also functions as a theoretical tool, a “marvelous map of the whole geography of the elements.”7
The two rows offset as “footnotes” from the main body of the periodic table, each consisting of 15 elements. The top row, from lanthanum (Z = 57) to lutetium (Z = 71), along with two elements in the main body of the table, scandium and yttrium, are termed the “rare earths.” The 15 rare earths in the offset sit below yttrium with properties so similar to one another that the Czech chemist, Bohuslav Brauner (1855–1935), once proposed that they should all occupy the same space.8
Today, we take the placement of the actinides in the table for granted. However, initially, the first‐discovered members of this group were placed in the main body of the table with actinium in the yttrium group, thorium under hafnium, protactinium under tantalum, and uranium under tungsten. Any transuranium elements to be yet discovered were expected to fall into place to complete period 6, with the last element in the row, Z = 104, fitting under radon.
The differences in chemical properties between some of these supposed homologs soon made this assumption untenable. In 1893, Henry Bassett (ca. 1837–1920),9 followed by Alfred Werner (1866–1919), who is often given the credit, first suggested that the heavier elements beyond uranium might need an intergroup accommodation similar to that of the rare earths.10 Decades later, in 1940, when Edwin McMillan (1907–1991) and Philip Abelson (1913–2004) discovered element 93, and shortly afterward, Glenn Seaborg (1912–1999) and his team discovered element 94, they had a surprise waiting. Chemical tests revealed that the properties of both new elements were more similar to those of uranium than to their supposed homologs, rhenium and osmium.11 At this point in the group's struggle to place the new elements in the periodic table, its extreme utility became spectacularly evident as both a flexible and a predictive theoretical tool. Seaborg took up the Bassett‐Werner idea and made it his own:
I began to believe it was correct to propose a second lanthanide‐style series of elements …[starting]…with element number 89, actinium, the element directly below lanthanum in the periodic table. Perhaps there was another inner electron shell being filled. This would make the series directly analogous to the lanthanides, which would make sense, but it would require a radical change in the periodic table…[I was told] that such an outlandish proposal would ruin my scientific reputation. Fortunately, that was no deterrent because at the time I had no scientific reputation to lose.12
So, the initial stages of discovery of the transuranium elements gave rise to a reconfiguration of the periodic table. The two new elements were appropriately named neptunium and plutonium after the two planets that lay beyond Uranus in the solar system. The rest of the actinides, as they were discovered, fell right into place under their rare earth homologs, and the transactinides, from atomic numbers 104 to 118 populated period 7 to its completion. It remains to be seen how the future treats the superactinides beginning with atomic number 119.a.
4 The Pre‐uranium Actinides: Actinium, Protactinium, and Thorium
4.1 The Discovery of Thorium
Element number 90, thorium, was the first of this trio to be discovered in 1829. One of the most famous chemists of the time, Jöns Jacob Berzelius (1779–1848), Professor at the Karolinska University, Stockholm, in examining a curious mineral sent to him by Jens Esmark (1763–1839), a Norwegian mineralogist, thought that he could discern the presence of a new element. He isolated the impure metal by reducing its fluoride salt with elemental potassium, and named it thorium, after the Scandinavian god, Thor. The mineral was subsequently called thorite.14 In 1898, working independently, Marie Curie and Gerhard C. Schmidt (1865–1949) reported almost simultaneously that thorium, such as uranium, was radioactive.15, 16
4.2 The Discovery of Actinium
Seventy years were to pass before the announcement of the discovery of actinium (Z = 89), the element that gives its name to the entire actinide series.17 Parisian André‐Louis Debierne (1874–1949) began his studies at the École de Physique et de Chemie and began to study mineral chemistry following the death of his mentor, Charles Friedel (1832–1899). Welcomed into the Curies' laboratory, he began to treat the enormous quantities of pitchblende they supplied to him until he soon discovered a new element; he was one of the youngest chemists ever to do so.18 He called it actinium from the Ancient Greek word, aktinos, meaning beam or ray.
The year 1913 was a landmark one for science: in that year H. G. J. Moseley (1887–1915) conferred a number and identity on every atom by reason of its number of nuclear protons, and Frederick Soddy (1877–1956) discovered isotopes, atoms with differing neutron numbers in atoms with like atomic numbers. He also formulated the law of chemical displacement: α‐emitters produce a daughter product two atomic numbers lower and β‐emitters one atomic number higher. Moseley's work defined the list of elements still missing in the periodic table, namely elements 43, 61, 72, 75, 85, 87, and 91.19 Soddy's work solved the puzzle of the myriad of new “elements” spawned by radioactive decay and his chemical displacement law had predictive properties. All of these facts figured weightily in the discovery of protactinium over the period from 1913 to 1917.
4.3 The Discovery of Protactinium
The hunt was now on for the missing element 91. Kasimir Fajans (1887–1975) and Ostwald Helmuth Göhring (b. 1889) took up the challenge. Fajans was the first to succeed in deciphering the radioactive decay cascade of 238U as the following:
which translates in modern terminology to:
They found that the substance UX2, a β‐emitter with a very short half‐life of about 1 min, did not correspond to any radioisotope already known, realizing that it should occupy a vacant space in the periodic table. Owing to its short half‐life, they named this new element brevium.
Soon after Fajans's announcement, Otto Hahn (1879–1968) and Lise Meitner (1878–1968), working in Berlin, began to search for longer‐lived isotopes of the same element. Hampered by the outbreak of World War I, especially by Hahn's conscription, Meitner carried on alone with a miniscule sample (21 g) of pitchblende, doing preliminary separations. It was only a year later that she received a kilogram sample of radioactive salts from which she was able to isolate an isotope of element 23191 with a half‐life of about 32 700 years.20 They named it protoactinium (later changed to protactinium by IUPAC (International Union of Pure and Applied Chemistry) in 1949), recognizing it as the mother substance of actinium.b.
In June of that same year, Frederick Soddy and his young student, John Arnold Cranston (1891–1972), published the results22 of their heat treatments of pitchblende that yielded small sublimated amounts of protactinium for which they were unable to characterize the decay scheme. Obviously, the case of protactinium, tangled by a publication that appeared 5 years before that of Hahn and Meitner, as well as a new claim in the same year, became even more so. Eventually, the priority was awarded to the team that had discovered the longest‐lived isotope, Hahn and Meitner, but not without dealing delicately with the aggressive character and imperious temperament of Kasimir Fajans. Cranston and Soddy, having published their papers 3 months after those of Hahn and Meitner, immediately recognized their priority.23, 24
This little protactinium story was told at some length because it presages the multiple contentious priority disputes to follow: who gets the recognition for the discovery, and who gets to name the new element? The naming, in the end, came to be the most controversial issue, for as paleobotanist Hope Jahren (b. 1969) observes:
The scientific rights to naming a new species, a new mineral, a new atomic particle, a new compound, or a new galaxy are considered the highest honor and the grandest task to which any scientist may aspire.25
5 Discovery of Uranium Fission
5.1 Enrico Fermi's Neutron Bombardment Experiments
The facts that uranium was discovered in 1789 and its radioactivity was recognized in 1896 seem to be almost trivial in light of the shattering discovery of its most important, and most all‐encompassing property: its ability to undergo nuclear fission with the consequent release of immense amounts of energy. This property was undreamed of, and in fact dismissed, when, in April of 1934, Enrico Fermi (1901–1954) and his team, the legendary “Ragazzi di via Panisperna,” began to bombard uranium with neutrons. Fermi, convinced that knowledge of the atom was in large part complete, decided to investigate the properties of the atomic nucleus. He was one of the first to recognize the tremendous importance of artificial radioactivity, discovered by Frédéric Joliot (1900–1958) and Irène Joliot‐Curie (1897–1956), and for which they received the Nobel Prize in Chemistry in 1935.26
