Lanthanides & Actinides

Dr S.J. Heyes

Four Lectures in the 2^ndYear Inorganic Chemistry Course

Hilary Term 1998

If you have any comments please contact stephen.heyes@chem.ox.ac.uk

IMPORTANT! Information about best utilising this resource

Introduction

1 Some Definitions and Viewpoints

2 Occurrence and History of the Elements

3 Nature of f-electrons

4 Electronic Properties

5 Periodicity in the f-Block

Lanthanides

1 Abundance & Distribution

2 Extraction

3 Separation

4 The Metals

5 Examination of the predominance of the 3+ Oxidation State

6 General Features of Lanthanide Chemistry

7 Solution Chemistry

• Hydrated Ions
• Coordination Compounds
• Redox Chemistry - Oxidation States other than +3

8 Magnetism

• Paramagnetism
• Ferro- and Ferri-Magnetism

9 Electronic Spectroscopy

• Luminescence
• Phosphors
• Bioinorganic Chemistry
• Lasers

  Solids

  ~ Includes: Structures, Magnetism, Spectroscopy, Electronic & Optical Properties, Technological Importance

10 Halides

• LnX₃
• LnX₂
• SmI₂ ~ a versatile organic reagent
• Lower Halides

11 Hydrides

• LnH₂
• Hydrogen Storage

12 Oxides

13 Borides

14 Carbides

15 Organometallic Chemistry

• Cyclopentadienides
• Cyclooctatetraenides
• Arenes
• Mixed Alkyl Cyclopentadienides

16 Comparisons/Contrasts

• Is Y a rare earth?
• Should Sc be considered with the Lanthanides, Transition Metals or as Main Group 3?
• Contrasts between Lanthanides & Transition Metals
• Similarities between Lanthanides & Other Elements

Actinides

1 Periodicity

2 Occurrence

3 Synthesis of Trans-Uranium Elements

4 Uses of Trans-Uranium Elements

5 The Metals

6 General Observations on Actinides

Including Comparisons with Lanthanides & Transition Metals

7 Oxidation States

8 Aqueous Chemistry

9 Coordination Stereochemistries

10 Uranium Chemistry

• Halides
• Hydrides
• Oxides
• Aqueous Chemistry
  • especially the uranyl ion

11 Nuclear Technology

12 Organometallics

13 Super-Heavy Elements?

Problems Set

BIBLIOGRAPHY

Standard Textbook Accounts of increasing degree of sophistication:

J.E. Huheey, E.A. & R.L. Keiter, Inorganic Chemistry, 4^th ed., HarperCollins, N.Y., 1993 p. 599-617

A.G. Sharpe, Inorganic Chemistry, 3^rd ed., Longmans, London, 1992 Ch. 1, 26, 27

N.N. Greenwood & A. Earnshaw, Chemistry of the Elements, 2^nd ed., Butterworth-Heinman, London, 1997 Ch. 30, 31

F.A. Cotton & G. Wilkinson, Advanced Inorganic Chemistry, 5^th ed., Wiley, N.Y., 1988 Ch. 20, 21

C.S.G. Phillips & R.J.P. Williams, Inorganic Chemistry, OUP, Oxford, 1966 Vol. 2, Ch. 21, 22

Books on lanthanides and actinides

S.A. Cotton, Lanthanides and Actinides, Macmillan, London, 1991 pp. 191

Open University, The Chemistry of the Lanthanides and the Transactinium Elements, Open University Press, Milton Keynes, 1977 S304 (The Nature of Chemistry) Unit 27 pp. 61

G.T. Seaborg & W.D. Loveland, The Elements beyond Uranium, Wiley, N.Y., 1990 (An enjoyable account of trans-uranium elements by the discoverer of many)

J.J. Katz, G.T. Seaborg & L.R. Morss, The Chemistry of the Actinides, 2^nd ed., Chapman & Hall, London, 1986 (a major reference work, see especially Ch. 14 Summary & Comparative Aspects)

Books with useful sections

D.A. Johnson, Some Thermodynamic Aspects of Inorganic Chemistry, 2^nd ed., CUP, Cambridge, 1982 p. 158-193 (a very good account of the thermodynamic underpinning of lanthanide/actinide chemistry)

S.F.A. Kettle, Physical Inorganic Chemistry, Freeman, N.Y., 1996, Ch 11. (f-Electron Systems)

R.D. Cowan, Theory of Atomic Structure & Spectra, UCP, Berkley, 1981 p. 598-613 (Lanthanide/Actinide Configurations)

J.A. Cowan, Inorganic Biochemistry, VCH, Weinheim, 1993 p. 300-307 (Ln³⁺ probes in biology)

C. Elschenbroich & A. Salzer, Organometallics, a Concise Introduction, 2^nd ed., VCH, Weinheim, 1992 p. 363-5 (Uranocene) p. 442-445 (organolanthanides)

T. Imamoto, Lanthanides in Organic Synthesis, Academic Press, London, 1994 parts of Ch. 4, 5, 6

P.A. Cox, The Electronic Structure and Chemistry of Solids, OUP, 1987, p.137-145 (Lanthanides)

A.R. West, Solid State Chemistry, Wiley, London, 1984 Ch. 16 (Magnetism), Ch 17. (Optical Properties)

K. Kosuge, Chemistry of Non-Stoichiometric Compounds, OUP, 1994 p. 219-230 (Hydrogen-absorption)

Article of Interest

W.B. Jensen, The Positions of Lanthanum(Actinium) and Lutetium(Lawrencium) in the Periodic Table, Journal of Chemical Education, 1982, 59, p. 634-636

Lanthanides & Actinides on the World-Wide Web

Periodicity & Physical Data:

• Mark Winter's WebElements: Invaluable compilation of data on the elements, accessed via a Periodic Table interface

• In Search of ... Elements: descriptions of the discovery of elements

• AMODS Atomic Energy Levels for Lanthanides from the Korean Atomic Energy Research Institute

Production & Supply of Lanthanides:

• Molycorp: One of the world's largest supplier of Lanthanides from a huge deposit of Bastnaesite in the Sierra Nevada, California, USA

• Mountain Pass Mine
• List of Technological Uses of Cerium

• Pacific Industrial Development Corporation (PIDC): - suppliers of rare earth compounds

Lanthanide & Actinide Chemistry:

• Lanthanide & Actinide complexes with Calixarenes: Mark Ogden's homepage contains entertaining displays of animated molecular models of some complexes

(Requires the Chime Plug-in)

• Current Research in Organo-Actinide Chemistry: A poster by Carol J. Burns, Los Alamos National Lab., USA

Lanthanides in Technology:

• Sandia National Lab.: Hydrogen Storage with Metals and Alloys

• The Luminescent Lanthanide Homepage

• Luminescent Lanthanide Labelling for DNA Sequencing

Nuclear Technology:

• British Nuclear Fuels

• Nuclear Materials Technology Division of Los Alamos National Laboratory, USA

Superheavy Elements:

• Heavy Ion Research at GSI, Darmstadt, Germany

• Synthesis of Superheavy Elements using the accelerator
• Discovery of Element 112
• Jon Petter Omtvedt's Work using SISAK to study the chemistry of some transactinide elements produced at GSI

If you have any comments please contact stephen.heyes@chem.ox.ac.uk