~ f .. " f C

') i. oj' f £ii'

Ia i' ~ f if

it

f !l- n ~

I H 2

3 4

Li 2

0 Be

26

II

12

Na21

M

g27

19 .

. 20

K

22

Ca 2

8

37

38

Rb24

5r

29

55

56

Cs 2

5 Ba

30

87

88

Fr25

a Ra

31

**La

ntha

n ide

s 39

1***

Acti

n ide

s

i I .

I I I I I , I I I I

21

22

So 3

9 Ti

41

39

40

Y 39

Zr

42

57**

72

La

39

Hf43

89**

* 10

4 Ac

40

71

58

59

Co

Pr

90

Th44

91

Pa

51

Perio

dic

Tabl

e of

the

Elem

ents

with

the

Gm

elin

Sys

tem

Num

bers

I I

, I

I i

I

I I

I , I

I I

I ,

5 , .

I ,

I I

I B

13

i ,

I I

I I

13

I

I I I

AI 3

5 :

23

24

25

26

27

28

29

30

31

V 48

Cr

52

Mn

56

Fe 5

9 Co

58

Ni 5

7 Cu

60

Zn 3

2 Ga

36

41

42

43

44

45

46

47

48

49

Nb49

M

053

Tc

69

Ru 6

3 Rh

64

Pd 6

5 Ag

61

Cd 3

3 In

37

73

74

75

76

77

78

79

80

81

Ta50

W

54

Re 7

0 Os

66

Ir 67

PI

68

Au 6

2 H g

34

TI 3

8

105

71

60

61

62

63

64

65

66

67

68

Nd

Pm

5m

Eu

Gd

Tb

Oy

Ho

Er

92 U 55

93

Np

71

94

Pu 7

1 95

Am

71

96

Cm71

97

Bk

71

98

Cf 7

1 99

Es

71

100

Fm 7

1

I I

2 H

2 He

l

6 7

8 9

10

C 1

4 N

4

o 3

F5

Ne I

14

15

16

17

18

5i 15

P

16

5 9

CI6

Ar 1

32

33

34

35

36

Ge45

As

17

5e 1

0 Br

7

Kr I

50

51

52

53

54

5n46

5b

18

To II

1

8 Xo

l

82

83

84

85

86

Pb4 7

Bi

19

P ol2

At

8a

Rn I

I~Hl31

69

70

71

Tm

Vb

Lu

101 Md

71

102 No 7

1 10

3 Lr 7

1

Gmelin Handbook of Inorganic Chemistry

8th Edition

Grnelin Handbook of Inorganic Chemistry

Prepared and issued by

Founded by

8th Edition

Continued by

8th Edition

Gmelin Handbuch der Anorganischen Chemie

Achte, voUig neu bearbeitete Auflage

Gmelin-Institut fUr Anorganische Chemie der Max-Planck-Gesellschaft zur Forderung der Wissenschaften

Director: Ekkehard Fluck

Leopold Gmelin

8th Edition begun under the auspices of the Deutsche Chemische GeseUschaft by R. J. Meyer

E. H. E. Pietsch and A. Kotowski, and by Margot Becke-Goehring

Springer-Verlag Berlin Heidelberg GmbH 1989

GmeLin-lnstitut fUr Anorganische Chemie der Max-PLanck-GeseLLsc.haft zur Forderung der Wissenschaften

ADVISORY BOARD

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Prof. Dr. Dr. h. c. Ekkehard Fluck Dr. W. Lippert

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Gmelin Handbook of Inorganic Chemistry

AUTHORS

CHIEF EDITORS

8th Edition

Th Thorium Supplement Volume A 4

General Properties. Spectra. Recoil Reactions

With 54 illustrations

Robert G. Behrens, Los Alamos National Laboratory, Los Alamos, New Mexico, USA Michael Bickel, Kernforschungszentrum Karlsruhe, Karlsruhe, Federal Republic of Germany Rolf Engleman Jr., University of Arizona, Tucson, Arizona, USA

Jean Fuger, Commission of the European Communities, Institute for Transuranium Elements, Karlsruhe, Federal Republic of Germany

Lawrence E. Grimes, Weapons Laboratory, Kirtland Air Force Base, New Mexico, USA Basil Kanellakopulos, Kernforschungszentrum Karlsruhe, Karlsruhe, Federal Republic of Germany Daniel J. Lam, Argonne National Laboratory, Argonne, Illinois, USA

Kurt Roessler, Kernforschungsanlage Julich, JUlich, Federal Republic of Germany

Boyd W. Veal, Argonne National Laboratory, Argonne, Illinois, USA

Rudolf Keirn, Gmelin-Institut, Frankfurt am Main Cornelius Keller, Supervising Scientific Coordinator for the Thorium Supplement Volumes, Schule fur Kerntechnik, Kernforschungszentrum Karlsruhe

System Number 44

Springer-Verlag Berlin Heidelberg GmbH 1989

LITERATURE CLOSING DATE: MID OF 1987

IN SOME CASES MORE RECENT DATA HAVE BEEN CONSIDERED

Library of Congress Catalog Card Number: Agr 25-1383

ISBN 978-3-662-07412-1 ISBN 978-3-662-07410-7 (eBook) DOI 10.1007/978-3-662-07410-7

This work is subject to copyright. All rights are reserved. whether the whole or part of the material is concerned. specifically those of translation, reprinting, reuse of illustrations, broadcasting. reproduction by photocopying machine or similar means, and storage in data banks. Under § 54 of the German Copyright Law where copies are made for other than private use, a fee is payable to "Verwertungsgesellschaft Wort", Munich.

© by Springer-Verlag Berlin Heidelberg 1989 Originally published by Springer-Verlag Berlin Heidelberg New York London Paris Tokyo in 1989 Softcover reprint of the hardcover 8th edition 1989

The use of registered names, trademarks, etc., in this publication does not Imply, even in the absence of a specific statement. that such names are exempt from the relevant protective laws and regulations and therefore free for general use.

Typesetting, printing, and bookbinding: LN-Druck Lubeck

Preface

The present volume describes the general properties of the thorium atom and ions, the thermodynamics of its compounds and solutions, the behavior of solutions and solid com­pounds under the influence of its own radiation as well as an external radiation field, and spectroscopic data in great detail.

The different chapters are of special interest to scientists who work in these fields, and also in the corresponding fields of other elements. In some special fields there exists a detailed knowledge of this radioelement whereas in other fields, such as M6Bbauer spectra, lower oxidation states, or radiation stability, there are large gaps. Due to the fact that the significance of thorium as a breeder fuel (232"fh to be converted to fissile 233U after thermal neutron capture) has decreased within the last decade, the behavior of thorium is not as yet so thoroughly investigated as the heavier radioactive element uranium.

Many of these data, however, are not only of academic interest, e.g., the knowledge of atomic spectra is needed for some analytical methods, especially in the trace concentration region. Due to the noble gaS-like electronic configuration of the tetravalent ion, there are no absorption bands in the visible region so that in general spectra and data are very scarce.

This volume is a very detailed and critically reviewed compilation, written by experts from the Federal Republic of Germany, Belgium, and the United States.

I want to thank the authors for their excellent contributions and good cooperation. Special thanks also to the Gmelin Institute, especially to the editor-in-charge Dr. R. Keim and the Institutes director, Prof. Dr. E. Fluck.

Karlsruhe June 1989

Cornelius Keller

Volumes published on "Radium and Actinides"

Ac Actinium

Main Volume

Suppl. Vol. 1: Element and Compounds

Np, Pu, ... Transuranium Elements

Main Volume

Part A: The Elements

A 1, I History, Occurrence, Properties of Atomic Nuclei A 1, II Nuclides: Manufacture, Recovery, Enrichment A 2 General Properties, Uses, Storage, Biology

Part B: The Metals

B 1 Metals B 2 Binary Alloy Systems 1 B 3 Binary Alloy Systems 2

Part C: The Compounds

C Compounds

Part 0: Chemistry in Solution

D 1 Aqueous Solutions. Coordination Chemistry D 2 Extraction, Ion Exchange. Molten Salts

Index

Pa Protactinium Main Volume

Suppl. Vol. 1: Element

Suppl. Vol. 2: Metal. Alloys. Compounds. Chemistry in Solution

Ra Radium

Main Volume

Suppl. Vol. 1: History. Cosmochemistry. Geochemistry Suppl. Vol. 2: Element. Compounds

Th Thorium

Main Volume

Suppl. Vol. Part A: The Element A 1 Thorium Deposits. Geochemistry (in preparation) A 2 History. Isotopes. Recovery of Thorium from Ores A 3 Technology. Uses. Irradiated Fuel. Reprocessing A 4 General Properties. Spectra. Recoil Reactions (present volume)

- 1942

- 1981

- 1973 - 1974 - 1973

- 1976 - 1976 - 1977

- 1972

- 1975 - 1975

- 1979

- 1942

- 1977

- 1977

- 1928

- 1977 - 1977

- 1955

- 1986 - 1988 - 1989

SuppL VoL Part C: The Compounds C 1 Compounds with Noble Gases, Hydrogen, Oxygen - 1978 C 2 Ternary and Polynary Oxides - 1976 C 3 Compounds with Nitrogen - 1987 C 5 Compounds with S, Se, Te, B - 1986 C 7 Compounds with Carbon: Carbonates, Thiocyanates, Alkoxides, Carboxylates - 1988

Suppl. VoL Part D: Chemistry in Solution D 1 Properties of Ions in Solutions - 1988 D 2 Solvent Extraction - 1985

Suppl. VoL Part E: Coordination Compounds E Coordination Compounds - 1985

U Uranium

Main Volume - 1936

SuppL VoL Part A: The Element A 1 Uranium Deposits - 1979 A2 Isotopes - 1980 A 3 Technology. Uses - 1981 A 4 Irradiated Fuel. Reprocessing - 1982 A5 Spectra - 1982 A 6 General Properties. Criticality - 1983 A 7 Analysis. Biology - 1982

Suppl. VoL Part B: The Alloys (in preparation)

Suppl. VoL Part C: The Compounds C 1 Compounds with Noble Gases and Hydrogen. Uranium-Oxygen System - 1977 C 2 Oxides U30 a and U03. Hydroxides, Oxide Hydrates, and Peroxides - 1978 C 3 Ternary and Polynary Oxides - 1975 C 4 U02, Preparation and Crystallographic Properties - 1984 C 5 U02, Physical Properties. Electrochemical Behavior - 1986 C 6 U02, Chemical Properties (in preparation) C 7 Compounds with Nitrogen - 1981 C 8 Compounds with Fluorine - 1980 C 9 Compounds with Chlorine, Bromine, and Iodine - 1979 C 10 Compounds with Sulfur - 1984 C 11 Compounds with Selenium, Tellurium, and Boron - 1981 C 12 Carbides - 1987 C 13 Carbonates, Cyanides, Thiocyanates, Alkoxides, Carboxylates - 1983

Compounds with Silicon C 14 Compounds with Phosphorus, Arsenic, Antimony, Bismuth, and Germanium - 1981

SuppL VoL Part D: Chemistry in Solution D 1 Properties of the Ions. Molten Salts - 1984 D 2 Solvent Extraction - 1982 D 3 Anion Exchange - 1982 D 4 Cation Exchange and Chromatography - 1983

Suppl. VoL Part E: Coordination Compounds E 1 Coordination Compounds 1 - 1979 E 2 Coordination Compounds 2 (including Organouranium Compounds) - 1980

XIII

Table of Contents Page

1 General Properties of the Thorium Atom and Thorium Ions .................... 1

1.1 Introduction ......................................................... .

1.2 Electronic Structure ................................................... 2

1.3 Metallic Radius ....................................................... 6

1.4 Ionic Radii . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

1.5 Coordination Numbers ................................................. 7

1.6 Oxidation-Reduction Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

1.7 Excited Electronic Configurations. .. . ... . . . . ... . .. . . . . . . . . . .. . . . .. . .. . . .. 10

1.8 Spin-Orbit Coupling Parameters, Radial Integrals .......................... 10

1.9 Ionization Potentials ................................................... 12

1.10 Magnetic Susceptibility ............................................... 13

2 Spectra 17

2.1 The Atomic Spectroscopy of Thorium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.1.1 Historical Background ................................................ 17

2.1.2 General Description of Thorium Spectra ................................. 17

2.1.3 Line Lists and Energy Levels ........................................... 18 Th I .................................................................... 18 Th II . . . . .. . .. . . . . . . . .. . .. . ... . . . . .. . . . . ....... .. . . . . .. . . . . . . . . . . . . ... . . . 48 Th III ................................................................... 66 ThIV ................................................................... 79 Higher Ion Stages ........................................................ 81

2.1.4 Ionization Potentials .................................................. 81

2.1.5 Zeeman Stud ies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82

2.1.6 Isotope Shifts........................................................ 82

2.1.7 Hyperfine Structure................................................... 83

2.1.8 Transition Probabilities ............................................... 84

2.1.9 Wavelength Standards ................................................ 85

2.2 Absorption Spectra .................................................... 88

2.3 Thorium X-Ray Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

Gmelin Handbook Th Suppl. Vol. A4

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Page

2.3.1 X-Ray Emission Spectra ............................................... 90 General Remarks ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

Energies, Wavelengths .................................................. 90 Radiative and Nonradiative Transition Probabilities, Intensities,

Line Widths, Fluorescence Yields. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91 X-Rays from lon-Ion Collisions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

The K Series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 Emission Lines ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 Transition Probabilities, Intensities, Line Widths ............................. 93 Fluorescence Yield ..................................................... 94

The L Series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 Emission Lines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 Transition Probabilities, Intensities, Line Widths ............................. 96 Fluorescence Yields .................................................... 97

The M Series ............................................................ 100 Emission Lines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 Radiative Rates, Fluorescence Yields, Level Widths. . . . . . . . . . . . . . . . . . . . . . . . . . . 100

The Nand 0 Series ........................................................ 102 Emission Lines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102 Radiative Rates, Fluorescence Yields, Level Widths. . . . . . . . . . . . . . . . . . . . . . . . . . . 102

2.3.2 Auger and Coster-Kronig Transitions .................................... 103

2.3.3 Absorption Edges .................................................... 106

2.3.4 Muonic X-Rays ...................................................... 106

2.4 Photoemission Spectra ................................................ 11 0

2.4.1 Introduction ................................ :......................... 110

2.4.2 Core Levels ......................................................... 111 Binding Energies - Thorium Metal .......................................... 111 Intensities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 Satellites ........... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

2.4.3 Thorium Metal ....................................................... 117 Valence Bands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117 Chemisorption ........................................................... 119

2.4.4 Intermetallic Compounds and Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119 NaCI-Type Compounds..... .............. .. .. .. . . .. . . . .. . . .. .. .. . .. . ... .. . 120 Angle-Resolved UP5-ThPd3 and UPd3 .....••••.........••................... 122 Other Th and U Alloys and Intermetalllc Compounds ........................... 125 Thorium Hydrides and Hydrogen Absorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127 Catalytic Activity ......................................................... 128

2.4.5 Oxygen Compounds.... ............. . ... . . . . . .. . . . . . . .. . . .. .. . . .. .. . . 129 Th02 and U02 - Electronic Structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129 Binding Energies of Thorium-Oxygen Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130

2.4.6 Thorium-Halogen Compounds ......................................... 132

2.4.7 Organometallic Complexes 134

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Page

2.5 Electron Paramagnetic Resonance (EPR) ................................. 137

2.6 Nuclear Magnetic Resonance (NMR) ..................................... 139

2.7 Mossbauer Spectroscopy .............................................. 140

2.8 Thorium Mass Spectrometry ............................................ 143

2.8.1 Measurement of Atomic Mass of Thorium by Mass Spectrometry ............. 143

2.8.2 The Ionization Potential of Thorium by Mass Spectrometry .................. 144

2.8.3 Phase Equilibria, Vaporization Processes, and Thermochemical Studies of Thorium Compounds Using Mass Spectrometry. . . . . . . . . . . . . . . . . . . . . . . . . 145

Introduction ............................................................. 145 The Thorium-Oxygen System. .. . . . . . . . . . .. ... . . ... .. .. .. . . . . . .. . . .. . . . . .... 147 The Thorium-Nitrogen System. ........ .. ...... ..... . .. ... . . . . . .. . . . . ...... . 151 The Thorium-Fluorine System .............................................. 151 The Thorium-Iodine System ................................................ 151 The Thorium-Carbon System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152 The NaF-Th F 4 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 156 The U02- Th02 System .................................................... 157 Intermetallic Systems Containing Thorium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158 The Thorium-Ozone System.. . ........... . .... . ... ... .. . .. . . . . . . . . . . . . . . . . . 160

2.8.4 Structural Chemistry of Thorium-Containing Complexes Using Mass Spectrometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 162

2.8.5 Analytical Mass Spectrometric Techniques for Thorium . . . . . . . . . . . . . . . . . . . . . 163 Thermal Ionization Mass Spectrometry (TIMS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163 Isotope Dilution Mass Spectrometry (IDMS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165 Field Desorption and Field Ionization Mass Spectrometry (FDMS and FIMS) ........ 167 Spark Source Mass Spectrometry (SSMS) .................................... 168 Inductively Coupled Plasma Mass Spectrometry (ICPMS) . . . . . . . . . . . . . . . . . . . . . . . . 170 Resonance Ionization Mass Spectrometry (RIMS) ..... . . . . . . . . . . . . . . . . . . . . . . . . . 171 Scanning Laser Mass Spectrometry Milliprobe (SLMS) ......................... 172 Secondary Ionization Mass Spectrometry (SIMS) .............................. 173

3 Chemical Thermodynamic Properties - Selected Values . . . . . . . . . . . . . . . . . . . . . . 175

4 Effects of Ionizing Radiations ....... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191

Introduction 191

Metals and Alloys .......................................................... 191

Refractory Compounds ..................................................... 193

Other Compounds ......................................................... 196

5 Thorium Recoil Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199

5.1 Introduction

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5.2 Primary Energy, Differential Energy Loss, and Range of Thorium Recoils ...... 201

5.3 Charge States of Energetic Thorium Species .............................. 210

5.4 Physical Consequences of Energetic Motion of Thorium. . . . . . . . . . . . . . . . . . . .. 217

5.5 Classic Hot Atom Chemistry ............................................ 225

5.6 Thorium Recoils in Geochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 228

5.7 A New Model of a-Recoil Chemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240

Physical Constants and Conversion Factors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247

Gmelin Handbook Th Suppl. Vol. A 4