Appendix A: Ionisation • energies

Lanthanide ionisation energies (kJ mol-I)

II h h 14

Sc 631 1235 2389 7089 Y 616 1181 1980 5963 La 538.1 1067 1850 4819 Ce 527.4 1047 1949 3547 Pr 523.1 1018 2086 3761 Nd 529.6 1035 2130 3899 Pm 523.9 1052 2150 3970 Sm 543.3 1068 2260 3990 Eu 546.7 1085 2404 4110 Gd 592.5 1167 1990 4250 Tb 564.6 1112 2114 3839 Dy 571.9 1126 2200 4501 Ho 580.7 1139 2204 4150 Er 588.7 1151 2194 4115 Tm 596.7. 1163 2285 4119 Yb 603.4 1176 2415 4220 Lu 523.5 1340 2022 4360 Data from W. C. Martin et al., J. Phys. Chern. Ref. Data, 3 (1974) 771.

Actinide ionisation energies (kJ mol-I)

II h h 14

Ac 499 1170 1900 (4700) Th 587 1110 1978 2780 Pa 568 1128 2991 U 584 1420 1900 3145 Np 597 1128 1997 3242 Pu 585 1128 2084 3338 Am 578 1158 2132 3493 Cm 581 1196 2026 3550 Bk 601 1186 2152 3434 Cf 608 1206 2267 3599 Es 620 1216 2334 3734 Fm 627 1225 2363 3792 Md 635 1235 2470 3840 No 642 1254 2643 3956 Lr 444 1428 2228 4910

170

Appendix B: Ionic radii

Lanthanide and actinide ionic radii (A)

CN 6 CN 8 CN 6 CN 8

Sc3+ 0.745 0.870 yH 0.900 1.019 LaH 1.032 1.160 AcH 1.12 CeH 1.01 1.143 ThH PrH 0.99 1.126 PaH 1.04 NdJ + 0.983 1.109 UH 1.025 PmH 0.97 1.093 NpH 1.01 SmH 0.958 1.079 PuH 1.00 EuH 0.947 1.066 AmH 0.975 1.09 GdJ+ 0.938 1.053 CmH 0.97 Tb3+ 0.923 1.040 BkH 0.96 DyH 0.912 1.027 CfH 0.95 HOH 0.901 1.015 Er-'+ 0.890 1.004 TmH 0.880 0.994 Yb3+ 0.868 0.985 LuH 0.861 0.977

Nd~+ 1.29 Sm~+ 1.27 Eu~+ 1.17 1.25 Dy~+ 1.07 1.19 Tm~+ 1.03 Yb~+ 1.02 1.14 CeH 0.87 0.97 ThH 0.94 1.05 PrH 0.85 0.96 PaH 0.90 Ull TbH 0.76 0.88 UH 0.89 1.00

NpH 0.87 0.98 PuH 0.86 0.96 AmH 0.85 0.95 CmH 0.85 0.95 BkH 0.83 0.93 CfH 0.821 0.92

Pa5+ 0.78 0.91 U'+ 0.76 NpH 0.75 Pu5+ 0.74

UH 0.73 0.86 NpH 0.72 PuH 0.71

Data from R. D. Shannon. Acta Cryswl/ographim A. 32 (1976) 752.

171

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37

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85

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Ba

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138.

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ctIn

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) 12

26l

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2 (2

10)

VII

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•

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I A

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hlo

.. n

. A

rgo

n

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126.

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(210

)

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CD~ ~ -. >< n ••

-a CD .. _. o ~

-. "

Bibliography

Because of the increasing selectivity of libraries, where possible more than one source of further reading on a topic has been given.

For general properties of the elements, consult:

1. J. Emsley, The Elements, Oxford, 1989. 2. R. C. Weast (ed.), CRC Handbook of Chemistry and Physics, 70th edn,

Central Rubber Company Press, 1989-90.

For a particular compound, three avenues are open:

1. A search via Chemical Abstracts. 2. Consult the appropriate volume of 'Gmelin'. 3. Consult either the Dictionary of Organometallic Compounds (Chapman and

Hall, 1984, five supplements to 1989) or Dictionary of Inorganic Compounds (Chapman and Hall, due to be published in early 1992). Between them they contain data on well over 2000 lanthanide and actinide compounds.

General sources

Abbreviations used in text

ACE J. J. Katz, G. J. Seaborg and L. R. Morss (eds), The Chemistry of the Actinide Elements, 2nd edn, Chapman and Hall, 1986.

CCC G. Wilkinson, R. D. Gillard and J. A. McCleverty, (eds), Comprehensive Coordination Chemistry, Pergamon, 1987.

CIC J. e. Bailar Jr, H. J. Emeleus, R. S. Nyholm and A. F. Trotman-Dickenson (eds), Comprehensive Inorganic Chemistry, Pergamon, 1973.

LPL J-e. G. Bunzli and G. R. Choppin (eds), Lanthanide Probes in Life, Chemical and Earth Sciences, Elsevier, 1989.

HRE K. A. Gschneider Jr and LeRoy Eyring (eds), Handbook on the Physics and Chemistry of Rare Earths, North-Holland, 1978 onwards, vols 1-12.

173

174

HAC

LAS

AlP MTPI MTP2 SPL

IAR

GMEL

Lanthanides and adinides

A. J. Freeman and G. H. Lander (eds), Handbook on the Physics and Chemistry of the Actinides, North-Holland, 1984 onwards, vols 1-5. N. M. Edelstein (ed), Lanthanide and Actinide Chemistry and Spectroscopy, ACS Symposium Series, 1980, vol. HI. N. M. Edelstein (ed), Actinides in Perspective, Pergamon, 1982. K. W. Bagnall (ed), MTP International Review of Science, Inorganic Chemistry, Series 1 (1972) vol. 7; Series 2 (1975) vol. 7. S. P. Sinha (ed), Systematics and Properties of the Lanthanides, D. Reidel, 1983. K. A. Gschneider Jr (ed.), Industrial Application of Rare Earth Elements, ACS Symposium Series, 198I. Gmelins Handbuch der Anorganischer Chemie.

Chapter 1 - Scandium

The Gmelin System covers scandium as a 'rare earth' in Syst. No. 39. C. T. Horowitz (ed.), Scandium, Academic Press, 1975. R. C. Vickery, CIC, 3, 329 (general chemistry). G. A. Melson et al., Coord. Chem. Revs, 7 (1971) 133 (complexes). F. A. Hart, CCC, 3, 1059 (complexes).

Organometallics are generally reviewed with the lanthanides (see Chapter 2).

For the pentamethylcyclopentadienyls, see: M. E. Thompson et at., Pure Appl. Chem., 56 (1984) 1; J. Amer. Chem. Soc.,

109 (1987) 203.

Chapter 2 - The lanthanides

For historical perspective and general coverage: D. M. Yost, H. Russell Jr and C. S. Gamer, The Rare Earths and their

Compounds, John Wiley, 1947. R. C. Vickery, The Chemistry of Yttrium and Scandium, Pergamon, 1960; CIC,

3,329. T. Moeller, CIC, 4, I. N. E. Topp, The Chemistry of the Rare Earth Elements, Elsevier, 1965. G. R. Choppin, LPL, 1.

Gmelin coverage of these elements in Series 39 is well up to date: Series A covers occurrence and minerals; Series B separation and metals; Series C binary compounds and salts; and Series D coordination compounds and organometallics.

Bibliography 175

Sedion 2.1

T. Moeller, J. Chem. Educ., 47 (1970) 417 (principles). w. B. Jensen, J. Chem. Educ., 59 (1982) 634 (positions of La, Lu). D. R. Lloyd, J. Chem. Educ., 63 (1986) 502 (lanthanide contraction). H. G. Friedman et al., J. Chem. Educ., 41 (1964) 354 (f orbitals).

Sedion 2.2

H. E. Kremers, J: Chem. Educ., 62 (1985) 665 (extraction). G. W. de Vore, LPL, 321 (geochemistry). J.-c. Duchesne, SPL, 543 (geochemistry). P. Moller, SPL, 561 (geochemistry). S. R. Taylor and M. M. McLennan, HRE, 11, 485 (geochemistry). L. A. Haskin and T. P. Paster, HRE, 3, 1 (geochemistry).

Sedion 2.3

B. J. Beaudry and K. A. Gschneider Jr, HRE, 1, 173. H. F. Linebarger and T. K. McCluhan; L. A. Luyckx; K. E. Davies, in IAR, 3;

19; 167 (applications). E. L. Huston and J. J. Sheridan III, IAR, 223 (hydrides). G. G. Libowitz and A. J. Maeland, HRE, 3, 299 (hydrides).

Sedion 2.5

L. J. Nugent, J. Inorg. Nucl. Chem., 37 (1975) 1767; MTP2, 7,195 (redox potentials, oxidation states).

D. A. Johnson, Some Thermodynamic Aspects of Inorganic Chemistry, 2nd edn, Cambridge V.P., 1982,50-54,158-168; J. Chem. Educ., 57 (1980) 475.

D. W. Smith, Inorganic Substances, Cambridge V.P., 1990, 145-149, 163-167; J. Chem. Educ., 63 (1986) 228.

Sedion 2.6

Electronic spectra F. A. Hart, CCC, 3, 1105. T. Moeller, CIC, 4, 9. K. B. Yatsimirskii and N. H. Davidenko, Coord. Chem. Revs, 27 (1979) 223. S. Hufner, SPL, 313. W. T. Carnall et al., SPL, 389; HRE, 3, 171. C. A. Morrison and R. P. Leavitt, HRE, 5, 461. J. W. O'Laughlin, HRE, 4, 341. B. R. Judd, HRE, 11, 81.

176 lanthanides and actinides

Fluorescence R. E. Whan and G. A. Crosby, 1. Mol. Spectrosc., 8 (1962) 315. F. S. Richardson, Chern. Revs, 82 (1982) 541. J-c. G. Bunzli, LPL, 219. G. Biasse, HRE, 4, 237.

Colour TV J. R. McColl and F. C. Palilla, IAR, 177. G. Biasse, HRE, 4, 237.

Lasers M. J. Weber, HRE, 4, 275.

Magnetisrn F. A. Hart, CCC, 3, 1109. T. Moeller, CIC, 4, 9. J. Rossat-Mignod, SPL, 255.

Section 2.7 (see also Section 2.6)

T. Moeller, MTPI, 7, 275 (rev.). J. H. Forsberg, Coord. Chern. Revs, 10 (1973) 195 (rev.). D. G. Karraker, Inorg. Chern., 7 (1968) 473 (hypersens.). B. R. Judd, LAS, 267. J. L. Ryan and C. K. Jorgensen, J. Phys. Chern., 70 (1966) 2845. E. M. Stephens, LPL, 181 (Gd ESR). A. Abragam and B. Bieaney, Electron Pararnagnetic Resonance of Transition

Ions, Oxford, 1970 (Ln ESR). J. Reuben and G. A. Elgarish, HRE, 4, 483 (NMR). F. A. Hart, CCC, 3, 1100 (NMR). J-C. G. Bunzli, LPL, 219 (bioprobes). W de W. Horrocks Jr and D. R. Sudnick, Acc. Chern. Res., 14 (1981) 384

(bioprobes) . J. Reuben, HRE, 4, 515 (bioprobes). J. R. Ascenso and A. V. Xavier, SPL, 501 (bioprobes). F. S. Richardson, Chern. Revs, 82 (1982) 541 (bioprobes).

Section 2.8

D. Brown, Halides afthe Lanthanides and Actinides, John Wiley, 1968. J. Burgess and J. Kijorski, Adv. Inorg. Chern. Radiochern., 24 (1981) 51

(halides). J. M. Haschke, HRE, 4, 89 (halides). L. Eyring, HRE, 3, 337 (oxides). GMEL: CI (oxides), C2 (hydroxides), C3, C4alb, C6 (halides), C7 (sulphides),

ClI a (borides). P. P. Edwards et at., Chern. Brit., 23 (1987) 962 (superconductivity).

Bibliography 177

K. A. Bednorz and J. G. Muller, Science, 237 (1987) 1133; Angew. Chem. Int. Ed., 27 (1988) 735 (superconductivity).

C. N. R. Rao (ed.), Chemistry of Oxide Superconductors, Blackwell, Oxford, 1988.

Sedion 2.9

T. Moeller, CIC, 4 (1973) 28; MTPl, 285 (stability constants). A. E. Martell and R. M. Smith, Critical Stability Constants, Plenum, 1974

onwards, vols 1-6.

Sedlon 2.10

GMEL, DI-D5. F. A. Hart, CCC, 3, 1059. L. Niinsto and M. Leskala, HRE, 8, 203; 9, 91 (inorganic complexes). L. C. Thompson, HRE, 3, 209. J. F. Desreux, LPL, 43. J-c. G. Bunzli, HRE, 9, 321; LPL, 219 (macrocycles).

Sedion 2.11

Reviews on shift reagents include: J. Reuben, Prog. Nucl. Magn. Res. Spectrosc., 9 (1975) 1. J. Reuben and G. A. Elgarish, HRE, 4, 483. A. D. Sherry and C.F.G.C. Geraldes, LPL, 219. M. R. Peterson Jr and G. H. Wahl Jr, J. Chem. Educ., 49 (1972) 790. R. E. Sievers, Nuclear Magnetic Shift Reagents, Academic Press, 1973. F. A. Hart, CCC, 3, 1105.

M. F. Tweedle, LPL, 127 (NMR imaging). R. B. Lauffer, Chem. Rev., 87 (1987) 901 (NMR imaging).

Sedion 2.12

D. A. Johnson, Adv. Inorg. Chem. Radiochem., 20 (1977) 1. F. A. Hart, CCC, 3, 1109, 1113. T. Moeller, CIC, 4, 75, 97.

Sedlon 2.13

F. Weigel, Chem. Zeitung, 108 (1978) 339. G. E. Boyd, J. Chem. Educ., 36 (1959) 3. E. J. Wheelwright (ed.), Promethium Technology, American Nuclear Society,

1973.

178 Lanthanides and actinides

W. R. Wilmarth et at., J. Less Common Metals, 141 (1988) 275; J. Raman Spectroscopy, 19 (1988) 271.

Sedlon 2.14

T. J. Marks and R. D. Fischer (eds), Organometallic Chemistry of the f-block Elements, Reidel, 1979.

W. J. Evans, Adv. Organomet. Chem., 24 (1985) 13l. H. Schumann and W. Genthe, HRE, 7, 440. T. J. Marks, Progr. Inorg. Chem., 24 (1978) 5l. S. A. Cotton, J. Organomet. Chem. Library, 3 (1977) 217. P. L. Watson and G. W. Parshall, Acc. Chem. Res., 88 (1985) 51 (catalysis). G. Jeske et al., J. Amer. Chem. Soc., 107 (1985) 8111 (catalysis). H. B. Kagan and J. L. Namy, HRE, 6, 523 (organic synthesis). J. R. Long, HRE, 8, 235; Inorg. Chim. Acta, 18 (1985) 87 (organic synthesis). T. J. Marks and R. D. Ernst, Comprehensive Organometallic Chemistry,

Pergamon,3 (1982) 173.

Chapter 3 - The adinides

Apart from the text by Katz, Seaborg and Morss, general (though less up to date) coverage is given by:

C. Keller, The Chemistry of the Transuranium Elements, Verlag Chemie, 1971. K. W. Bagnall, The Actinide Elements, Elsevier, 1972.

Sedlon 3.2

J. J. Katz, G. T. Seaborg and L. R. Morss, ACE, 2, 1122. C. Keller, Angew. Chem. Int. Ed., 4 (1965) 903. G. T. Seaborg, Man-made Transuranium Elements, Prentice-Hall, 1963.

Complete lists of isotopes with half lives can be found in, for example, ACE, pp. 1654-1668; CRC Handbook of Chemistry and Physics (Rubber Handbook), B228-448 (1989 edition).

Sedlon 3.3

M. S. Fred, ACE, 2, 1196. J. J. Katz, L. R. Morss and G. T. Seaborg, ACE, 2, 1133, 1142. L. J. Nugent, J. Inorg. Nucl. Chem., 37 (1975) 1767; MTP2, 7, 195. K. W. Bagnall, Essays in Chemistry, 3 (1972) 39.

Bibliography

Sedlon 3.5

L. I. Katzin and D. C. Sonnenberger, ACE, 1,46 (thorium). Z. Kolaria, HAC, 3, 431. Z. Yong-jun, HAC, 3, 469. F. Weigel, ACE, 1, 196-211 (uranium). H. W. Kirby, ACE, 1, 112-118 (protactinium).

Sedion 3.6

F. Weigel, ACE, 1, 173. S. Villani, Isotope Separation, American Nuclear Society, 1976; Uranium

Enrichment, Springer-Verlag, 1979.

Sedion 3.7

B. Allard et at., Inorg. Chim. Acta, 94 (1984) 205. K. N. Raymond et at., AlP, 491; Inorg. Chim. Acta, 94 (1984) 193; Inorg.

Chem., 2S (1985) 605. R. A. Belman, Struct. Bonding, 34 (1978) 39. J. J. Katz, G. T. Seaborg and L. R. Morss, ACE, 2, 1169. J. R. Duffield and D. M. Taylor, HAC, 4, 129. G. R. Choppin and B. Allard, HAC, 3, 407.

Sedion 3.8

E. K. Hulet and D. D. Bode, MTPI, 7, 1. F. Weigel, J. J. Katz and G. T. Seaborg, ACE, 1, 505-577.

Sedlon 3.9

E. K. Hulet et at., 1. Inorg. Nucl. Chem., 42 (1980) 79.

Sedion 3.10

179

D. Brown, Halides of Lanthanides and Actinides, John Wiley, 1968; MTP, 1, 87. J. C. Taylor, Coord. Chem. Revs, 20 (1976) 197.

Sedlon 3.11

J. L. Ryan, MTPl, 7, 323 (UV-visible). W. T. Camall and H. M. Crosswhite, ACE, 2, 1235 (UV-visible).

180 Lanthanides and adinides

S. Ahrland, CIC, S, 473 (UV-visible). J. P. Hessler and W. T. Camall, LAS, 349 (UV-visible). N. M. Edelstein and J. Goffart, ACE, 2, 1361 (magnetic). J. W. Gonsalves et al., Inorg. Chim. Acta, 21 (1977) 167; S. Afr. 1. Chem., 30

(1977) 62 (magnetic).

For the elements covered in sections 3.12-3.20, the following references should particularly be consulted: K. W. Bagnall, CCC, 3, 1129; various authors, CIC, vol. 5.

Sedion 3.12

GMEL, Supplement No. 40, Main Volume 1942, Supplement 1981. H. W. Kirby, ACE, 1, 14. C. Keller, Chem. Zeitung, 101 (1977) 500.

Sedion 3.13

GMEL, Supplement No. 44, Main Volume 1955, Supplements A1-A4 (elements), C1-C7 (compounds), D1-D2 (solution), E (coordination compounds) .

L. I. Katzin and D. C. Sonnenberger, ACE, 1,41. J. F. Smith et at., Thorium, Preparation and Properties, Iowa State University

Press, 1978. L. Grainger, Uranium and Thorium, Newnes, 1958. I. Santos et at., Adv. Inorg. Chem. Radiochem., 34 (1989) 65.

Sedion 3.14

GMEL, System No. 51, Main Volume 1942, 2 Supplements 1977. D. Brown, AlP, 343; Adv. Inorg. Chem. Radiochem., 12 (1969) 1.

Sedion 3.15

F. Weigel, ACE, 1, 169. E. H. P. Cordfunke, The Chemistry of Uranium, Elsevier, 1969. W. Bacher and E. Jacob, HAC, 4, 1 (UF3). J. Selbin and J. D. Ortego, Chem. Revs, 69 (1969) 657 (U(V». U. Castellato et at., Coord. Chem. Revs, 36 (1981) 183 (nitrate complexes). D. Brown, MTP2, 7, 111 (nitrate complexes). D. Brown, MTPl, 7,87 (halide complexes). K. W. Bagnall, MTPl, 7,139 (thiocyanate complexes). I. Santos et al., Adv. Inorg. Chem. Radiochem., 34 (1989) 65. W. G. van der Sluys and A. P. Sattelberger, Chem. Revs, 90 (1990) 1027

(alkoxides) .

Bibliography

GMEL, Supt. No. 55, Main Volume 1936, Supplements from 1975; AI-7 (element), H2 (alloys), CI-14 (compounds), DI-4 (solution), EI-2 (coordination compounds).

For the uranyl ion, see, for example: S. P. McGlynn and J. K. Smith, 1. Mol. Spectrosc., 6 (1961) 164. R. G. Denning et al., LAS, 313; Mol. Phys., 37 (1979) 1109. W. R. Wadt, 1. Amer. Chem. Soc., 103 (1981) 6053. P. Pyykko et al., lnorg. Chem., 28 (1989) 1801.

181

For the transuranium elements, GMEL, Supplement No. 71, 1973-79 should be consulted.

Section 3.16

J. A. Fahey, ACE, 1, 443. S. K. Patel, Coord. Chem. Revs, 25 (1978) 133.

Sedion 3.17

G. T. Seaborg, AlP, 1. F. Weigel, J. J. Katz and G. T. Seaborg, ACE, 1,499. J. M. Cleveland, The Chemistry of Plutonium, American Nuclear Society, 1979. W. T. Carnall and G. R. Choppin (eds), ACS Symp. Series 1983, vol. 216.

Sedion 3.18

W. W. Schulz and R. A. Pennemann, ACE, 2, 887. J. D. Navratil, W. W. Schulz and G. T. Seaborg, 1. Chem. Educ., 67 (1990) 15. N. M. Edelstein, J. D. Navratil and W. W. Schulz, Americium and Curium

Chemistry and Technology, Reidel, 1985.

For syntheses of trans-americium halides see, for example, J. R. Peterson et al., 1. lnorg. Nucl. Chem. 35 (1973) 1525, 1711; 40 (1978) 811; 43 (1981) 2425; 1. Radioanal. Chem., 43 (1978) 479; lnorg. Chem., 25 (1986) 3779.

Sedion 3.21

T. J. Marks, HAC, 4, 491; ACE, 2, 1588. T. J. Marks and A. Streitweiser, ACE, 2, 1547. T. J. Marks and I. L. Fragala (eds), Fundamental and Technological Aspects of

Organo f-element Chemistry, Reidel, 1985. T. J. Marks and R. D. Ernst, Comprehensive Organometallic Chemistry,

Pergamon, 3 (1982) 173.

182 Lanthanides and actinides

Sedion 3.22

E. K. Hulet et ai., 1. lnorg. Nucl. Chem., 42 (1980) 79. R. J. Silva, ACE, 2, 1103. I. Zvara, lnorg. Nucl. Chem. Lett., 7 (1971) 1107. A. Ghiorso, AlP, 23. G. T. Seaborg and O. L. Keller, Jr, ACE, 2, 1629. Y. T. Organessian et ai., Radiochim. Acta, 37 (1984) 113. P. Armbruster et ai., Ann. Rev. Nucl. Part. Sci., 35 (1985) 135; 1. Less

Common Metals, 122 (1986) 581. B. Fricke, Structure and Bonding, 21 (1975) 89 (predicted properties).

For an outline of nuclear stability, see: G. T. Seaborg, l. Chem. Educ., 46 (1969) 626.

Index

NOTE: owing to the general similarity of lanthanide(lII) compounds, the following simplified procedure has been adopted. A comprehensive index is found under the heading LANTHANIDES. A compound such as, say, praesodymium(III) chloride is only indexed under PRAESODYMIUM if specifically mentioned in the text. General information relevant to Prel will however be found by looking up 'chlorides' under the LANTHA­NIDES heading.

ACTINIDES acetates 131, 145, 151, 156 acetylacetonates 119, 125, 140,

146, 151, 156 alkoxides 125, 135 alkylamides 120, 135, 141 alloys 116 aquo ions 115, 117, 122, 126, 143,

151 as fuels 96 borides 116 borohydrides 125, 141-2, 146, 151 bromides 101ft, 115, 118, 122, 144,

148, 155 carbides 116 carbonates 131, 133, 145, 150, 156 characteristics 88, 91 chlorides 101ft, 115, 122, 133, 144,

148 complexes 117/, 119ft, 124, 131/,

145/ coordination numbers 118/, 145/ diketonates 119, 125, 140, 156 dioxo ions 91, 122, 126ft, 143ft,

151/, 154 electron configurations 89 electronic spectra 107ft

183

elements 116, 122, 126, 143, 146, 152

extraction 92ff fission 97 fluorides 101ft, 115, 122, 133, 144,

148, 155 half-lives 87 halide complexes 119/, 124, 138/,

149, 155 halides 100-7, 115, 118, 122, 144,

148, 155 handling 99-100 hydrides 116, 122, 142, 148 hydroxides 92, 144, 151 iodides 101ft, 115, 118, 122, 136,

144, 148, 157 ionic radii 171 ionisation energies 89, 170 isotopes 87, 94 magnetic properties 111/ metals 115, 116, 122, 126, 143,

146, 152, 157 mixed oxides 144, 147 nitrates 117, 119, 122, 131, 138/,

145, 151 occurrence 85/ ores 92/

184 Index

ACTINIDES (cont'd.) organometallics 160ft oxalates 115 oxidation states

general 88-91, 100/ unusual:O state 166

+2 state 89/, 101//, 121 +6 state 101ft, 127//,

143/, 147/ + 7 state 100, 103, 143,

147, 151 oxides 115, 116, 122, 127/, 144,

147, 154 oxyhalides 115, 122, 134, 145, 157 phospine oxide complexes 119,

139, 150 reduction potentials 89-91, 99, 114 separation 96--9, 115 stability constants 52, 118 sulphates 117, 122, 142, 156 sulphides 116 synthesis 85-8 thiocyanates 119, 125, 144 toxicity 95/

ACTINIUM aquo ion 115 bromide 106, 115 chloride 104, 115 electron configuration 89 fluoride 104, 115 half-life 87 iodide 106/ isotopes 87 oxalate 115 oxidation states 88 oxide 115 oxyhalides 115 reduction potentials 90, 114 separation 115

ALLANITE 15 AMERICIUM

acetate complex 156 aquo ions 153 bromides 155 carbonate complex 156 chlorides 105 diketonates 156 electron configuration 89 element 152 fluorides 103/, 155 half-life 87, 152 halide complexes 155 halides 100/, 155 hydroxide 154

iodides 107,155, 157 isotopes 86/ metal 152, 154 organometallics 160 oxalates 156 oxidation states

general 88/, 153/, 157 +2 state 89, 101, 157 + 3 state 101, 153, 157 +4 state 101, 157 +5 state 154/ +6 state 101/, 154/ +7 state 154

oxides 154 oxyhalides 155, 157 reduction potentials 90/, 153 sulphate 156 synthesis 186

ARENE COMPLEXES 81/ AUTUNITE 93

BASTNASITE 15 BERKELIUM

bromide 105 chloride 104 element 157 fluoride 104, 158 half-life 87 halides 101/, 157 isotopes 87 oxidation states 88/, 156/

+4 state 89-91 oxide 157 reduction potentials 90 synthesis 86

CALIFORNIUM bromide 105 chloride 157 element 157 fluoride 157 half-life 87 halides 101/, 157/ iodide 157 isotopes 87 oxalate 158 oxidation states 88/, 156/

+ 2 state 89/, 157 +4 state 89/, 157

oxide 158 reduction potentials 90 synthesis 86

CARBONYLS 81, 166/ CARNOTITE 93

CERIC see CERIUM, oxidation state (+4)

CERITE 15 CERIUM

acetate 58 acetylacetonate 72 alkoxides 56, 72 alloys 18 aquo ion 70 arsine oxide complexes 72 bromide 71 carbonate 71 chloride 53 diketonates 72 discovery 10 electron configuration 11-12 electronic spectra 30 element 18 energy levels of ion 29 fluoride 70 halide complexes 71 halides 21f, 41f, 70f hydroxide 70 ionisation energies 25, 170 lower halides 43f magnetic properties 11, 39 nitrate 53, 71 ores 15 oxidation state (+4) 21f, 70ft, 82 oxide 45,70 phosphate 15, 70 phosphine oxide complexes 71f reduction potentials 26, 70 sulphate 53, 71 sulphide 47 sulphoxide complexes 72

COLOUR TELEVISION 32 COORDINATION NUMBERS

(UNUSUAL) Three 5, 7,56,61, 74, 76, 166 Four 5, 56, 61, 62, 74, 76, 118,

120, 135, 141 Five 62, 77, 135, 141 Ten 53, 54, 60, 65, 71, 119, 140 Eleven 53, 65, 71, 119, 140 Twelve 53,60, 65, 71, 119, 141,

142, 146, 151 Fourteen 125, 141

CURIUM bromide 157 chloride 105, 157 element 88, 157 fluorides 105, 157 half-life 88, 157

Index

halides 101, 104f, 157 iodide 157 isotopes 88,99 oxidation states 88f, 157

+4 state 157 oxides 157 reduction potentials 90 synthesis 86

DAVIDITE 1 DIDYMIUM 10 DYSPROSIUM

dimethylsulphoxide complex 54 electron configuration 11 energy levels of ion 29 halide complexes 63 halides 41ff ionisation energies 170 lower halides 43, 44 luminescence 31 magnetic moment 11 oxidation state (+2) 43f reduction potentials 26 shift reagents 69 sulphides 46f

EINSTEINIUM bromide 105 chloride 105, 158 fluoride 91, 158 half-life 86 halides 101, 104f isotopes 88 oxidation states 88f, 157

+ 2 state 90, 157 oxide 157 reduction potentials 90 synthesis 86

ELECTRON SPIN

185

RESONANCE 38, 108 ELECTRONIC CONFIGURATIONS

atoms 11f, 89 ions 11, 89, 157

ELEMENT 104 100f, 167 ELEMENT 105 168 ELEMENT 106 168 ELEMENT 107 168 ELEMENT 108 168 ELEMENT 109 168 ELEMENT 110 168 ELEMENT 116 169 ENERGY LEVEL DIAGRAMS

lanthanide ions 29

186

ERBIUM acetate 58 aquo ions 53 crown ether complex 65 dimethylsulphoxide complex 54 electron configuration 11 electronic spectrum 31, 35 energy levels of ion 29 halide complexes 62 halides 41/1 hypersensitive transitions 31 ionisation energies 170 magnetic moment 11 organometallics 79 phthalocyanine 66 reduction potentials 26 thiocyanate complex 62

EUROPIUM acetylacetonate 59 bioprobe 40 borides 48 bromides 41f carbonate 73 carbonyl 81 chloride 41f crown ether complex 65 diketonates 58 electron configuration 11 electronic spectra 30 element 171 energy levels of ion 29 fluorescence see luminescence fluorides 41/ halides 41ft hydride 19 hydroxide 73 in colour TV 32 iodides 421 ionisation energies 170 luminescence 31,36 magnetic properties 11, 39 Mossbauer spectra 39 naphthyridyl complex 60 nitrates 65 organometallics 761 oxalates 73 oxidation states

general 23ft +2 state 44, 73

. oxides 45 reduction potentials 26 separation 16, 73 shift reagents 66 sulphates 73

Index

sulphides 46 terpyridyl complex 61

EUXENlTE 15, 93

IORBITALS 14,129/,163 FERGUSONITE 93 FERMIUM

aquo ion 158 chloride 89 fluoride 158 half-life 87 halides 89, 158 hydroxide 158 isotopes 87 oxidation states 88

+ 2 state 89, 156 reduction potentials 90 synthesis 86

FLUORESCENCE SPECTRA 31, 36/,40

GADOLINITE 15 GADOLINIUM

alkylamides 39 aquo ion 53 bioprobe 40 diketonates 59 DTP A complex 63 electron configuration 11 electron spin resonance 39 energy levels of ion 29 halides 41 halides, lower 441 iodide 44 ionisation energies 170 magnetic moment 11 organometallics 761 phosphine oxide complex 55 reduction potentials 26 sulphide 47

HAHNIUM see ELEMENT 104 HOLMIUM

acetylacetonate 59 electron configuration 11 electronic spectrum 11 energy levels of ion 29 halides 41f hypersensitive transitions 35 ionisation energies 170 magnetic moment 11 organometallics 761 reduction potentials 26 sulphides 47

HUND'S RULES 28 HYPERSENSITIVE

TRANSITIONS 31,35

KOLBECKITE 1 KUCHATOVIUM see ELEMENT

104

LANTHANIDES acetates 58 acetylacetonates 59 alkoxides 55f, 74 alkylamides 61, 74 alloys 18 aquo ions 53 arene complexes 81 arsine oxide complexes 54 bioprobes 40 bipyridyl complexes 60 bodyscanners 63 borides 48 bromides 41f carbides 48 carbonyls 81 carboxylates 58 characteristics 20 chlorides 41f colour TV 32 complexes 49ft crown ether complex 64 cyclopentadienyls 78f diketonates 50, 58f EDT A complexes 50 electron configurations 11 electron spin resonance 38 electronic hypersensitive

transitions 31, 35 elements 17f extraction 15 f orbitals 14 fluorescence see luminescence fluorides 41f halide complexes 52, 62, 71 halides 21f, 41ft halides, lower 43f hydrides 19 hydroxides 46 iodides 42f ionisation energies 170 lasers 33 lower halides 43f luminescence 31f, 36f macrocycle complexes 64f magnetic properties 11, 33f, 39

Index

magnetic resonance imaging 63 metal see individual element Mossbauer spectra 39 naphthyridine complexes 60 nitrates 53 NMR spectra 39, 63, 66 occurrence 15 ores 15 organometallics 76ft oxalates 58 oxidation states

general 21f +2 state 73f +4 state 70f

oxides 45, 70, 72 phenanthroline complexes 60 phosphates 15 phosphine oxide complexes 54 phthalocyanines 66 physical methods in 34ff porphyrins 66 pyridine N-oxide complexes 54 radioactive 75

187

reduction (redox) potentials 26 Russell-Saunders (RS), coupling in 27f salts 53 separation 16 shift reagents 63, 66f stability constants 49f, 52 sulphates 53 sulphides 46 sulphoxide complexes 54 superconductors 46 terpyridyl complexes 37 thiocyanates 58, 61f

LANTHANUM acetylacetonate 59 alloys 18 aquo ion 53 boride 48 crown ether complex 65 cryptate 65 dimethylsulphoxide complex 54 discovery 10 electron configuration 11 element 17f energy levels of ion 29 fluorides 41f halides 41f iodide 42 ionisation energies 170 lower oxidation states 44 magnetic moment 11 nitrate complexes 53,60

188

LANTHANUM (cont' d) organometallics 76f oxide 45 phosphine oxide complexes 55 pyridine N-oxide complex 54 reduction potentials 26 stability constants 52 sulphides 46 terpyridyl complex 61

LASERS 33 LAWRENCIUM

half-life 87 isotopes 87 oxidation states 88 reduction potentials 90 synthesis 88

LUMINESCENCE see FLUORESCENCE SPECTRA

LUTETIUM alloys 18 aquo ion 53 diketonate 59 dimethylsulphoxide complex 54 electron configuration 11 energy levels in ion 29 halides 41f hydroxide 46 ionisation energies 170 magnetic moment 11 organometallics 76ff reduction potential 26 stability constants 52 sulphide 46 terpyridyl complex 61

MAGNETIC PROPERTIES actinides ll1ff lanthanides 11, 33f, 39

MENDELEVIUM half-life 87 isotopes 87 oxidation states 88 reduction potentials 90 synthesis 88

MISCHMET AL 16, 18 MONAZITE 15, 92 MOSSBAUER

SPECTROSCOPY 39

NEODYMIUM acetylacetonates 59 alkoxides 55 alkylamides 61 alloys 18

Index

aquo ion 35 chloride 23 crown ether complex 65 diketonate complexes 59f dimethylsulphoxide complex 54 electron configurations 11 electronic spectra 35 energy levels of ion 29 halide complexes 63 halides 41f halides, lower 23, 44 hypersensitive transitions 35 ionisation energies 170 lasers 33 magnetic moment 11 nitrate 65 organometallics 70ft oxidation state (+2) 23,45 oxide 45 pyridine N-oxide complex 54 reduction potentials 26

NEPTUNIUM acetate 145 acetylacetonate 146 aquo ions 143 borohydride 146 bromide 105f, 144 carbide 145 carbonate 145 chloride 105, 144 complexes 145f coordination numbers 145f discovery 86, 143 electron configuration 89 element 143 fluorides 104, 144f half-life 87,143 halide complexes 146 halides 10 If, 144 hydride 145 hydroxide 144 iodide 144 ionisation energies 170 isotopes 87 nitrate 145f nitride 145 organometallics 160f oxidation states

general 88 +3 state 146 +4 state 143f +5 state 143 +6 state 143f + 7 state 143, 144

oxides 144 oxyhalides 145 phosphine oxide complexes 146 reduction potentials 143 synthesis 86 thiocyanate 146

NEPTUNYL IONS 143f NOBELIUM

aquo ion 159 fluoride 159 half-life 87 halides 159 isotopes 87 oxidation states 88

+2 state 159 reduction potentials 90 synthesis 88

NUCLEAR fission 97 syntheses 86f, 167f

PITCHBLENDE 93 PLUTONIUM

acetate 151 acetylacetonate 151 aquo ions 151 borohydride 151 bromide 105f, 148 carbonate 150 characteristics 146 chlorides 104f, 148 complexes 149f diketonates 151 EDT A complexes 96 electron configuration 89 element 146 fission 97 fluorides 103f, 148 half-life 87 halide complexes 149f halides 10, 148 handling 95f, 146 hydrides 148 hydroxide 151 iodide 107, 148 ionisation energies 170 isotopes 87 nitrates 98, 147, 151 nitride 148 occurrence 86 organometallics 160f oxalate 147, 150

Index

oxidation states general 88, 151 + 3 state 146, 148 +4 state 146, 149f +5 state 151 +6 state 147f + 7 state 147, 151

oxides 147 oxo ions 147f oxyhalides 149 phosphine oxide complexes 150 recycling 97 reduction potentials 90, 151 separation 97f sulphoxide complexes 150 synthesis 86 thiocyanates 150 toxicity 95

PLUTONYL IONS 147ff POL YCRASE 151 PRAESODYMIUM

acetyl ace to nate 59 alkoxide 56 diketonate complexes 59, 60, 67 dimethylsulphoxide complex 54 electron configuration 11 electronic spectra 30 energy levels of ion 29 fluorides 22 halide complexes 62 halides 41f iodide 44 ionisation energies 170 magnetic moment 11 naphthyridine complex 60 nitrate complexes 53-4 organometallics 78 oxidation state (+4) 22, 72 oxides 72 reduction potentials 26 shift reagents 67 terpyridyl complexes 61 trifluoroacetate 58

PROMETHIUM bromide 75 chloride 75 electron configuration 11 element 76 fluoride 75 half-life 75 hydroxide 75 iodide 42, 75 isotopes 75 magnetic moment 11

189

190

PROMETHIUM (cont'd.) nitrate 76 occurrence 75 oxalate 75/ oxide 76 reduction potential 26

PROTACTINIUM acetylacetonate 125 alkoxide 125 aquo ion 122 bromide 122/ chloride 103, 122/ complexes 124 coordination numbers 123-5 diketonates 125. discovery 87 electron configuration 89 element 122 extraction 92 fluoride 103, 122/ half-life 87, 121 halide complexes 124 halides 101, 122 hydride 122 iodides 103, 122/ ionisation energies 170 isotopes 87, 121 metal 122 nitrate 122 nitride 122 ores 92 organometallics 161 oxidation states

general 88 + 3 state 122/ +4 state 122/

oxide 122 oxyhalides 122/ reduction potentials 90 salts 122 sulphate 122 thiocyanate 125

REDUCTION POTENTIALS actinides 89ft, 99, 126, 143, 151 lanthanides 26/

RUSSELL-SAUNDERS COUPLING 27/

RUTHERFORDIUM see ELEMENT 104

SAMARIUM alloys 18 aquo ion 53

Index

boiling point 18 dimethylsulphoxide complex 54 electron configuration 11 element 18 energy levels of ion 29 halide complexes 63 halides 41/ ionisation energies 170 luminescence 36 magnetic moment 11 organometallics 76/ oxidation state (+2) 24,44/, 73 oxide 17,45 reduction potentials 26 sulphide 46 synthesis 17

SARMARSKITE 93 SCANDIUM

acetylacetonate 5 alkoxides 5/ alkylamide 7 aquo ion 4 boride 4 bromide 3 carbide 4 chloride 3/ complexes 5/ coordination numbers 2 diketonates 5 element 3 fluoride 3 halide complexes 3, 5 halides 3 halides, lower 4 hydride 4 iodide 3 nitrate 5 ores 1 organometallics 7 oxalate 5 oxide 3 porphyrins 6 salts 4/ stability constants 52 sulphate 5 tropolonate 5

SHIFT REAGENTS 66--70 STABILITY CONSTANTS 52,118 STERRITE 1 SUPERHEA VY ELEMENTS 167-9

TERBIUM aquo ion 53 bioprobe 40

chloride 42 diketonates 59 electron configuration 11 electronic spectra 30 energy levels in ion 29 fluoride 45, 73 halide complexes 62, 73 halides 41f ionisation energies 170 lower halides 45 luminescence 31,40 magnetic moment 11 nitrate 72 oxidation state (+4) 72f oxide 45, 72 reduction potentials 26

THORIUM acetylacetonate 119 alkylamides 120 alloy 116 aquo ion 117 borides 116 bromide 118 carbide 116 characteristics in chemistry 115 chloride 118 complexes 117f coordination numbers 118f cyc100ctatetraenyl complexes 163f cyc10pentadienyl complexes 121,

160f diketonates 119f dithiocarbamates 121 EDT A complex 118 electron configuration 89 element 116 extraction 15, 92 fluoride 91, 118 half-life 87 halide complexes 119f halides 91, 101, 118 halides, lower 91 hydrides 116 hydroxide 92 iodides 91, 103, 118 ionisation energies 89, 170 isotopes 87 nitrate 117 nitrate complexes 117 nitride 116 occurrence 15, 92 ores 92 organometallics 160ft oxalates 117

Index

oxidation states general 88f +2 state 121 +3 state 121 +4 state 117f

oxide 116 perchlorate 117 phosphate 92, 117 phosphine complexes 121 phosphine oxide complexes 119f reduction potentials 90 salts 117

191

stability constants of complexes 52, 118

sulphate 117 sulphides 116 thiocyanate 119f

THORTVEITITE 1 THULIUM

electron configuration 11 energy levels of ion 29 halides 41f ionisation energies 170 lower halides 44 magnetic moment 11 oxidation state (+2) 44, 73 reduction potential 26 sulphide 47

TOBERNITE 93

UNNILENIUM see ELEMENT 109 UNNILHEXIUM see ELEMENT

106 UNNILOCTIUM see ELEMENT

108 UNNILPENTIUM see ELEMENT

105 UNNILQUADIUM see ELEMENT

104 UNNILSEPTIUM see ELEMENT

107 UNUNILIUM see ELEMENT 110 URANATES 131f URANINITE 93 URANIUM

acetate 131 acetylacetonate 140 alkoxide 135 alkylamides 133, 141 aquo ions 126 arsine oxide complexes 131, 138ft borohydride 144 bromides 102f, 134f

192

URANIUM (cont'd.) carbonate 131, 133 chlorides 102/, 133/ complexes 129/ diketonate 140 electron configurations 89 electronic spectra 108/ element 126 extraction 92 fission 97 fluorides 102/, 133/ fuel 96 half-life 87 halides 100/

adducts of 135, 138/ hydride 142 iodides 102/, 136/ ionisation energies 170 isotopes 87, 94 magnetic properties 107 metal 92, 126 nitrate 98, 131/ occurrence 92 ores 92 organometallics 160/ oxidation states 88

+3 state 91, 142 +4 state 91, 108/, 136ft +5 state 108, 134/ +6 state 127ft

oxides 127 oxyhalides 129/, 134 phosphine complexes 139 phosphine oxide complexes 131,

135,138ft reduction potentials 90, 126 stability constants 52 sulphate 142 superphthalocyanine 131

URANOPHANE 93 URANYL ION 127ft, 133

Index

XENOTIME 15

YELLOW CAKE 93 Y1TERBIUM

acetylacetonate 59 alkoxides 74 alkylamides 61, 74 aquo ion 53 boride 48 dimethylsulphoxide complex 54 electron configuration 11 electronic spectra 30 energy levels of ion 29 halides 41ft ionisation energies 170 magnetic moment 11 nitrate complex 54 organometallics 76/ oxidation state (+2) 44/, 73/ oxides 45 reduction potentials 26 sulphide 47

YITRIA 10 YITRIUM

acetylacetonate 59 alkoxides 55/ alkylamide 61 borides 48 chemical properties 13 crown ether complex 65 electron configuration 11 fluoride 42 formate 58 halide complexes 63 halides 41ft in superconductors 46 ionisation energies 170 magnetic moment 11 ores 15 organometallics 76/ reduction potentials 26 stability constants 52