Compounds of berkelium

Berkelium(IV) oxide

Berkelium forms a number of chemical compounds where it normally exists in an oxidation state of +3 or +4 and behaves similarly to its lanthanide analogue, terbium.

Chemical properties of berkelium

Like all actinides, berkelium easily dissolves in various aqueous inorganic acids, liberating gaseous hydrogen and converting into the berkelium(III) state. This trivalent oxidation state is most stable, especially in aqueous solutions, but tetravalent and possibly divalent berkelium compounds are also known. The existence of divalent berkelium salts is uncertain and has only been reported in mixed lanthanum chloride-strontium chloride melts.^[1][2] A similar behavior is observed for the lanthanide analogue of berkelium, terbium.^[3] Aqueous solutions of Bk³⁺ ions are green in most acids. The color of the Bk⁴⁺ ions is yellow in hydrochloric acid and orange-yellow in sulfuric acid.^[1][4][5] Berkelium does not react rapidly with oxygen at room temperature, possibly due to the formation of a protective oxide surface layer. However, it reacts with molten metals, hydrogen, halogens, chalcogens and pnictogens to form various binary compounds.^[6][7]

Oxides

Two oxides of berkelium are known, with the Bk oxidation state of +3 (Bk₂O₃) and +4 (BkO₂).^[8] Berkelium(IV) oxide is a brown solid that crystallizes in a cubic (fluorite) crystal structure with the space group Fm3m and the coordination numbers of Bk[8] and O[4]. The lattice parameter is 533.4 ± 0.5 pm.^[9]

Berkelium(III) oxide is formed from BkO₂ by reduction with hydrogen:

$\mathrm{2\ BkO_2\ +\ H_2\ \longrightarrow \ Bk_2O_3\ +\ H_2O}$

It is a yellow-green solid with a melting point of 1920 °C,^[10] body-centered cubic crystal lattice and a lattice constant a = 1088.0 ± 0.5 pm.^[9] Upon heating to 1200 °C, the cubic Bk₂O₃ transforms to a monoclinic structure, which further converts to a hexagonal phase at 1750 °C, and the latter transition is reversible. Such three-phase behavior is typical for the actinide sesquioxides.^[11]

A divalent oxide BkO has been reported as a brittle gray solid with a face centered cubic (fcc) structure and a lattice constant a = 496.4 pm, but its exact chemical composition remains uncertain.^[11]

Halides

In halides, berkelium assumes the oxidation states +3 and +4.^[12] The +3 state is most stable, especially in solutions, and the tetravalent halides BkF₄ and Cs₂BkCl₆ are only known in the solid phase.^[13] The coordination of berkelium atom in its trivalent fluoride and chloride is tricapped trigonal prismatic, with the coordination number of 9. In trivalent bromide, it is bicapped trigonal prismatic (coordination 8) or octahedral (coordination 6),^[14] and in the iodide it is octahedral.^[15]

Oxidation number	F	Cl	Br	I
+4	Berkelium(IV) fluoride BkF4 Yellow[15]	Cs2BkCl6 Orange[11]
+3	Berkelium(III) fluoride BkF3 Yellow[15]	Berkelium(III) chloride BkCl3 Green[15] Cs2NaBkCl6[16]	Berkelium(III) bromide[14][17] BkBr3 Yellow-green[15]	Berkelium(III) iodide BkI3 Yellow[15]

Berkelium(IV) fluoride (BkF₄) is a yellow-green ionic solid which crystallizes in the monoclinic crystal system (Pearson symbol mS60, space group C2/c No. 15, lattice constants a = 1247 pm, b = 1058 pm, c = 817 pm) and is isotypic with uranium tetrafluoride or zirconium(IV) fluoride.^[16][18][19]

Berkelium(III) fluoride (BkF₃) is also a yellow-green solid, but it has two crystalline structures. The most stable phase at low temperatures has an orthorhombic symmetry, isotypic with yttrium(III) fluoride (Pearson symbol oP16, space group Pnma, No. 62, a = 670 pm, b = 709 pm, c = 441 pm). Upon heating to 350 to 600 °C, it transforms to a trigonal structure found in lanthanum(III) fluoride (Pearson symbol hP24, space group P3c1, No. 165, a = 697 pm, c = 714 pm).^[16][18][20]

Visible amounts of berkelium(III) chloride (BkCl₃) were first isolated and characterized in 1962, and weighed only 3 billionths of a gram. It can be prepared by introducing hydrogen chloride vapors into an evacuated quartz tube containing berkelium oxide at a temperature about 500 °C.^[21] This green solid has a melting point of 603 °C^[12] and crystallized in the hexagonal crystal system isotypic with uranium(III) chloride (Pearson symbol hP8, space group P6₃/m, No. 176).^[22][23] Upon heating to nearly melting point, BkCl₃converts into an orthorhombic phase.^[24] The hexahydrate BkCl₃·6H₂O has a monoclinic structure with the lattice constants a = 966 pm, b = 654 pm and c = 797 pm.^[16][25] Another berkelium(III) chloride, Cs₂NaBkCl₆ can be crystallized from a chilled aqueous solution containing berkelium(III) hydroxide, hydrochloric acid and caesium chloride. It has an fcc structure where Bk(III) ions are surrounded by chloride ions in an octahedral configuration.^[24]

The ternary berkelium(IV) chloride Cs₂BkCl₆ is obtained by dissolving berkelium(IV) hydroxide in a chilled solution of caesium chloride in concentrated hydrochloric acid. It forms orange hexagonal crystals with the lattice constants a = 745.1 pm and c = 1209.7 pm. The average radius of BkCl₆^2– ion in this compound is estimated as 270 pm.^[11]

Two forms of berkelium(III) bromide are known: a monoclinic with berkelium coordination 6 and orthorhombic with coordination 8;^[26] the latter is less stable and transforms to the former phase upon heating to about 350 °C. An important for radioactive solids phenomenon has been studies on example of these two crystal forms: the structure of fresh and aged ²⁴⁹BkBr₃ samples was probed by X-ray diffraction over a period longer than 3 years, so that various fractions of ²⁴⁹Bk had converted to ²⁴⁹Cf. No change in structure was observed upon²⁴⁹BkBr₃—²⁴⁹CfBr₃ transformation, even though the orthorhombic bromide was previously unknown for californium. However, other differences were noted for ²⁴⁹BkBr₃ and ²⁴⁹CfBr₃. For example, the latter could be reduced with hydrogen to²⁴⁹CfBr₂, but the former could be not – this result was reproduced on individual ²⁴⁹BkBr₃ and²⁴⁹CfBr₃ samples, as well on the samples containing both bromides.^[14] The intergrowth of californium in berkelium occurs at a rate of 0.22% per day and is an intrinsic obstacle in studying berkelium properties. Beside a chemical contamination, ²⁴⁹Cf, as an alpha emitter brings undesirable self-damage of the crystal lattice and the resulting self-heating. The chemical effect however can be avoided by performing measurements as a function of time and extrapolating the obtained results.^[13]

Berkelium(III) iodide forms hexagonal crystals with the lattice constants a = 758.4 pm and c = 2087 pm.^[16] The known oxyhalides of berkelium include BkOCl, BkOBr and BkOI; they all crystallize in a tetragonal lattice.^[27]

Pnictides and chalcogenides

The pnictides of berkelium-249 of the type BkX are known for the elements nitrogen,^[28] phosphorus, arsenic and antimony. They are prepared by the reaction of either berkelium(III) hydride (BkH₃) or metallic berkelium with these elements at elevated temperature (about 600 °C) under high vacuum in quartz ampoules. They crystallize in the rock-salt structure with the lattice constant of 495.1 pm for BkN, 566.9 pm for BkP, 582.9 for BkAs and 619.1 pm for BkSb.^[29] These lattice constant values are smaller than those in curium pnictides but are comparable to those of terbium pnictides.^[27]

Berkelium(III) sulfide Bk₂S₃ was prepared by either treating berkelium oxide with a mixture of hydrogen sulfide and carbon disulfidevapors at 1130 °C, or by directly reacting metallic berkelium with sulfur. These procedures yielded brownish-black crystals with a cubic symmetry and the lattice constant a = 844 pm.^[27]

Organometallic and other compounds

Berkelium(III) and berkelium(IV) hydroxides are both stable in 1 M sodium hydroxide solutions. Berkelium(III) phosphate (BkPO₄) has been prepared as a solid, which shows strong fluorescence under argon laser (514.5 nm line) excitation.^[30] Berkelium hydrides are produced by reacting metal with hydrogen gas at temperatures about 250 °C.^[28] They are non-stoichiometric with the nominal formula BkH_2+x (0 < x < 1). Whereas the trihydride has a hexagonal symmetry, the dihydride crystallizes in an fcc structure with the lattice constant a = 523 pm.^[27] Several other salts of berkelium are known, including Bk₂O₂S, (BkNO₃)₃·4H₂O, BkCl₃·6H₂O, Bk₂(SO₄)₃·12H₂O and Bk₂(C₂O₄)₃·4H₂O.^[13] Thermal decomposition at about 600 °C in an argon atmosphere (to avoid oxidation to Bk₂O) of Bk₂(SO₄)₃·12H₂O yields the body-centered orthorhombic crystals of berkelium(IV) oxysulfate (Bk₂O₂SO₄). This compound is thermally stable to at least 1000 °C in inert atmosphere.^[31]

Berkelium forms a trigonal (η⁵–C₅H₅)₃Bk complex with three cyclopentadienyl rings, which can be synthesized by reacting berkelium(III) chloride with the molten Be(C₅H₅)₂ at about 70 °C. It has an amber color and orthorhombic symmetry, with the lattice constants of a = 1411 pm, b = 1755 pm and c = 963 pm and the calculated density of 2.47 g/cm³. The complex is stable to heating to at least 250 °C, and sublimates without melting at about 350 °C. The high radioactivity of berkelium gradually destroys the compound (within a period of weeks).^[21][32] One C₅H₅ ring in (η⁵–C₅H₅)₃Bk can be substituted by chlorine to yield [Be(C₅H₅)₂Cl]₂. The optical absorption spectra of this compound are very similar to those of (η⁵–C₅H₅)₃Bk.^[31][33]

References

1. ^ ^{a b} Peterson, p. 55
2. ^ Sullivan, Jim C.; Schmidt, K. H.; Morss, L. R.; Pippin, C. G.; Williams, C. (1988). "Pulse radiolysis studies of berkelium(III): preparation and identification of berkelium(II) in aqueous perchlorate media". Inorganic Chemistry 27: 597. doi:10.1021/ic00277a005. 
3. ^ Thompson, Stanley G.; Seaborg, Glenn T. (1950). doi:10.2172/932812. http://www.osti.gov/bridge/purl.cover.jsp?purl=/932812-Rk9Mcq/. 
4. ^ Holleman, p. 1956
5. ^ Greenwood, p. 1265
6. ^ Hobart, David E.; Peterson, Joseph R. (2006). "Berkelium". In Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean. The Chemistry of the Actinide and Transactinide Elements. 3 (3rd ed.). Dordrecht, the Netherlands: Springer. pp. 1444–98. doi:10.1007/1-4020-3598-5_10. http://radchem.nevada.edu/classes/rdch710/files/berkelium.pdf. 
7. ^ Peterson, p. 45
8. ^ Peterson, J (1967). "Crystal structures and lattice parameters of the compounds of berkelium I. Berkelium dioxide and cubic berkelium sesquioxide". Inorganic and Nuclear Chemistry Letters 3: 327. doi:10.1016/0020-1650(67)80037-0. 
9. ^ ^{a b} Baybarz, R.D. (1968). "The berkelium oxide system☆". Journal of Inorganic and Nuclear Chemistry 30: 1769. doi:10.1016/0022-1902(68)80352-5. 
10. ^ Holleman, p. 1972
11. ^ ^{a b c d} Peterson, p. 51
12. ^ ^{a b} Holleman, p. 1969
13. ^ ^{a b c} Peterson, p. 47
14. ^ ^{a b c} Young, J. P.; Haire, R. G.; Peterson, J. R.; Ensor, D. D.; Fellows, R. L. (1980). "Chemical consequences of radioactive decay. 1. Study of californium-249 ingrowth into crystalline berkelium-249 tribromide: a new crystalline phase of californium tribromide". Inorganic Chemistry 19: 2209. doi:10.1021/ic50210a003. 
15. ^ ^{a b c d e f} Greenwood, p. 1270
16. ^ ^{a b c d e} Peterson, p. 48
17. ^ Burns, J (1975). "Crystallographic studies of some transuranic trihalides: 239PuCl3, 244CmBr3, 249BkBr3 and 249CfBr3". Journal of Inorganic and Nuclear Chemistry 37: 743. doi:10.1016/0022-1902(75)80532-X. 
18. ^ ^{a b} Ensor, D (1981). "Absorption spectrophotometric study of berkelium(III) and (IV) fluorides in the solid state". Journal of Inorganic and Nuclear Chemistry 43: 1001. doi:10.1016/0022-1902(81)80164-9. 
19. ^ Keenan, Thomas K.; Asprey, Larned B. (1969). "Lattice constants of actinide tetrafluorides including berkelium". Inorganic Chemistry 8: 235. doi:10.1021/ic50072a011. 
20. ^ Peterson, J.R.; Cunningham, B.B. (1968). "Crystal structures and lattice parameters of the compounds of berkelium—IV berkelium trifluoride☆". Journal of Inorganic and Nuclear Chemistry 30: 1775. doi:10.1016/0022-1902(68)80353-7. 
21. ^ ^{a b} Laubereau, Peter G.; Burns, John H. (1970). "Microchemical preparation of tricyclopentadienyl compounds of berkelium, californium, and some lanthanide elements". Inorganic Chemistry 9: 1091. doi:10.1021/ic50087a018. 
22. ^ Peterson, J.R.; Cunningham, B.B. (1968). "Crystal structures and lattice parameters of the compounds of berkelium—IIBerkelium trichloride". Journal of Inorganic and Nuclear Chemistry 30: 823. doi:10.1016/0022-1902(68)80443-9. 
23. ^ Peterson, J. R.; Young, J. P.; Ensor, D. D.; Haire, R. G. (1986). "Absorption spectrophotometric and x-ray diffraction studies of the trichlorides of berkelium-249 and californium-249". Inorganic Chemistry 25: 3779. doi:10.1021/ic00241a015. 
24. ^ ^{a b} Peterson, p. 52
25. ^ Burns, John H.; Peterson, Joseph Richard (1971). "Crystal structures of americium trichloride hexahydrate and berkelium trichloride hexahydrate". Inorganic Chemistry 10: 147. doi:10.1021/ic50095a029. 
26. ^ Peterson, p. 38
27. ^ ^{a b c d} Peterson, p. 53
28. ^ ^{a b} Stevenson, J; Peterson, J (1979). "Preparation and structural studies of elemental curium-248 and the nitrides of curium-248 and berkelium-249". Journal of the Less Common Metals 66: 201. doi:10.1016/0022-5088(79)90229-7. 
29. ^ Damien, D.; Haire, R.G.; Peterson, J.R. (1980). "Preparation and lattice parameters of ²⁴⁹Bk monopnictides". Journal of Inorganic and Nuclear Chemistry 42: 995. doi:10.1016/0022-1902(80)80390-3. 
30. ^ Peterson, pp. 39–40
31. ^ ^{a b} Peterson, p. 54
32. ^ Christoph Elschenbroich Organometallic Chemistry, 6th Edition, Wiesbaden 2008, ISBN 978-3-8351-0167-8, pp. 583–584
33. ^ Peterson, p. 41

Bibliography

• Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Oxford: Butterworth-Heinemann. ISBN 0080379419. 
• Holleman, Arnold F. and Wiberg, Nils Textbook of Inorganic Chemistry, 102 Edition, de Gruyter, Berlin 2007, ISBN 978-3-11-017770-1.
• Peterson J. R. and Hobart D. E. "The Chemistry of Berkelium" in Harry Julius Emeléus (Ed.) Advances in inorganic chemistry and radiochemistry, Volume 28, Academic Press, 1984 ISBN 0120236281, pp. 29–64, doi:10.1016/S0898-8838(08)60204-4

External links

• History of Element 117 Synthesis
• Element 'ununseptium' to fill periodic table gap