Berkelium

Berkelium ( , less commonly ), is a synthetic element with the symbol Bk and atomic number 97, a member of the actinide and transuranium element series. It is named after the city of Berkeley, California, the location of the University of California Radiation Laboratory where it was discovered in December 1949. This was the fifth transuranium element discovered after neptunium, plutonium, curium and americium.

The major isotope of berkelium, berkelium-249, is synthesized in minute quantities in dedicated high-flux nuclear reactors, mainly at the Oak Ridge National Laboratory in Tennessee, USA, and at the Research Institute of Atomic Reactors in Dimitrovgrad, Russia. The production of the second-important isotope berkelium-247 involves the irradiation of the rare synthetic isotope curium-244 with high-energy alpha particles.

Just over one gram of berkelium has been produced in the United States since 1967. There is no practical application of berkelium outside of scientific research which is mostly directed at the synthesis of heavier transuranic elements and transactinides. A 22 milligram batch of berkelium-249 was prepared during a 250-day irradiation period and then purified for a further 90 days at Oak Ridge in 2009. This sample was used to synthesize the element ununseptium for the first time in 2009 at the Joint Institute for Nuclear Research, Russia, after it was bombarded with calcium-48 ions for 150 days. This was a culmination of the Russia—US collaboration on the synthesis of elements 113 to 118.

Berkelium is a soft, silvery-white, radioactive metal. The berkelium-249 isotope emits low-energy electrons and thus is relatively safe to handle. However, it decays with a half-life of 330 days to californium-249, which is a strong and hazardous emitter of alpha particles. This gradual transformation is an important consideration when studying the properties of elemental berkelium and its chemical compounds, since the formation of californium brings not only chemical contamination, but also self-radiation damage, and self-heating from the emitted alpha particles.

History

Although very small amounts of berkelium were possibly produced in previous nuclear experiments, it was first intentionally synthesized, isolated and identified in December 1949 by Glenn T. Seaborg, Albert Ghiorso and Stanley G. Thompson. They used the 60-inch cyclotron at the University of California, Berkeley. Similar to the nearly simultaneous discovery of americium (element 95) and curium (element 96) in 1944, the new elements berkelium and californium (element 98) were both produced in 1949–1950.

The name choice for element 97 followed the previous tradition of the Californian group to draw an analogy between the newly discovered actinide and the lanthanide element positioned above it in the periodic table. Previously, americium was named after a continent as its analogue europium, and curium honored scientists Marie and Pierre Curie as the lanthanide above it, gadolinium, was named after the explorer of the rare earth elements Johan Gadolin. Thus the discovery report by the Berkeley group reads: "It is suggested that element 97 be given the name berkelium (symbol Bk) after the city of Berkeley in a manner similar to that used in naming its chemical homologue terbium (atomic number 65) whose name was derived from the town of Ytterby, Sweden, where the rare earth minerals were first found."

Between 70 K and room temperature, berkelium behaves as a Curie–Weiss paramagnetic material with an effective magnetic moment of 9.69 Bohr magnetons (µ_B) and a Curie temperature of 101 K. This magnetic moment is almost equal to the theoretical value of 9.72 µ_B calculated within the simple atomic L-S coupling model. Upon cooling to about 34 K, berkelium undergoes a transition to anantiferromagnetic state. Enthalpy of dissolution in hydrochloric acid at standard conditions is −600 kJ/mol⁻¹, from which the standard enthalpy change of formation(Δ_fH°) of aqueous Bk³⁺ ions is obtained as −601 kJ/mol⁻¹. The standard potential Bk³⁺/Bk⁰ is −2.01 V. The ionization potential of a neutral berkelium atom is 6.23 eV.

Allotropes

At ambient conditions, berkelium assumes its most stable α form which has a hexagonal symmetry, space group P6₃/mmc, lattice parameters of 341 pm and 1107 pm. The crystal has a double-hexagonal close packing structure with the layer sequence ABAC and so is isotypic with α-lanthanum and α-forms of actinides beyond curium.

Upon heating, α-berkelium transforms into another "metastable" phase (that is at ambient temperature it gradually converts back to α-berkelium). This phase has an fcc lattice (but slightly different from β-berkelium), space group Fmm and the lattice constant of 500 pm; this fcc structure is equivalent to the closest packing with the sequence ABC.

Chemical

Like all actinides, berkelium dissolves in various aqueous inorganic acids, liberating gaseous hydrogen and converting into the berkelium(III) state. This trivalent oxidation state is the 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. A similar behavior is observed for the lanthanide analogue of berkelium, terbium.

Occurrence

The longest-lived isotope of berkelium (²⁴⁷Bk) has a half-life of only 1,380 years. Therefore, all primordial berkelium, that is berkelium present on the Earth during its formation, should have decayed by now. On Earth, berkelium is mostly concentrated in certain areas, which were used for the atmospheric nuclear weapons tests between 1945 and 1980, as well as at the sites of nuclear incidents, such as Chernobyl disaster, Three Mile Island accident and 1968 Thule Air Base B-52 crash. Analysis of the debris at the testing site of the first U.S. hydrogen bomb, Ivy Mike, (1 November 1952, Enewetak Atoll), revealed high concentrations of various actinides, including berkelium. For reasons of military secrecy, this result was published only in 1956.

Nuclear reactors produce mostly, among the berkelium isotopes, berkelium-249. During the storage and before the fuel disposal, most of it breaks down to californium-249. The latter has a long half-life, of 351 years, and is therefore undesirable in the disposal products.

Synthesis and extraction

Preparation of isotopes

at Oak Ridge National Laboratory is one of the places where berkelium is produced|alt=A complex of buildings in the middle of a forest]] Berkelium is produced by bombarding lighter actinides uranium (²³⁸U) or plutonium (²³⁹Pu) with neutrons in a nuclear reactor. In a more common case of uranium fuel, plutonium is produced first by neutron capture (the so-called (n,γ) reaction or neutron fusion) followed by beta-decay:

:$\backslash mathrm\{^\{238\}\_\{\backslash \; 92\}U\backslash \; \backslash xrightarrow\; \{(n,\backslash gamma)\}\; \backslash \; ^\{239\}\_\{\backslash \; 92\}U\backslash \; \backslash xrightarrow\; [23.5\; \backslash \; min]\{\backslash beta^-\}\; \backslash \; ^\{239\}\_\{\backslash \; 93\}Np\backslash \; \backslash xrightarrow\; [2.3565\; \backslash \; d]\{\backslash beta^-\}\; \backslash \; ^\{239\}\_\{\backslash \; 94\}Pu\}$ (the times are half-lives)

Plutonium-239 is further irradiated by a source that has a high neutron flux,several times higher than a conventional nuclear reactor, such as the 85-megawatt High Flux Isotope Reactor (HFIR) at the Oak Ridge National Laboratory in Tennessee, USA. The higher flux promotes fusion reactions involving not one but several neutrons, converting ²³⁹Pu to ²⁴⁴Cm and then to ²⁴⁹Cm: :$\backslash mathrm\{^\{239\}\_\{\backslash \; 94\}Pu\backslash \; \backslash xrightarrow\; \{4(n,\backslash gamma)\}\; \backslash \; ^\{243\}\_\{\backslash \; 94\}Pu\backslash \; \backslash xrightarrow\; [4.956\; \backslash \; h]\{\backslash beta^-\}\; \backslash \; ^\{243\}\_\{\backslash \; 95\}Am\backslash \; \backslash xrightarrow\; \{(n,\backslash gamma)\}\; \backslash \; ^\{244\}\_\{\backslash \; 95\}Am\backslash \; \backslash xrightarrow\; [10.1\; \backslash \; h]\{\backslash beta^-\}\; \backslash \; ^\{244\}\_\{\backslash \; 96\}Cm\}\; \backslash quad;\; \backslash quad\; \backslash mathrm\{^\{244\}\_\{\backslash \; 96\}Cm\backslash \; \backslash xrightarrow\; \{5(n,\backslash gamma)\}\; \backslash \; ^\{249\}\_\{\backslash \; 96\}Cm\}$

Curium-249 has a short half-life of 64 minutes, and thus its further conversion to ²⁵⁰Cm has a low probability. Instead, it transforms by beta-decay into ²⁴⁹Bk: :$\backslash mathrm\{^\{249\}\_\{\backslash \; 97\}Bk\backslash \; \backslash xrightarrow\; \{(n,\backslash gamma)\}\; \backslash \; ^\{250\}\_\{\backslash \; 97\}Bk\backslash \; \backslash xrightarrow\; [3.212\; \backslash \; h]\{\backslash beta^-\}\; \backslash \; ^\{250\}\_\{\backslash \; 98\}Cf\}$

The above reactions illustrate that although ²⁴⁷Bk is the most stable isotope of berkelium, its production in nuclear reactors is very inefficient. This makes ²⁴⁹Bk the most accessible isotope of berkelium, which still, is available only in small quantities (only 0.66 grams have been produced in the US over the period 1967–1983) at a high price of the order 185 USD per microgram.

The isotope ²⁴⁸Bk was first obtained in 1956 by bombarding a mixture of curium isotopes with 25 MeV α-particles. Although its direct detection was hindered by strong signal interference with ²⁴⁵Bk, the existence of a new isotope was proven by the growth of the decay product ²⁴⁸Cf which had been previously characterized. The half-life of ²⁴⁸Cf was estimated as 23 ± 5 hours and a more reliable value still is not known. Berkelium-247 was produced during the same year by irradiating ²⁴⁴Cm with alpha-particles: :$\backslash mathrm\{^\{244\}\_\{\backslash \; 96\}Cm\backslash \; \backslash xrightarrow[]\{(\backslash alpha,n)\}\; \backslash \; ^\{247\}\_\{\backslash \; 98\}Cf\backslash \; \backslash xrightarrow[3,11\; \backslash \; h]\{\backslash epsilon\}\; \backslash \; ^\{247\}\_\{\backslash \; 97\}Bk\}$ :$\backslash mathrm\{^\{244\}\_\{\backslash \; 96\}Cm\backslash \; \backslash xrightarrow[]\{(\backslash alpha,p)\}\; \backslash \; ^\{247\}\_\{\backslash \; 97\}Bk\}$

Berkelium-242 was synthesized in 1979 by bombarding ²³⁵U with ¹¹B, ²³⁸U with ¹⁰B, ²³²Th with ¹⁴N or ²³²Th with ¹⁵N. It converts by electron capture to ²⁴²Cm with a half-life of 7.0 ± 1.3 minutes. A search for an initially suspected isotope ²⁴¹Bk was then unsuccessful. :$\backslash mathrm\{^\{235\}\_\{\backslash \; 92\}U\backslash \; +\backslash \; ^\{11\}\_\{\backslash \; 5\}B\backslash \; \backslash longrightarrow\; \backslash \; ^\{242\}\_\{\backslash \; 97\}Bk\backslash \; +\backslash \; 4\backslash \; ^\{1\}\_\{0\}n\; \backslash quad\; ;\; \backslash quad\; ^\{232\}\_\{\backslash \; 90\}Th\backslash \; +\backslash \; ^\{14\}\_\{\backslash \; 7\}N\backslash \; \backslash longrightarrow\; \backslash \; ^\{242\}\_\{\backslash \; 97\}Bk\backslash \; +\backslash \; 4\backslash \; ^\{1\}\_\{0\}n\}$ :$\backslash mathrm\{^\{238\}\_\{\backslash \; 92\}U\backslash \; +\backslash \; ^\{10\}\_\{\backslash \; 5\}B\backslash \; \backslash longrightarrow\; \backslash \; ^\{242\}\_\{\backslash \; 97\}Bk\backslash \; +\backslash \; 6\backslash \; ^\{1\}\_\{0\}n\; \backslash quad\; ;\; \backslash quad\; ^\{232\}\_\{\backslash \; 90\}Th\backslash \; +\backslash \; ^\{15\}\_\{\backslash \; 7\}N\backslash \; \backslash longrightarrow\; \backslash \; ^\{242\}\_\{\backslash \; 97\}Bk\backslash \; +\backslash \; 5\backslash \; ^\{1\}\_\{0\}n\}$

Separation

The fact that berkelium readily assumes oxidation state +4 in solids, and is relatively stable in this state in liquids greatly assists separation of berkelium away from many other actinides. These are inevitably produced in relatively large amounts during the nuclear synthesis and often favor the +3 state. This fact was not yet known in the initial experiments, which used a more complex separation procedure. Various oxidation agents can be applied to the berkelium(III) solutions to convert it to the +4 state, such as bromates (BrO₃^–), bismuthates (BiO₃^–), chromates (CrO₄^2– and Cr₂O₇^2–), silver(I) thiolate (), lead(IV) oxide (PbO₂), ozone (), or photochemical oxidation procedures. Berkelium(IV) is then extracted with ion exchange, extraction chromatography or liquid-liquid extraction using HDEHP (bis-(2-ethylhexyl) phosphoric scid), amines, tributyl phosphate or various other reagents. These procedures separate berkelium from most trivalent actinides and lanthanides, except for the lanthanide cerium (lanthanides are absent in the irradiation target but are created in various nuclear fission decay chains).

A more detailed procedure adopted at the Oak Ridge National Laboratory was as follows: the initial mixture of actinides is processed with ion exchange using lithium chloride reagent, then precipitated as hydroxides, filtered and dissolved in nitric acid. It is then treated with high-pressure elution from cation exchange resins, and the berkelium phase is oxidized and extracted using one of the procedures described above. Reduction of the thus-obtained berkelium(IV) to the +3 oxidation state yields a solution, which is nearly free from other actinides (but contains cerium). Berkelium and cerium are then separated with another round of ion-exchange treatment.

Bulk metal preparation

In order to characterize chemical and physical properties of solid berkelium and its compounds, a program was initiated in 1952 at the Material Testing Reactor, Arco, Idaho, US. It resulted in preparation of an eight-gram plutonium-239 target and in the first production of macroscopic quantities (0.6 micrograms) of berkelium by Burris B. Cunningham and Stanley G. Thompson in 1958, after a continuous reactor irradiation of this target for six years. This irradiation method was, and still is the only way of producing weighable amounts of the element, and most solid-state studies of berkelium have been conducted on microgram or submicrogram-sized samples.

The world's major irradiation sources are the 85-megawatt High Flux Isotope Reactor at the Oak Ridge National Laboratory in Tennessee, USA, and the SM-2 loop reactor at the Research Institute of Atomic Reactors (NIIAR) in Dimitrovgrad, Russia, which are both dedicated to the production of transcurium elements (atomic number greater than 96). These facilities have similar power and flux levels, and are expected to have comparable production capacities for transcurium elements, although the quantities produced at NIIAR are not widely reported. In a "typical processing campaign" at Oak Ridge, tens of grams of curium are irradiated to produce decigram quantities of californium, milligram quantities of berkelium-249 and einsteinium, and picogram quantities of fermium. In total, just over one gram of berkelium-249 has been produced at Oak Ridge since 1967. :$\backslash mathrm\{BkF\_3\backslash \; +\backslash \; 3\backslash \; Li\backslash \; \backslash longrightarrow\; \backslash \; Bk\backslash \; +\backslash \; 3\backslash \; LiF\}$

Similar results are obtained with berkelium(IV) fluoride. Berkelium metal can also be produced by the reduction of berkelium(IV) oxide with thorium or lanthanum.

Compounds

Oxides

Two oxides of berkelium are known, with the berkelium oxidation state of +3 (Bk₂O₃) and +4 (BkO₂). Berkelium(IV) oxide is a brown solid that crystallizes in a cubic (fluorite) crystal structure. Berkelium(III) oxide is formed from BkO₂ by reduction with molecular hydrogen: :$\backslash mathrm\{2\backslash \; BkO\_2\backslash \; +\backslash \; H\_2\backslash \; \backslash longrightarrow\; \backslash \; Bk\_2O\_3\backslash \; +\backslash \; H\_2O\}$

It is a yellow-green solid with a melting point of 1920 °C and a body-centered cubic (bcc) crystal lattice.(yellow-green) | BkI₃ (yellow) |}

Berkelium(IV) fluoride (BkF₄) is a yellow-green ionic solid which crystallizes in the monoclinic crystal system and is isotypic with uranium tetrafluoride or zirconium(IV) fluoride.

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. Upon heating to between 350 and 600 °C, it transforms to a trigonal structure found in lanthanum(III) fluoride.

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. Upon heating to nearly melting point, BkCl₃ converts into an orthorhombic phase.

Two forms of berkelium(III) bromide are known: a monoclinic one with berkelium having coordination 6, and an orthorhombic one with coordination 8. The latter is less stable and transforms to the former phase upon heating to about 350 °C. An important phenomenon for radioactive solids has been studied on 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 berkelium-249 had converted to californium-249. No change in structure was observed upon ²⁴⁹BkBr₃—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 to ²⁴⁹CfBr₂, but the former could be not – this result was reproduced on individual ²⁴⁹BkBr₃ and ²⁴⁹CfBr₃ samples, as well on the samples containing both bromides. phosphorus, arsenic and antimony. They crystallize in the rock-salt structure and 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.

Berkelium(III) sulfide, Bk₂S₃, was prepared by either treating berkelium oxide with a mixture of hydrogen sulfide and carbon disulfide vapors at 1130 °C, or by directly reacting metallic berkelium with elemental sulfur. These procedures yielded brownish-black crystals with a cubic symmetry.

Berkelium(III) and berkelium(IV) hydroxides are both stable in 1 molar solutions of sodium hydroxide. Berkelium(III) phosphate (BkPO₄) has been prepared as a solid, which shows strong fluorescence under excitation with a green light. Berkelium hydrides are produced by reacting metal with hydrogen gas at temperatures about 250 °C. One cyclopentadienyl 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.

Applications

(in dissolved state)|alt=A very small sample of a blue liquid in a plastic pipette held by a hand wearing heavy protection equipment]] There is no use for any isotope of berkelium outside of basic scientific research.

A 22 milligram batch of berkelium-249 was prepared in a 250-day irradiation and then purified for 90 days at Oak Ridge in 2009. This target yielded the first 6 atoms of element ununseptium at the Joint Institute for Nuclear Research (JINR), Dubna, Russia, after bombarding it with calcium ions in the U400 cyclotron for 150 days. This synthesis was a culmination of the Russia—US collaboration between JINR and Lawrence Livermore National Laboratory on the synthesis of elements 113 to 118 which was initiated in 1989.

Nuclear fuel cycle

The nuclear fission properties of berkelium are different from those of the neighboring actinides curium and californium, and they suggest berkelium to perform poorly as a fuel in a nuclear reactor. Specifically, berkelium-249 has a moderately large neutron capture cross section of 710 barns for thermal neutrons, 1200 barns resonance integral, but very low fission cross section for thermal neutrons. In a thermal reactor, much of it will therefore be converted to berkelium-250 which quickly decays to californium-250. In principle, berkelium-249 can sustain a nuclear chain reaction in a fast breeder reactor. Its critical mass is relatively high at 192 kg; it can be reduced with a water or steel reflector but would still exceed the world production of this isotope.

Berkelium-247 can maintain chain reaction both in a thermal-neutron and in a fast-neutron reactor, however, its production is rather complex and thus the availability is much lower than its critical mass, which is about 75.7 kg for a bare sphere, 41.2 kg with a water reflector and 35.2 kg with a steel reflector (30 cm thickness).

Most available berkelium toxicity data originate from research on animals. Upon ingestion by rats, only about 0.01% berkelium ends in the blood stream. From there, about 65% goes to the bones, where it remains for about 50 years, 25% to the lungs (biological half-life about 20 years), 0.035% to the testicles or 0.01% to the ovaries where berkelium stays indefinitely. The balance of about 10% is excreted. In all these organs berkelium might promote cancer, and in the skeletal system its radiation can damage red blood cells. The maximum permissible body burden for the isotope berkelium-249 in the human skeleton is 0.4 nanograms.

References

Bibliography

External links

History of Element 117 Synthesis

Element 'ununseptium' to fill periodic table gap

Category:Chemical elements Category:Actinides Category:University of California, Berkeley Category:Synthetic elements Category:Berkelium