Berkelium

Berkelium is a synthetic chemical element; it has symbol Bk and atomic number 97. It is a member of the actinide and transuranium element series. It is named after the city of Berkeley, California, the location of the Lawrence Berkeley National Laboratory where it was discovered in December 1949. Berkelium was the fifth transuranium element discovered after neptunium, plutonium, curium and americium.
The major isotope of berkelium, ²⁴⁹Bk, is synthesized in minute quantities in dedicated high-flux nuclear reactors, mainly at the Oak Ridge National Laboratory in Tennessee, United States, and at the Research Institute of Atomic Reactors in Dimitrovgrad, Russia. The longest-lived and second-most important isotope, ²⁴⁷Bk, can be synthesized via irradiation of ²⁴⁴Cm 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 scientific research which is mostly directed at the synthesis of heavier transuranium elements and superheavy elements. 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 new element tennessine 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 the culmination of the Russia–US collaboration on the synthesis of the heaviest elements on the periodic table.
Berkelium is a soft, silvery-white, radioactive metal. The berkelium-249 isotope emits low-energy beta particles and thus is relatively safe to handle. It decays with a half-life of 330 days to californium-249, which is a strong emitter of ionizing alpha particles. This gradual transmutation 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 free-radical effects and self-heating from the emitted alpha particles.

Characteristics

Physical

Berkelium is a soft, silvery-white, radioactive actinide metal. In the periodic table, it is located to the right of the actinide curium, to the left of the actinide californium and below the lanthanide terbium with which it shares many similarities in physical and chemical properties. Its density of 14.78 g/cm³ lies between those of curium and californium, as does its melting point of 986 °C, below that of curium but higher than that of californium. Berkelium is relatively soft and has one of the lowest bulk moduli among the actinides, at about 20 GPa.
ions shows two sharp fluorescence peaks at 652 nanometers and 742 nanometers due to internal transitions at the f-electron shell. The relative intensity of these peaks depends on the excitation power and temperature of the sample. This emission can be observed, for example, after dispersing berkelium ions in a silicate glass, by melting the glass in presence of berkelium oxide or halide.
Between 70 K and room temperature, berkelium behaves as a Curie–Weiss paramagnetic material with an effective magnetic moment of 9.69 Bohr magnetons 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 an antiferromagnetic state. The enthalpy of dissolution in hydrochloric acid at standard conditions is −600 kJ/mol, from which the standard enthalpy of formation of aqueous ions is obtained as −601 kJ/mol. The standard electrode potential /Bk 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. This crystal structure changes with pressure and temperature. When compressed at room temperature to 7 GPa, α-berkelium transforms to the β modification, which has a face-centered cubic symmetry and space group Fmm. This transition occurs without change in volume, but the enthalpy increases by 3.66 kJ/mol. Upon further compression to 25 GPa, berkelium transforms to an orthorhombic γ-berkelium structure similar to that of α-uranium. This transition is accompanied by a 12% volume decrease and delocalization of the electrons at the 5f electron shell. No further phase transitions are observed up to 57 GPa.
Upon heating, α-berkelium transforms into another phase with an fcc lattice, space group Fmm and the lattice constant of 500 pm; this fcc structure is equivalent to the closest packing with the sequence ABC. This phase is metastable and will gradually revert to the original α-berkelium phase at room temperature. The temperature of the phase transition is believed to be quite close to the melting point.

Chemical

Like all actinides, berkelium dissolves in various aqueous inorganic acids, liberating gaseous hydrogen and converting into the state. This trivalent oxidation state is the most stable, especially in aqueous solutions, but tetravalent, pentavalent, 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. Aqueous solutions of ions are green in most acids. The color of ions is yellow in hydrochloric acid and orange-yellow in sulfuric acid. Berkelium does not react rapidly with oxygen at room temperature, possibly due to the formation of a protective oxide layer surface. However, it reacts with molten metals, hydrogen, halogens, chalcogens and pnictogens to form various binary compounds.
In 2025 an organometallic compound containing berkelium was synthesized from 0.3 mg of berkelium and named berkelocene.

Isotopes

Nineteen isotopes and six nuclear isomers of berkelium have been characterized, with mass numbers ranging from 233 to 253. All of them are radioactive. The longest half-lives are observed for ²⁴⁷Bk, ²⁴⁸Bk, and ²⁴⁹Bk ; other isotopes are less than a week. The isotope which is the easiest to synthesize is berkelium-249. This emits mostly soft β-particles which are inconvenient for detection. Its alpha radiation is rather weak with respect to the β-radiation, but is sometimes used to detect this isotope. The second important berkelium isotope, berkelium-247, is beta-stable and an alpha emitter, as are most long-lived actinide isotopes.

Occurrence

All berkelium isotopes have a half-life far too short to be primordial. Therefore, any primordial berkelium − that is, berkelium present on the Earth during its formation − has 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 the 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 United States' first thermonuclear weapon, Ivy Mike,, revealed high concentrations of various actinides, including berkelium. For reasons of military secrecy, this result was not published until 1956.
Nuclear reactors produce mostly, among the berkelium isotopes, berkelium-249. During the storage and before the fuel disposal, most of it beta decays to californium-249. The latter has a half-life of 351 years, which is relatively long compared to the half-lives of other isotopes produced in the reactor, and is therefore undesirable in the disposal products.
The transuranic elements up to fermium, including berkelium, should have been present in the natural nuclear fission reactor at Oklo, but any quantities produced then would have long since decayed away.

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, Stanley Gerald Thompson, and Kenneth Street Jr. They used the 60-inch cyclotron at the University of California, Berkeley. Similar to the nearly simultaneous discovery of americium and curium in 1944, the new elements berkelium and californium 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 after the city of Berkeley in a manner similar to that used in naming its chemical homologue terbium whose name was derived from the town of Ytterby, Sweden, where the rare earth minerals were first found." This tradition ended with berkelium, though, as the naming of the next discovered actinide, californium, was not related to its lanthanide analogue dysprosium, but after the discovery place.
The most difficult steps in synthesising berkelium were its separation from the final products and the production of sufficient quantities of americium for the target material. First, americium nitrate solution was coated on a platinum foil, the solution was evaporated and the residue converted by annealing to americium dioxide. This target was irradiated with 35 MeV alpha particles for 6 hours in the 60-inch cyclotron at the Lawrence Radiation Laboratory, University of California, Berkeley. The reaction induced by the irradiation yielded the ²⁴³Bk isotope and two free neutrons:
After the irradiation, the coating was dissolved with nitric acid and then precipitated as the hydroxide using concentrated aqueous ammonia solution. The product was centrifugated and re-dissolved in nitric acid. To separate berkelium from the unreacted americium, this solution was added to a mixture of aqueous ammonia and ammonium sulfate and heated in the presence of atmospheric oxygen to convert all the dissolved americium into the oxidation state +6. Unoxidized residual americium was precipitated by the addition of hydrofluoric acid as americium fluoride. This step yielded a mixture of the accompanying product curium and the expected element 97 in form of trifluorides. The mixture was converted to the corresponding hydroxides by treating it with potassium hydroxide, and after centrifugation, was dissolved in perchloric acid.
File:Elutionskurven Tb Gd Eu und Bk Cm Am.png|thumb|Chromatographic elution curves revealing the similarity between the lanthanides terbium, gadolinium, and europium and their corresponding actinides berkelium, curium, and americium |alt=Graphs showing similar elution curves for terbium vs. berkelium, gadolinium vs. curium, europium vs. americium
Further separation was carried out in the presence of a citric acid/ammonium buffer solution in a weakly acidic medium, using ion exchange at elevated temperature. The chromatographic separation behavior was unknown for element 97 at the time but was anticipated by analogy with terbium. The first results were disappointing because no alpha-particle emission signature could be detected from the elution product. With further analysis, searching for characteristic X-rays and conversion electron signals, a berkelium isotope was eventually detected. Its mass number was uncertain between 243 and 244 in the initial report, but was later established as 243.