Berkelium

Berkelium, 97Bk
Berkelium metal.jpg
Berkelium
Pronunciation
Appearancesilvery
Mass number[247]
Berkelium in the periodic table
HydrogenHelium
LithiumBerylliumBoronCarbonNitrogenOxygenFluorineNeon
SodiumMagnesiumAluminiumSiliconPhosphorusSulfurChlorineArgon
PotassiumCalciumScandiumTitaniumVanadiumChromiumManganeseIronCobaltNickelCopperZincGalliumGermaniumArsenicSeleniumBromineKrypton
RubidiumStrontiumYttriumZirconiumNiobiumMolybdenumTechnetiumRutheniumRhodiumPalladiumSilverCadmiumIndiumTinAntimonyTelluriumIodineXenon
CaesiumBariumLanthanumCeriumPraseodymiumNeodymiumPromethiumSamariumEuropiumGadoliniumTerbiumDysprosiumHolmiumErbiumThuliumYtterbiumLutetiumHafniumTantalumTungstenRheniumOsmiumIridiumPlatinumGoldMercury (element)ThalliumLeadBismuthPoloniumAstatineRadon
FranciumRadiumActiniumThoriumProtactiniumUraniumNeptuniumPlutoniumAmericiumCuriumBerkeliumCaliforniumEinsteiniumFermiumMendeleviumNobeliumLawrenciumRutherfordiumDubniumSeaborgiumBohriumHassiumMeitneriumDarmstadtiumRoentgeniumCoperniciumNihoniumFleroviumMoscoviumLivermoriumTennessineOganesson
Tb

Bk

(Upu)
curiumberkeliumcalifornium
Atomic number (Z)97
Groupgroup n/a
Periodperiod 7
Blockf-block
Element category  Actinide
Electron configuration[Rn] 5f9 7s2
Electrons per shell2, 8, 18, 32, 27, 8, 2
Physical properties
Phase at STPsolid
Melting pointbeta: 1259 K ​(986 °C, ​1807 °F)
Boiling pointbeta: 2900 K ​(2627 °C, ​4760 °F)
Density (near r.t.)alpha: 14.78 g/cm3
beta: 13.25 g/cm3
Heat of fusion7.92 kJ/mol (calculated)
Atomic properties
Oxidation states+2, +3, +4, +5[1]
ElectronegativityPauling scale: 1.3
Ionization energies
  • 1st: 601 kJ/mol
Atomic radiusempirical: 170 pm
Color lines in a spectral range
Spectral lines of berkelium
Other properties
Natural occurrencesynthetic
Crystal structuredouble hexagonal close-packed (dhcp)
Double hexagonal close packed crystal structure for berkelium
Thermal conductivity10 W/(m·K)
Magnetic orderingparamagnetic
CAS Number7440-40-6
History
Namingafter Berkeley, California, where it was discovered
DiscoveryLawrence Berkeley National Laboratory (1949)
Main isotopes of berkelium
Iso­topeAbun­danceHalf-life (t1/2)Decay modePro­duct
245Bksyn4.94 dε245Cm
α241Am
246Bksyn1.8 dα242Am
ε246Cm
247Bksyn1380 yα243Am
248Bksyn>300 y[2]α244Am
249Bksyn330 dα245Am
SF
β249Cf
| references

Berkelium is a transuranic radioactive chemical element with the 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 (then the University of California Radiation 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, USA, and at the Research Institute of Atomic Reactors in Dimitrovgrad, Russia. The production of the second-most important isotope 247Bk involves the irradiation of the rare isotope 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 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 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 electrons 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 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 free-radical effects and self-heating from the emitted alpha particles.

Characteristics

Physical

Sequential layers of spheres arranged from top to bottom: GRGBGRGB (G=green, R=red, B=blue)
Double-hexagonal close packing with the layer sequence ABAC in the crystal structure of α-berkelium (A: green, B: blue, C: red)

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 (13.52 g/cm3) and californium (15.1 g/cm3), as does its melting point of 986 °C, below that of curium (1340 °C) but higher than that of californium (900 °C).[3] Berkelium is relatively soft and has one of the lowest bulk moduli among the actinides, at about 20 GPa (2×1010 Pa).[4]

Berkelium(III) ions shows two sharp fluorescence peaks at 652 nanometers (red light) and 742 nanometers (deep red – near infrared) 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.[5][6]

Between 70 K and room temperature, berkelium behaves as a Curie–Weiss paramagnetic material with an effective magnetic moment of 9.69 Bohr magnetonsB) and a Curie temperature of 101 K. This magnetic moment is almost equal to the theoretical value of 9.72 µB calculated within the simple atomic L-S coupling model. Upon cooling to about 34 K, berkelium undergoes a transition to an antiferromagnetic state.[7] Enthalpy of dissolution in hydrochloric acid at standard conditions is −600 kJ/mol, from which the standard enthalpy change of formationfH°) of aqueous Bk3+ ions is obtained as −601 kJ/mol. The standard potential Bk3+/Bk0 is −2.01 V.[8] The ionization potential of a neutral berkelium atom is 6.23 eV.[9]

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 (having a similar structure) with α-lanthanum and α-forms of actinides beyond curium.[10] This crystal structure changes with pressure and temperature. When compressed at room temperature to 7 GPa, α-berkelium transforms to the beta modification, which has a face-centered cubic (fcc) symmetry and space group Fm3m. This transition occurs without change in volume, but the enthalpy increases by 3.66 kJ/mol.[11] 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.[12] No further phase transitions are observed up to 57 GPa.[4][13]

Upon heating, α-berkelium transforms into another phase with an fcc lattice (but slightly different from β-berkelium), space group Fm3m 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.[10] The temperature of the phase transition is believed to be quite close to the melting point.[14][15][16]

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 (+3) is the most stable, especially in aqueous solutions,[17][18] but tetravalent (+4)[19] and possibly divalent (+2) 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.[20][21] A similar behavior is observed for the lanthanide analogue of berkelium, terbium.[22] Aqueous solutions of Bk3+ ions are green in most acids. The color of Bk4+ ions is yellow in hydrochloric acid and orange-yellow in sulfuric acid.[20][23][24] 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.[7][14]

Isotopes

About twenty isotopes and six nuclear isomers (excited states of an isotope) of berkelium have been characterized with the mass numbers ranging from 233 to 253 (except 235, 237, and 239).[25] All of them are radioactive. The longest half-lives are observed for 247Bk (1,380 years), 248Bk (over 300 years) and 249Bk (330 days); the half-lives of the other isotopes range from microseconds to several days. 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—1.45×103% with respect to the β-radiation—but is sometimes used to detect this isotope. The second important berkelium isotope, berkelium-247, is an alpha-emitter, as are most actinide isotopes.[25][26]

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 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.[27]

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 when compared to the other isotopes produced in the reactor,[28] and is therefore undesirable in the disposal products.

The transuranic elements from americium to fermium, including berkelium, occurred naturally in the natural nuclear fission reactor at Oklo, but no longer do so.[29]