Bohrium

Bohrium, ₁₀₇Bh

Bohrium
Pronunciation	​(BOR-ee-əm)
Mass number	[270] (unconfirmed: 278)
Bohrium in the periodic table
Hydrogen Helium Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson Re ↑ Bh ↓ (Uhu) seaborgium ← bohrium → hassium
Atomic number (Z)	107
Group	group 7
Period	period 7
Block	d-block
Electron configuration	[Rn] 5f14 6d5 7s2
Electrons per shell	2, 8, 18, 32, 32, 13, 2
Physical properties
Phase at STP	solid (predicted)
Density (near r.t.)	26–27 g/cm3 (predicted)
Atomic properties
Oxidation states	(+3), (+4), (+5), +7 (parenthesized: prediction)
Ionization energies	1st: 740 kJ/mol 2nd: 1690 kJ/mol 3rd: 2570 kJ/mol (more) (all but first estimated)
Atomic radius	empirical: 128 pm (predicted)
Covalent radius	141 pm (estimated)
Other properties
Natural occurrence	synthetic
Crystal structure	​hexagonal close-packed (hcp) (predicted)
CAS Number	54037-14-8
History
Naming	after Niels Bohr
Discovery	Gesellschaft für Schwerionenforschung (1981)
Isotopes of bohrium
Main isotopes Decay abun­dance half-life (t1/2) mode pro­duct 267Bh synth 17 s α 263Db 270Bh synth 2.4 min α 266Db 271Bh synth 2.9 s α 267Db 272Bh synth 8.8 s α 268Db 274Bh synth 40 s α 270Db 278Bh synth 11.5 min? SF –

Bohrium is a synthetic chemical element; it has symbol Bh and atomic number 107. It is named after Danish physicist Niels Bohr. As a synthetic element, it can be created in particle accelerators but is not found in nature. All known isotopes of bohrium are highly radioactive; the most stable known isotope is ²⁷⁰Bh with a half-life of approximately 2.4 minutes, though the unconfirmed ²⁷⁸Bh may have a longer half-life of about 11.5 minutes.

In the periodic table, it is a d-block transactinide element. It is a member of the 7th period and belongs to the group 7 elements as the fifth member of the 6d series of transition metals. Chemistry experiments have confirmed that bohrium behaves as the heavier homologue to rhenium in group 7. The chemical properties of bohrium are characterized only partly, but they compare well with the chemistry of the other group 7 elements.

Introduction

This section is an excerpt from Superheavy element § Introduction.

Synthesis of superheavy nuclei

A superheavy atomic nucleus is created in a nuclear reaction that combines two other nuclei of unequal size into one; roughly, the more unequal the two nuclei in terms of mass, the greater the possibility that the two react. The material made of the heavier nuclei is made into a target, which is then bombarded by the beam of lighter nuclei. Two nuclei can only fuse into one if they approach each other closely enough; normally, nuclei (all positively charged) repel each other due to electrostatic repulsion. The strong interaction can overcome this repulsion but only within a very short distance from a nucleus; beam nuclei are thus greatly accelerated in order to make such repulsion insignificant compared to the velocity of the beam nucleus. The energy applied to the beam nuclei to accelerate them can cause them to reach speeds as high as one-tenth of the speed of light. However, if too much energy is applied, the beam nucleus can fall apart.

Coming close enough alone is not enough for two nuclei to fuse: when two nuclei approach each other, they usually remain together for approximately 10⁻²⁰ seconds and then part ways (not necessarily in the same composition as before the reaction) rather than form a single nucleus. This happens because during the attempted formation of a single nucleus, electrostatic repulsion tears apart the nucleus that is being formed. Each pair of a target and a beam is characterized by its cross section—the probability that fusion will occur if two nuclei approach one another expressed in terms of the transverse area that the incident particle must hit in order for the fusion to occur. This fusion may occur as a result of the quantum effect in which nuclei can tunnel through electrostatic repulsion. If the two nuclei can stay close for past that phase, multiple nuclear interactions result in redistribution of energy and an energy equilibrium.

External videos
Visualization of unsuccessful nuclear fusion, based on calculations from the Australian National University

The resulting merger is an excited state—termed a compound nucleus—and thus it is very unstable. To reach a more stable state, the temporary merger may fission without formation of a more stable nucleus. Alternatively, the compound nucleus may eject a few neutrons, which would carry away the excitation energy; if the latter is not sufficient for a neutron expulsion, the merger would produce a gamma ray. This happens in approximately 10⁻¹⁶ seconds after the initial nuclear collision and results in creation of a more stable nucleus. The definition by the IUPAC/IUPAP Joint Working Party (JWP) states that a chemical element can only be recognized as discovered if a nucleus of it has not decayed within 10⁻¹⁴ seconds. This value was chosen as an estimate of how long it takes a nucleus to acquire its outer electrons and thus display its chemical properties.

Decay and detection

The beam passes through the target and reaches the next chamber, the separator; if a new nucleus is produced, it is carried with this beam. In the separator, the newly produced nucleus is separated from other nuclides (that of the original beam and any other reaction products) and transferred to a surface-barrier detector, which stops the nucleus. The exact location of the upcoming impact on the detector is marked; also marked are its energy and the time of the arrival. The transfer takes about 10⁻⁶ seconds; in order to be detected, the nucleus must survive this long. The nucleus is recorded again once its decay is registered, and the location, the energy, and the time of the decay are measured.

Stability of a nucleus is provided by the strong interaction. However, its range is very short; as nuclei become larger, its influence on the outermost nucleons (protons and neutrons) weakens. At the same time, the nucleus is torn apart by electrostatic repulsion between protons, and its range is not limited. Total binding energy provided by the strong interaction increases linearly with the number of nucleons, whereas electrostatic repulsion increases with the square of the atomic number, i.e. the latter grows faster and becomes increasingly important for heavy and superheavy nuclei. Superheavy nuclei are thus theoretically predicted and have so far been observed to predominantly decay via decay modes that are caused by such repulsion: alpha decay and spontaneous fission. Almost all alpha emitters have over 210 nucleons, and the lightest nuclide primarily undergoing spontaneous fission has 238. In both decay modes, nuclei are inhibited from decaying by corresponding energy barriers for each mode, but they can be tunnelled through.

Alpha particles are commonly produced in radioactive decays because mass of an alpha particle per nucleon is small enough to leave some energy for the alpha particle to be used as kinetic energy to leave the nucleus. Spontaneous fission is caused by electrostatic repulsion tearing the nucleus apart and produces various nuclei in different instances of identical nuclei fissioning. As the atomic number increases, spontaneous fission rapidly becomes more important: spontaneous fission partial half-lives decrease by 23 orders of magnitude from uranium (element 92) to nobelium (element 102), and by 30 orders of magnitude from thorium (element 90) to fermium (element 100). The earlier liquid drop model thus suggested that spontaneous fission would occur nearly instantly due to disappearance of the fission barrier for nuclei with about 280 nucleons. The later nuclear shell model suggested that nuclei with about 300 nucleons would form an island of stability in which nuclei will be more resistant to spontaneous fission and will primarily undergo alpha decay with longer half-lives. Subsequent discoveries suggested that the predicted island might be further than originally anticipated; they also showed that nuclei intermediate between the long-lived actinides and the predicted island are deformed, and gain additional stability from shell effects. Experiments on lighter superheavy nuclei, as well as those closer to the expected island, have shown greater than previously anticipated stability against spontaneous fission, showing the importance of shell effects on nuclei.

Alpha decays are registered by the emitted alpha particles, and the decay products are easy to determine before the actual decay; if such a decay or a series of consecutive decays produces a known nucleus, the original product of a reaction can be easily determined. (That all decays within a decay chain were indeed related to each other is established by the location of these decays, which must be in the same place.) The known nucleus can be recognized by the specific characteristics of decay it undergoes such as decay energy (or more specifically, the kinetic energy of the emitted particle). Spontaneous fission, however, produces various nuclei as products, so the original nuclide cannot be determined from its daughters.

The information available to physicists aiming to synthesize a superheavy element is thus the information collected at the detectors: location, energy, and time of arrival of a particle to the detector, and those of its decay. The physicists analyze this data and seek to conclude that it was indeed caused by a new element and could not have been caused by a different nuclide than the one claimed. Often, provided data is insufficient for a conclusion that a new element was definitely created and there is no other explanation for the observed effects; errors in interpreting data have been made.

History

Discovery

Two groups claimed discovery of the element. Evidence of bohrium was first reported in 1976 by a Soviet research team led by Yuri Oganessian, in which targets of bismuth-209 and lead-208 were bombarded with accelerated nuclei of chromium-54 and manganese-55 respectively. Two activities, one with a half-life of one to two milliseconds, and the other with an approximately five-second half-life, were seen. Since the ratio of the intensities of these two activities was constant throughout the experiment, it was proposed that the first was from the isotope bohrium-261 and that the second was from its daughter dubnium-257. Later, the dubnium isotope was corrected to dubnium-258, which indeed has a five-second half-life (dubnium-257 has a one-second half-life); however, the half-life observed for its parent is much shorter than the half-lives later observed in the definitive discovery of bohrium at Darmstadt in 1981. The IUPAC/IUPAP Transfermium Working Group (TWG) concluded that while dubnium-258 was probably seen in this experiment, the evidence for the production of its parent bohrium-262 was not convincing enough.

In 1981, a German research team led by Peter Armbruster and Gottfried Münzenberg at the GSI Helmholtz Centre for Heavy Ion Research (GSI Helmholtzzentrum für Schwerionenforschung) in Darmstadt bombarded a target of bismuth-209 with accelerated nuclei of chromium-54 to produce 5 atoms of the isotope bohrium-262:

²⁰⁹
₈₃Bi + ⁵⁴
₂₄Cr → ²⁶²
₁₀₇Bh +
n

This discovery was further substantiated by their detailed measurements of the alpha decay chain of the produced bohrium atoms to previously known isotopes of fermium and californium. The IUPAC/IUPAP Transfermium Working Group (TWG) recognised the GSI collaboration as official discoverers in their 1992 report.

Proposed names

In September 1992, the German group suggested the name nielsbohrium with symbol Ns to honor the Danish physicist Niels Bohr. The Soviet scientists at the Joint Institute for Nuclear Research in Dubna, Russia had suggested this name be given to element 105 (which was finally called dubnium) and the German team wished to recognise both Bohr and the fact that the Dubna team had been the first to propose the cold fusion reaction, and simultaneously help to solve the controversial problem of the naming of element 105. The Dubna team agreed with the German group's naming proposal for element 107.

There was an element naming controversy as to what the elements from 104 to 106 were to be called; the IUPAC adopted unnilseptium (symbol Uns) as a temporary, systematic element name for this element. In 1994 a committee of IUPAC recommended that element 107 be named bohrium, not nielsbohrium, since there was no precedent for using a scientist's complete name in the naming of an element. This was opposed by the discoverers as there was some concern that the name might be confused with boron and in particular the distinguishing of the names of their respective oxyanions, bohrate and borate. The matter was handed to the Danish branch of IUPAC which, despite this, voted in favour of the name bohrium, and thus the name bohrium for element 107 was recognized internationally in 1997; the names of the respective oxyanions of boron and bohrium remain unchanged despite their homophony.

Isotopes

Bohrium has no stable or naturally occurring isotopes. Several radioactive isotopes have been synthesized in the laboratory, either by fusing two atoms or by observing the decay of heavier elements. Twelve different isotopes of bohrium have been reported with atomic masses 260–262, 264–267, 270–272, 274, and 278, one of which, bohrium-262, has a known metastable state. All of these but the unconfirmed ²⁷⁸Bh decay only through alpha decay, although some unknown bohrium isotopes are predicted to undergo spontaneous fission.

The lighter isotopes usually have shorter half-lives; half-lives of under 100 ms for ²⁶⁰Bh, ²⁶¹Bh, ²⁶²Bh, and ^262mBh were observed. ²⁶⁴Bh, ²⁶⁵Bh, ²⁶⁶Bh, and ²⁷¹Bh are more stable at around 1 s, and ²⁶⁷Bh and ²⁷²Bh have half-lives of about 10 s. The heaviest isotopes are the most stable, with ²⁷⁰Bh and ²⁷⁴Bh having measured half-lives of about 2.4 min and 40 s respectively, and the even heavier unconfirmed isotope ²⁷⁸Bh appearing to have an even longer half-life of about 11.5 minutes.

The most proton-rich isotopes with masses 260, 261, and 262 were directly produced by cold fusion, those with mass 262 and 264 were reported in the decay chains of meitnerium and roentgenium, while the neutron-rich isotopes with masses 265, 266, 267 were created in irradiations of actinide targets. The five most neutron-rich ones with masses 270, 271, 272, 274, and 278 (unconfirmed) appear in the decay chains of ²⁸²Nh, ²⁸⁷Mc, ²⁸⁸Mc, ²⁹⁴Ts, and ²⁹⁰Fl respectively. The half-lives of bohrium isotopes range from about ten milliseconds for ^262mBh to about one minute for ²⁷⁰Bh and ²⁷⁴Bh, extending to about 11.5 minutes for the unconfirmed ²⁷⁸Bh, which may have one of the longest half-lives among reported superheavy nuclides.

Predicted properties

Very few properties of bohrium or its compounds have been measured; this is due to its extremely limited and expensive production and the fact that bohrium (and its parents) decays very quickly. A few singular chemistry-related properties have been measured, but properties of bohrium metal remain unknown and only predictions are available.

Chemical

Bohrium is the fifth member of the 6d series of transition metals and the heaviest member of group 7 in the periodic table, below manganese, technetium and rhenium. All the members of the group readily portray their group oxidation state of +7 and the state becomes more stable as the group is descended. Thus bohrium is expected to form a stable +7 state. Technetium also shows a stable +4 state whilst rhenium exhibits stable +4 and +3 states. Bohrium may therefore show these lower states as well. The higher +7 oxidation state is more likely to exist in oxyanions, such as perbohrate, BhO⁻
₄, analogous to the lighter permanganate, pertechnetate, and perrhenate. Nevertheless, bohrium(VII) is likely to be unstable in aqueous solution, and would probably be easily reduced to the more stable bohrium(IV).

The lighter group 7 elements are known to form volatile heptoxides M₂O₇ (M = Mn, Tc, Re), so bohrium should also form the volatile oxide Bh₂O₇. The oxide should dissolve in water to form perbohric acid, HBhO₄. Rhenium and technetium form a range of oxyhalides from the halogenation of the oxide. The chlorination of the oxide forms the oxychlorides MO₃Cl, so BhO₃Cl should be formed in this reaction. Fluorination results in MO₃F and MO₂F₃ for the heavier elements in addition to the rhenium compounds ReOF₅ and ReF₇. Therefore, oxyfluoride formation for bohrium may help to indicate eka-rhenium properties. Since the oxychlorides are asymmetrical, and they should have increasingly large dipole moments going down the group, they should become less volatile in the order TcO₃Cl > ReO₃Cl > BhO₃Cl: this was experimentally confirmed in 2000 by measuring the enthalpies of adsorption of these three compounds. The values are for TcO₃Cl and ReO₃Cl are −51 kJ/mol and −61 kJ/mol respectively; the experimental value for BhO₃Cl is −77.8 kJ/mol, very close to the theoretically expected value of −78.5 kJ/mol.

Physical and atomic

Bohrium is expected to be a solid under normal conditions and assume a hexagonal close-packed crystal structure (^c/_a = 1.62), similar to its lighter congener rhenium. Early predictions by Fricke estimated its density at 37.1 g/cm³, but newer calculations predict a somewhat lower value of 26–27 g/cm³.

The atomic radius of bohrium is expected to be around 128 pm. Due to the relativistic stabilization of the 7s orbital and destabilization of the 6d orbital, the Bh⁺ ion is predicted to have an electron configuration of [Rn] 5f¹⁴ 6d⁴ 7s², giving up a 6d electron instead of a 7s electron, which is the opposite of the behavior of its lighter homologues manganese and technetium. Rhenium, on the other hand, follows its heavier congener bohrium in giving up a 5d electron before a 6s electron, as relativistic effects have become significant by the sixth period, where they cause among other things the yellow color of gold and the low melting point of mercury. The Bh²⁺ ion is expected to have an electron configuration of [Rn] 5f¹⁴ 6d³ 7s²; in contrast, the Re²⁺ ion is expected to have a [Xe] 4f¹⁴ 5d⁵ configuration, this time analogous to manganese and technetium. The ionic radius of hexacoordinate heptavalent bohrium is expected to be 58 pm (heptavalent manganese, technetium, and rhenium having values of 46, 57, and 53 pm respectively). Pentavalent bohrium should have a larger ionic radius of 83 pm.

Experimental chemistry

In 1995, the first report on attempted isolation of the element was unsuccessful, prompting new theoretical studies to investigate how best to investigate bohrium (using its lighter homologs technetium and rhenium for comparison) and removing unwanted contaminating elements such as the trivalent actinides, the group 5 elements, and polonium.

In 2000, it was confirmed that although relativistic effects are important, bohrium behaves like a typical group 7 element. A team at the Paul Scherrer Institute (PSI) conducted a chemistry reaction using six atoms of ²⁶⁷Bh produced in the reaction between ²⁴⁹Bk and ²²Ne ions. The resulting atoms were thermalised and reacted with a HCl/O₂ mixture to form a volatile oxychloride. The reaction also produced isotopes of its lighter homologues, technetium (as ¹⁰⁸Tc) and rhenium (as ¹⁶⁹Re). The isothermal adsorption curves were measured and gave strong evidence for the formation of a volatile oxychloride with properties similar to that of rhenium oxychloride. This placed bohrium as a typical member of group 7. The adsorption enthalpies of the oxychlorides of technetium, rhenium, and bohrium were measured in this experiment, agreeing very well with the theoretical predictions and implying a sequence of decreasing oxychloride volatility down group 7 of TcO₃Cl > ReO₃Cl > BhO₃Cl.

2 Bh + 3 O
₂ + 2 HCl → 2 BhO
₃Cl + H
₂

The longer-lived heavy isotopes of bohrium, produced as the daughters of heavier elements, offer advantages for future radiochemical experiments. Although the heavy isotope ²⁷⁴Bh requires a rare and highly radioactive berkelium target for its production, the isotopes ²⁷²Bh, ²⁷¹Bh, and ²⁷⁰Bh can be readily produced as daughters of more easily produced moscovium and nihonium isotopes.