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Not to be confused with the chemical compound borium or elements boron (B) or barium (Ba).

Bohrium, 107Bh
Bohrium
Pronunciation/ˈbɔːriəm/ ⓘ ​(BOR-ee-əm)
Mass number[270] (data not decisive)[a]
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
↓
—
seaborgium ← bohrium → hassium
Atomic number (Z)107
Groupgroup 7
Periodperiod 7
Block  d-block
Electron configuration[Rn] 5f14 6d5 7s2[3][4]
Electrons per shell2, 8, 18, 32, 32, 13, 2
Physical properties
Phase at STPsolid (predicted)[5]
Density (near r.t.)26–27 g/cm3 (predicted)[6][7]
Atomic properties
Oxidation statescommon: (none)
(+3), (+4), (+5), (+7)[4]
Ionization energies
  • 1st: 740 kJ/mol
  • 2nd: 1690 kJ/mol
  • 3rd: 2570 kJ/mol
  • (more) (all but first estimated)[4]
Atomic radiusempirical: 128 pm (predicted)[4]
Covalent radius141 pm (estimated)[8]
Other properties
Natural occurrencesynthetic
Crystal structure ​hexagonal close-packed (hcp)
Hexagonal close-packed crystal structure for bohrium

(predicted)[5]
CAS Number54037-14-8
History
Namingafter Niels Bohr
DiscoveryGesellschaft für Schwerionenforschung (1981)
Isotopes of bohrium
Main isotopes[9] 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[10] α 267Db
272Bh synth 8.8 s α 268Db
274Bh synth 40 s[11] α 270Db
278Bh synth 11.5 min?[2] SF –
 Category: Bohrium
| references

Bohrium is a synthetic chemical element with the symbol Bh and atomic number 107. It is named after Danish physicist Niels Bohr. As a synthetic element, it can be created in a laboratory but is not found in nature. All known isotopes of bohrium are extremely radioactive; the most stable known isotope is 270Bh with a half-life of approximately 61 seconds, though the unconfirmed 278Bh may have a longer half-life of about 690 seconds.

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 transcluded from Introduction to the heaviest elements. (edit | history)
"Transactinide element" redirects here. Not to be confused with Transuranium element.
Superheavy elements
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
Z ≥ 104 (Rf)

Superheavy elements, also known as transactinide elements, transactinides, or super-heavy elements, or superheavies for short, are the chemical elements with atomic number greater than 104.[12] The superheavy elements are those beyond the actinides in the periodic table; the last actinide is lawrencium (atomic number 103). By definition, superheavy elements are also transuranium elements, i.e., having atomic numbers greater than that of uranium (92). Depending on the definition of group 3 adopted by authors, lawrencium may also be included to complete the 6d series.[13][14][15][16]

Glenn T. Seaborg first proposed the actinide concept, which led to the acceptance of the actinide series. He also proposed a transactinide series ranging from element 104 to 121 and a superactinide series approximately spanning elements 122 to 153 (though more recent work suggests the end of the superactinide series to occur at element 157 instead). The transactinide seaborgium was named in his honor.[17][18]

Superheavies are radioactive and have only been obtained synthetically in laboratories. No macroscopic sample of any of these elements has ever been produced. Superheavies are all named after physicists and chemists or important locations involved in the synthesis of the elements.

IUPAC defines an element to exist if its lifetime is longer than 10−14 seconds, which is the time it takes for the atom to form an electron cloud.[19]

The known superheavies form part of the 6d and 7p series in the periodic table. Except for rutherfordium and dubnium (and lawrencium if it is included), even the longest-lived known isotopes of superheavies have half-lives of minutes or less. The element naming controversy involved elements 102–109. Some of these elements thus used systematic names for many years after their discovery was confirmed. (Usually the systematic names are replaced with permanent names proposed by the discoverers relatively soon after a discovery has been confirmed.)

Introduction

Synthesis of superheavy nuclei

See also: Nucleosynthesis and Nuclear reaction
A graphic depiction of a nuclear fusion reaction
A graphic depiction of a nuclear fusion reaction. Two nuclei fuse into one, emitting a neutron. Reactions that created new elements to this moment were similar, with the only possible difference that several singular neutrons sometimes were released, or none at all.

A superheavy[b] atomic nucleus is created in a nuclear reaction that combines two other nuclei of unequal size[c] into one; roughly, the more unequal the two nuclei in terms of mass, the greater the possibility that the two react.[25] 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.[26] 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.[26]

Coming close enough alone is not enough for two nuclei to fuse: when two nuclei approach each other, they usually remain together for about 10−20 seconds and then part ways (not necessarily in the same composition as before the reaction) rather than form a single nucleus.[26][27] This happens because during the attempted formation of a single nucleus, electrostatic repulsion tears apart the nucleus that is being formed.[26] 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.[d] 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 past that phase, multiple nuclear interactions result in redistribution of energy and an energy equilibrium.[26]

External videos
video icon Visualization of unsuccessful nuclear fusion, based on calculations from the Australian National University[29]

The resulting merger is an excited state[30]—termed a compound nucleus—and thus it is very unstable.[26] To reach a more stable state, the temporary merger may fission without formation of a more stable nucleus.[31] 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 about 10−16 seconds after the initial nuclear collision and results in creation of a more stable nucleus.[31] 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 electrons and thus display its chemical properties.[32][e]

Decay and detection

See also: Gaseous ionization detector

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.[34] In the separator, the newly produced nucleus is separated from other nuclides (that of the original beam and any other reaction products)[f] 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.[34] The transfer takes about 10−6 seconds; in order to be detected, the nucleus must survive this long.[37] The nucleus is recorded again once its decay is registered, and the location, the energy, and the time of the decay are measured.[34]

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.[38] 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.[39][40] Superheavy nuclei are thus theoretically predicted[41] and have so far been observed[42] to predominantly decay via decay modes that are caused by such repulsion: alpha decay and spontaneous fission.[g] Almost all alpha emitters have over 210 nucleons,[44] and the lightest nuclide primarily undergoing spontaneous fission has 238.[45] In both decay modes, nuclei are inhibited from decaying by corresponding energy barriers for each mode, but they can be tunneled through.[39][40]

Apparatus for creation of superheavy elements
Scheme of an apparatus for creation of superheavy elements, based on the Dubna Gas-Filled Recoil Separator set up in the Flerov Laboratory of Nuclear Reactions in JINR. The trajectory within the detector and the beam focusing apparatus changes because of a dipole magnet in the former and quadrupole magnets in the latter.[46]

Alpha particles are commonly produced in radioactive decays because the 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.[47] Spontaneous fission is caused by electrostatic repulsion tearing the nucleus apart and produces various nuclei in different instances of identical nuclei fissioning.[40] 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),[48] and by 30 orders of magnitude from thorium (element 90) to fermium (element 100).[49] 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.[40][50] 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.[40][50] 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.[51] Experiments on lighter superheavy nuclei,[52] as well as those closer to the expected island,[48] have shown greater than previously anticipated stability against spontaneous fission, showing the importance of shell effects on nuclei.[h]

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.[i] (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.)[34] 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).[j] Spontaneous fission, however, produces various nuclei as products, so the original nuclide cannot be determined from its daughters.[k]

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.[l]

History

Early predictions

The heaviest element known at the end of the 19th century was uranium, with an atomic mass of about 240 (now known to be 238) amu. Accordingly, it was placed in the last row of the periodic table; this fueled speculation about the possible existence of elements heavier than uranium and why A = 240 seemed to be the limit. Following the discovery of the noble gases, beginning with argon in 1895, the possibility of heavier members of the group was considered. Danish chemist Julius Thomsen proposed in 1895 the existence of a sixth noble gas with Z = 86, A = 212 and a seventh with Z = 118, A = 292, the last closing a 32-element period containing thorium and uranium.[63] In 1913, Swedish physicist Johannes Rydberg extended Thomsen's extrapolation of the periodic table to include even heavier elements with atomic numbers up to 460, but he did not believe that these superheavy elements existed or occurred in nature.[64]

In 1914, German physicist Richard Swinne proposed that elements heavier than uranium, such as those around Z = 108, could be found in cosmic rays. He suggested that these elements may not necessarily have decreasing half-lives with increasing atomic number, leading to speculation about the possibility of some longer-lived elements at Z = 98–102 and Z = 108–110 (though separated by short-lived elements). Swinne published these predictions in 1926, believing that such elements might exist in Earth's core, iron meteorites, or the ice caps of Greenland where they had been locked up from their supposed cosmic origin.[65]

Discoveries

Work performed from 1961 to 2013 at four labs – Lawrence Berkeley National Laboratory in the US, the Joint Institute for Nuclear Research in the USSR (later Russia), the GSI Helmholtz Centre for Heavy Ion Research in Germany, and Riken in Japan – identified and confirmed the elements lawrencium to oganesson according to the criteria of the IUPAC–IUPAP Transfermium Working Groups and subsequent Joint Working Parties. These discoveries complete the seventh row of the periodic table. The next two elements, ununennium (Z = 119) and unbinilium (Z = 120), have not yet been synthesized. They would begin an eighth period.

List of elements

Characteristics

Due to their short half-lives (for example, the most stable known isotope of seaborgium has a half-life of 14 minutes, and half-lives decrease with increasing atomic number) and the low yield of the nuclear reactions that produce them, new methods have had to be created to determine their gas-phase and solution chemistry based on very small samples of a few atoms each. Relativistic effects become very important in this region of the periodic table, causing the filled 7s orbitals, empty 7p orbitals, and filling 6d orbitals to all contract inward toward the atomic nucleus. This causes a relativistic stabilization of the 7s electrons and makes the 7p orbitals accessible in low excitation states.[18]

Elements 103 to 112, lawrencium to copernicium, form the 6d series of transition elements. Experimental evidence shows that elements 103–108 behave as expected for their position in the periodic table, as heavier homologs of lutetium through osmium. They are expected to have ionic radii between those of their 5d transition metal homologs and their actinide pseudohomologs: for example, Rf4+ is calculated to have ionic radius 76 pm, between the values for Hf4+ (71 pm) and Th4+ (94 pm). Their ions should also be less polarizable than those of their 5d homologs. Relativistic effects are expected to reach a maximum at the end of this series, at roentgenium (element 111) and copernicium (element 112). Nevertheless, many important properties of the transactinides are still not yet known experimentally, though theoretical calculations have been performed.[18]

Elements 113 to 118, nihonium to oganesson, should form a 7p series, completing the seventh period in the periodic table. Their chemistry will be greatly influenced by the very strong relativistic stabilization of the 7s electrons and a strong spin–orbit coupling effect "tearing" the 7p subshell apart into two sections, one more stabilized (7p1/2, holding two electrons) and one more destabilized (7p3/2, holding four electrons). Lower oxidation states should be stabilized here, continuing group trends, as both the 7s and 7p1/2 electrons exhibit the inert-pair effect. These elements are expected to largely continue to follow group trends, though with relativistic effects playing an increasingly larger role. In particular, the large 7p splitting results in an effective shell closure at flerovium (element 114) and a hence much higher than expected chemical activity for oganesson (element 118).[18]

Element 118 is the last element that has been synthesized. The next two elements, 119 and 120, should form an 8s series and be an alkali and alkaline earth metal respectively. The 8s electrons are expected to be relativistically stabilized, so that the trend toward higher reactivity down these groups will reverse and the elements will behave more like their period 5 homologs, rubidium and strontium. The 7p3/2 orbital is still relativistically destabilized, potentially giving these elements larger ionic radii and perhaps even being able to participate chemically. In this region, the 8p electrons are also relativistically stabilized, resulting in a ground-state 8s28p1 valence electron configuration for element 121. Large changes are expected to occur in the subshell structure in going from element 120 to element 121: for example, the radius of the 5g orbitals should drop drastically, from 25 Bohr units in element 120 in the excited [Og] 5g1 8s1 configuration to 0.8 Bohr units in element 121 in the excited [Og] 5g1 7d1 8s1 configuration, in a phenomenon called "radial collapse". Element 122 should add either a further 7d or a further 8p electron to element 121's electron configuration. Elements 121 and 122 should be similar to actinium and thorium respectively.[18]

At element 121, the superactinide series is expected to begin, when the 8s electrons and the filling 8p1/2, 7d3/2, 6f5/2, and 5g7/2 subshells determine the chemistry of these elements. Complete and accurate calculations are not available for elements beyond 123 because of the extreme complexity of the situation:[66] the 5g, 6f, and 7d orbitals should have about the same energy level, and in the region of element 160 the 9s, 8p3/2, and 9p1/2 orbitals should also be about equal in energy. This will cause the electron shells to mix so that the block concept no longer applies very well, and will also result in novel chemical properties that will make positioning these elements in a periodic table very difficult.[18]

Beyond superheavy elements

It has been suggested that elements beyond Z = 126 be called beyond superheavy elements.[67] Other sources refer to elements around Z = 164 as hyperheavy elements.[68]

See also

Notes

  1. ^ The most stable isotope of bohrium cannot be determined based on existing data due to uncertainty that arises from the low number of measurements. The half-life of 270Bh corresponding to two standard deviations is, based on existing data, 2.4+8.8
    −1.8     minutes[1], whereas that of 274Bh is 44+68
    −26     seconds; these measurements have overlapping confidence intervals. It is also possible that the unconfirmed 278Bh is more stable than both of these, with its half-life being 11.5 minutes.[2]
  2. ^ In nuclear physics, an element is called heavy if its atomic number is high; lead (element 82) is one example of such a heavy element. The term "superheavy elements" typically refers to elements with atomic number greater than 103 (although there are other definitions, such as atomic number greater than 100[20] or 112;[21] sometimes, the term is presented an equivalent to the term "transactinide", which puts an upper limit before the beginning of the hypothetical superactinide series).[22] Terms "heavy isotopes" (of a given element) and "heavy nuclei" mean what could be understood in the common language—isotopes of high mass (for the given element) and nuclei of high mass, respectively.
  3. ^ In 2009, a team at the JINR led by Oganessian published results of their attempt to create hassium in a symmetric 136Xe + 136Xe reaction. They failed to observe a single atom in such a reaction, putting the upper limit on the cross section, the measure of probability of a nuclear reaction, as 2.5 pb.[23] In comparison, the reaction that resulted in hassium discovery, 208Pb + 58Fe, had a cross section of ~20 pb (more specifically, 19+19
    -11     pb), as estimated by the discoverers.[24]
  4. ^ The amount of energy applied to the beam particle to accelerate it can also influence the value of cross section. For example, in the 28
    14    Si
     + 1
    0    n
     → 28
    13    Al
     + 1
    1    p
     reaction, cross section changes smoothly from 370 mb at 12.3 MeV to 160 mb at 18.3 MeV, with a broad peak at 13.5 MeV with the maximum value of 380 mb.[28]
  5. ^ This figure also marks the generally accepted upper limit for lifetime of a compound nucleus.[33]
  6. ^ This separation is based on that the resulting nuclei move past the target more slowly then the unreacted beam nuclei. The separator contains electric and magnetic fields whose effects on a moving particle cancel out for a specific velocity of a particle.[35] Such separation can also be aided by a time-of-flight measurement and a recoil energy measurement; a combination of the two may allow to estimate the mass of a nucleus.[36]
  7. ^ Not all decay modes are caused by electrostatic repulsion. For example, beta decay is caused by the weak interaction.[43]
  8. ^ It was already known by the 1960s that ground states of nuclei differed in energy and shape as well as that certain magic numbers of nucleons corresponded to greater stability of a nucleus. However, it was assumed that there was no nuclear structure in superheavy nuclei as they were too deformed to form one.[48]
  9. ^ Since mass of a nucleus is not measured directly but is rather calculated from that of another nucleus, such measurement is called indirect. Direct measurements are also possible, but for the most part they have remained unavailable for superheavy nuclei.[53] The first direct measurement of mass of a superheavy nucleus was reported in 2018 at LBNL.[54] Mass was determined from the location of a nucleus after the transfer (the location helps determine its trajectory, which is linked to the mass-to-charge ratio of the nucleus, since the transfer was done in presence of a magnet).[55]
  10. ^ If the decay occurred in a vacuum, then since total momentum of an isolated system before and after the decay must be preserved, the daughter nucleus would also receive a small velocity. The ratio of the two velocities, and accordingly the ratio of the kinetic energies, would thus be inverse to the ratio of the two masses. The decay energy equals the sum of the known kinetic energy of the alpha particle and that of the daughter nucleus (an exact fraction of the former).[44] The calculations hold for an experiment as well, but the difference is that the nucleus does not move after the decay because it is tied to the detector.
  11. ^ Spontaneous fission was discovered by Soviet physicist Georgy Flerov,[56] a leading scientist at JINR, and thus it was a "hobbyhorse" for the facility.[57] In contrast, the LBL scientists believed fission information was not sufficient for a claim of synthesis of an element. They believed spontaneous fission had not been studied enough to use it for identification of a new element, since there was a difficulty of establishing that a compound nucleus had only ejected neutrons and not charged particles like protons or alpha particles.[33] They thus preferred to link new isotopes to the already known ones by successive alpha decays.[56]
  12. ^ For instance, element 102 was mistakenly identified in 1957 at the Nobel Institute of Physics in Stockholm, Stockholm County, Sweden.[58] There were no earlier definitive claims of creation of this element, and the element was assigned a name by its Swedish, American, and British discoverers, nobelium. It was later shown that the identification was incorrect.[59] The following year, RL was unable to reproduce the Swedish results and announced instead their synthesis of the element; that claim was also disproved later.[59] JINR insisted that they were the first to create the element and suggested a name of their own for the new element, joliotium;[60] the Soviet name was also not accepted (JINR later referred to the naming of the element 102 as "hasty").[61] This name was proposed to IUPAC in a written response to their ruling on priority of discovery claims of elements, signed 29 September 1992.[61] The name "nobelium" remained unchanged on account of its widespread usage.[62]

References

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  3. ^ Johnson, E.; Fricke, B.; Jacob, T.; Dong, C. Z.; Fritzsche, S.; Pershina, V. (2002). "Ionization potentials and radii of neutral and ionized species of elements 107 (bohrium) and 108 (hassium) from extended multiconfiguration Dirac–Fock calculations". The Journal of Chemical Physics. 116 (5): 1862–1868. Bibcode:2002JChPh.116.1862J. doi:10.1063/1.1430256.
  4. ^ a b c d Hoffman, Darleane C.; Lee, Diana M.; Pershina, Valeria (2006). "Transactinides and the future elements". In Morss; Edelstein, Norman M.; Fuger, Jean (eds.). The Chemistry of the Actinide and Transactinide Elements (3rd ed.). Dordrecht, The Netherlands: Springer Science+Business Media. ISBN 978-1-4020-3555-5.
  5. ^ a b Östlin, A.; Vitos, L. (2011). "First-principles calculation of the structural stability of 6d transition metals". Physical Review B. 84 (11). Bibcode:2011PhRvB..84k3104O. doi:10.1103/PhysRevB.84.113104.
  6. ^ Gyanchandani, Jyoti; Sikka, S. K. (10 May 2011). "Physical properties of the 6 d -series elements from density functional theory: Close similarity to lighter transition metals". Physical Review B. 83 (17): 172101. doi:10.1103/PhysRevB.83.172101.
  7. ^ Kratz; Lieser (2013). Nuclear and Radiochemistry: Fundamentals and Applications (3rd ed.). p. 631.
  8. ^ Chemical Data. Bohrium - Bh, Royal Chemical Society
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  10. ^ FUSHE (2012). "Synthesis of SH-nuclei". Retrieved August 12, 2016.
  11. ^ Oganessian, Yuri Ts.; Abdullin, F. Sh.; Bailey, P. D.; et al. (2010-04-09). "Synthesis of a New Element with Atomic Number Z=117". Physical Review Letters. 104 (142502). American Physical Society. Bibcode:2010PhRvL.104n2502O. doi:10.1103/PhysRevLett.104.142502. PMID 20481935. (gives life-time of 1.3 min based on a single event; conversion to half-life is done by multiplying with ln(2).)
  12. ^ "Superheavy Element Discovery | Glenn T. Seaborg Institute". seaborg.llnl.gov. Retrieved 2024-09-02.
  13. ^ a b Neve, Francesco (2022). "Chemistry of superheavy transition metals". Journal of Coordination Chemistry. 75 (17–18): 2287–2307. doi:10.1080/00958972.2022.2084394. S2CID 254097024.
  14. ^ a b Mingos, Michael (1998). Essential Trends in Inorganic Chemistry. Oxford University Press. p. 387. ISBN 978-0-19-850109-1.
  15. ^ "A New Era of Discovery: the 2023 Long Range Plan for Nuclear Science" (PDF). U.S. Department of Energy. October 2023. Archived from the original (PDF) on 2023-10-05. Retrieved 20 October 2023 – via OSTI. Superheavy elements (Z > 102) are teetering at the limits of mass and charge.
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Bibliography

History

Element 107 was originally proposed to be named after Niels Bohr, a Danish nuclear physicist, with the name nielsbohrium (Ns). This name was later changed by IUPAC to bohrium (Bh).

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.[1] 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.[2]

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:[3]

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.[2]

Proposed names

File:Bohrium hassium meitnerium ceremony.jpg
Naming ceremony conducted at the GSI on 7 September 1992 for the namings of elements 107, 108, and 109 as nielsbohrium, hassium, and meitnerium

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 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.[4]

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.[5] 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.[5][6] 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;[5] the names of the respective oxyanions of boron and bohrium remain unchanged despite their homophony.[7]

Isotopes

Main article: Isotopes of bohrium
List of bohrium isotopes
Isotope
 Half-life
[8][9]		 Decay
mode[8][9]		 Discovery
year		 Reaction
260Bh 35 ms α 2007 209Bi(52Cr,n)[10]
261Bh 11.8 ms α 1986 209Bi(54Cr,2n)[11]
262Bh 84 ms α 1981 209Bi(54Cr,n)[3]
262mBh 9.6 ms α 1981 209Bi(54Cr,n)[3]
264Bh 0.97 s α 1994 272Rg(—,2α)[12]
265Bh 0.9 s α 2004 243Am(26Mg,4n)[13]
266Bh 0.9 s α 2000 249Bk(22Ne,5n)[14]
267Bh 17 s α 2000 249Bk(22Ne,4n)[14]
270Bh 61 s α 2006 282Nh(—,3α)[15]
271Bh 1.2 s α 2003 287Mc(—,4α)[15]
272Bh 9.8 s α 2005 288Mc(—,4α)[15]
274Bh 40 s α 2009 294Ts(—,5α)[16]
278Bh 11.5 min? SF 1998? 290Fl(e−,νe3α)?

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.[8]

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 61 s and 40 s respectively, and the even heavier unconfirmed isotope 278Bh appearing to have an even longer half-life of about 690 s.

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. These eleven isotopes have half-lives ranging from about ten milliseconds for 262mBh to about one minute for 270Bh and 274Bh, extending to about twelve minutes for the unconfirmed 278Bh, one of the longest-lived known superheavy nuclides.[17]

Predicted properties

Very few properties of bohrium or its compounds have been measured; this is due to its extremely limited and expensive production[18] 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.[19] 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).[20]

Technetium and rhenium are known to form volatile heptoxides M2O7 (M = 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.[21] 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.[20]

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.[22] It should be a very heavy metal with a density of around 37.1 g/cm3, which would be the third-highest of any of the 118 known elements, lower than only meitnerium (37.4 g/cm3) and hassium (41 g/cm3), the two following elements in the periodic table. In comparison, the densest known element that has had its density measured, osmium, has a density of only 22.61 g/cm3. This results from bohrium's high atomic weight, the lanthanide and actinide contractions, and relativistic effects, although production of enough bohrium to measure this quantity would be impractical, and the sample would quickly decay.[20]

The atomic radius of bohrium is expected to be around 128 pm.[20] 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.[20] 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.[20]

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.[23]

In 2000, it was confirmed that although relativistic effects are important, bohrium behaves like a typical group 7 element.[24] 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.[25] 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.[20]

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.[26]

Notes

References

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  21. ^ Hans Georg Nadler "Rhenium and Rhenium Compounds" Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2000. doi:10.1002/14356007.a23_199
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  23. ^ Malmbeck, R.; Skarnemark, G.; Alstad, J.; Fure, K.; Johansson, M.; Omtvedt, J. P. (2000). "Chemical Separation Procedure Proposed for Studies of Bohrium". Journal of Radioanalytical and Nuclear Chemistry. 246 (2): 349. doi:10.1023/A:1006791027906.
  24. ^ Gäggeler, H. W.; Eichler, R.; Brüchle, W.; Dressler, R.; Düllmann, Ch. E.; Eichler, B.; Gregorich, K. E.; Hoffman, D. C.; Hübener, S. (2000). "Chemical characterization of bohrium (element 107)". Nature. 407 (6800): 63–5. Bibcode:2000Natur.407...63E. doi:10.1038/35024044. PMID 10993071. {{cite journal}}: Unknown parameter |displayauthors= ignored (|display-authors= suggested) (help)
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  26. ^ Moody, Ken (2013-11-30). "Synthesis of Superheavy Elements". In Schädel, Matthias; Shaughnessy, Dawn (eds.). The Chemistry of Superheavy Elements (2nd ed.). Springer Science & Business Media. pp. 24–8. ISBN 9783642374661.

Bibliography

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