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Bohrium

  • ️Sun Mar 15 2020
Bohrium, 107Bh
Bohrium
Pronunciation ⓘ ​(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
Group group 7
Period period 7
Block   d-block
Electron configuration [Rn] 5f14 6d5 7s2[3][4]
Electrons per shell 2, 8, 18, 32, 32, 13, 2
Physical properties
Phase at STP solid (predicted)[5]
Density (near r.t.) 26–27 g/cm3 (predicted)[6][7]
Atomic properties
Oxidation states common: (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 radius empirical: 128 pm (predicted)[4]
Covalent radius 141 pm (estimated)[8]
Other properties
Natural occurrence synthetic
Crystal structure ​hexagonal close-packed (hcp)

Hexagonal close-packed crystal structure for bohrium


(predicted)[5]
CAS Number 54037-14-8
History
Naming after Niels Bohr
Discovery Gesellschaft 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 57 s α 270Db
278Bh synth 11.5 min?[2] SF –
 Category: Bohrium
| references

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.

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.[54] 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.[55]

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:[56]

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.[55]

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.[57]

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.[58] 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.[58][59] 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;[58] the names of the respective oxyanions of boron and bohrium remain unchanged despite their homophony.[60]

List of bohrium isotopes
Isotope Half-life[m] Decay
mode 		Discovery
year 		Discovery
reaction
Value ref
260Bh 41 ms [9] α 2007 209Bi(52Cr,n)[61]
261Bh 12.8 ms [9] α 1986 209Bi(54Cr,2n)[62]
262Bh 84 ms [9] α 1981 209Bi(54Cr,n)[56]
262mBh 9.5 ms [9] α 1981 209Bi(54Cr,n)[56]
264Bh 1.07 s [9] α 1994 272Rg(—,2α)[63]
265Bh 1.19 s [9] α 2004 243Am(26Mg,4n)[64]
266Bh 10.6 s [9] α 2000 249Bk(22Ne,5n)[65]
267Bh 22 s [9] α 2000 249Bk(22Ne,4n)[65]
270Bh 2.4 min [1] α 2006 282Nh(—,3α)[66]
271Bh 2.9 s [1] α 2003 287Mc(—,4α)[66]
272Bh 8.8 s [1] α 2005 288Mc(—,4α)[66]
274Bh 57 s [9] α 2009 294Ts(—,5α)[67]
278Bh 11.5 min? [2] 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.[68]

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.[69]

Very few properties of bohrium or its compounds have been measured; this is due to its extremely limited and expensive production[70] 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.

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.[71] 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).[4]

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.[72] 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.[4]

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.[5] Early predictions by Fricke estimated its density at 37.1 g/cm3,[4] but newer calculations predict a somewhat lower value of 26–27 g/cm3.[6][7]

The atomic radius of bohrium is expected to be around 128 pm.[4] 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.[4] 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.[4]

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.[73]

In 2000, it was confirmed that although relativistic effects are important, bohrium behaves like a typical group 7 element.[74] 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.[75] 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.[4]

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.[76]

  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[11] or 112;[12] sometimes, the term is presented an equivalent to the term "transactinide", which puts an upper limit before the beginning of the hypothetical superactinide series).[13] 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.[14] 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.[15]
  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.[19]
  5. ^ This figure also marks the generally accepted upper limit for lifetime of a compound nucleus.[24]
  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.[26] 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.[27]
  7. ^ Not all decay modes are caused by electrostatic repulsion. For example, beta decay is caused by the weak interaction.[34]
  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.[39]
  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.[44] The first direct measurement of mass of a superheavy nucleus was reported in 2018 at LBNL.[45] 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).[46]
  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).[35] 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,[47] a leading scientist at JINR, and thus it was a "hobbyhorse" for the facility.[48] 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.[24] They thus preferred to link new isotopes to the already known ones by successive alpha decays.[47]
  12. ^ For instance, element 102 was mistakenly identified in 1957 at the Nobel Institute of Physics in Stockholm, Stockholm County, Sweden.[49] 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.[50] 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.[50] JINR insisted that they were the first to create the element and suggested a name of their own for the new element, joliotium;[51] the Soviet name was also not accepted (JINR later referred to the naming of the element 102 as "hasty").[52] This name was proposed to IUPAC in a written response to their ruling on priority of discovery claims of elements, signed 29 September 1992.[52] The name "nobelium" remained unchanged on account of its widespread usage.[53]
  13. ^ Different sources give different values for half-lives; the most recently published values are listed.
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