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Not to be confused with borium.

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 states(+3), (+4), (+5), +7[4][8] (parenthesized: prediction)
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)[9]
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[10] 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[11] α 267Db
272Bh synth 8.8 s α 268Db
274Bh synth 40 s[12] 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 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

See also: Superheavy element § Introduction
This section is an excerpt from Superheavy element.[edit]
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 103. 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 second, 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.)

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.[20] 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.[21]

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:[22]

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.[21]

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.[23]

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.[24] 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.[24][25] 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;[24] the names of the respective oxyanions of boron and bohrium remain unchanged despite their homophony.[26]

Isotopes

Main article: Isotopes of bohrium
List of bohrium isotopes
Isotope
 Half-life
[27][28]		 Decay
mode[27][28]		 Discovery
year		 Reaction
260Bh 35 ms α 2007 209Bi(52Cr,n)[29]
261Bh 11.8 ms α 1986 209Bi(54Cr,2n)[30]
262Bh 84 ms α 1981 209Bi(54Cr,n)[22]
262mBh 9.6 ms α 1981 209Bi(54Cr,n)[22]
264Bh 0.97 s α 1994 272Rg(—,2α)[31]
265Bh 0.9 s α 2004 243Am(26Mg,4n)[32]
266Bh 0.9 s α 2000 249Bk(22Ne,5n)[33]
267Bh 17 s α 2000 249Bk(22Ne,4n)[33]
270Bh 2.4 min[1] α 2006 282Nh(—,3α)[34]
271Bh 2.9 s[1] α 2003 287Mc(—,4α)[34]
272Bh 8.8 s[1] α 2005 288Mc(—,4α)[34]
274Bh 40 s α 2009 294Ts(—,5α)[12]
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.[27]

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, one of the longest-lived known superheavy nuclides.[35]

Predicted properties

Very few properties of bohrium or its compounds have been measured; this is due to its extremely limited and expensive production[36] 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.[8] 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]

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.[37] 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]

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.[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]

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.[38]

In 2000, it was confirmed that although relativistic effects are important, bohrium behaves like a typical group 7 element.[39] 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.[40] 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.[41]

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]

References

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Bibliography

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