\( \require{mhchem} \)
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
See also: Superheavy element § Introduction
The heaviest[a] atomic nuclei are created in nuclear reactions that combine two other nuclei of unequal size[b] into one; roughly, the more unequal the two nuclei in terms of mass, the greater the possibility that the two react.[18] 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 fuse into one only 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.[19] Coming close 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.[19][20] If fusion does occur, the temporary merger—termed a compound nucleus—is an excited state. To lose its excitation energy and reach a more stable state, a compound nucleus either fissions or ejects one or several neutrons,[c] which carry away the energy. This occurs in approximately 10−16 seconds after the initial collision.[21][d]
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.[24] In the separator, the newly produced nucleus is separated from other nuclides (that of the original beam and any other reaction products)[e] 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.[24] The transfer takes about 10−6 seconds; in order to be detected, the nucleus must survive this long.[27] The nucleus is recorded again once its decay is registered, and the location, the energy, and the time of the decay are measured.[24]
Stability of a nucleus is provided by the strong interaction. However, its range is very short; as nuclei become larger, their influence on the outermost nucleons (protons and neutrons) weakens. At the same time, the nucleus is torn apart by electrostatic repulsion between protons, as it has unlimited range.[28] Nuclei of the heaviest elements are thus theoretically predicted[29] and have so far been observed[30] to primarily decay via decay modes that are caused by such repulsion: alpha decay and spontaneous fission;[f] these modes are predominant for nuclei of superheavy elements. 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 determined arithmetically.[g] Spontaneous fission, however, produces various nuclei as products, so the original nuclide cannot be determined from its daughters.[h]
The information available to physicists aiming to synthesize one of the heaviest elements 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.[i]
Niels Bohr
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.[42] 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.[43]
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:[44]
20983Bi+ 5424Cr→ 262107Bh+ 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.[43]
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.[45]
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.[46] 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.[46][47] 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;[46] the names of the respective oxyanions of boron and bohrium remain unchanged despite their homophony.[48]
Isotopes
Main article: Isotopes of bohrium
List of bohrium isotopes
vte
| Isotope | Half-life[j] | Decay mode |
Discovery year |
Discovery reaction |
|
|---|---|---|---|---|---|
| Value | ref | ||||
| 260Bh | 41 ms | [8] | α | 2007 | 209Bi(52Cr,n)[49] |
| 261Bh | 12.8 ms | [8] | α | 1986 | 209Bi(54Cr,2n)[50] |
| 262Bh | 84 ms | [8] | α | 1981 | 209Bi(54Cr,n)[44] |
| 262mBh | 9.5 ms | [8] | α | 1981 | 209Bi(54Cr,n)[44] |
| 264Bh | 1.07 s | [8] | α | 1994 | 272Rg(—,2α)[51] |
| 265Bh | 1.19 s | [8] | α | 2004 | 243Am(26Mg,4n)[52] |
| 266Bh | 10.6 s | [8] | α | 2000 | 249Bk(22Ne,5n)[53] |
| 267Bh | 22 s | [8] | α | 2000 | 249Bk(22Ne,4n)[53] |
| 270Bh | 2.4 min | [54] | α | 2006 | 282Nh(—,3α)[55] |
| 271Bh | 2.9 s | [54] | α | 2003 | 287Mc(—,4α)[55] |
| 272Bh | 8.8 s | [54] | α | 2005 | 288Mc(—,4α)[55] |
| 274Bh | 57 s | [8] | α | 2009 | 294Ts(—,5α)[10] |
| 278Bh | 11.5 min? | [11] | 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.[56]
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.[57]
Predicted properties
Very few properties of bohrium or its compounds have been measured; this is due to its extremely limited and expensive production[58] 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.[6] 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).[2]
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.[59] 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.[2]
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.[3] Early predictions by Fricke estimated its density at 37.1 g/cm3,[2] but newer calculations predict a somewhat lower value of 26–27 g/cm3.[4][5]
The atomic radius of bohrium is expected to be around 128 pm.[2] 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.[2] 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.[2]
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.[60]
In 2000, it was confirmed that although relativistic effects are important, bohrium behaves like a typical group 7 element.[61] 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.[62] 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]
- 2 Bh + 3 O2 + 2 HCl → 2 BhO3Cl + H2
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.[63]
Notes
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[13] or 112;[14] sometimes, the term is presented an equivalent to the term "transactinide", which puts an upper limit before the beginning of the hypothetical superactinide series).[15] 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.
In 2009, a team at 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.[16] 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.[17]
The greater the excitation energy, the more neutrons are ejected. If the excitation energy is lower than energy binding each neutron to the rest of the nucleus, neutrons are not emitted; instead, the compound nucleus de-excites by emitting a gamma ray.[21]
The definition by the IUPAC/IUPAP Joint Working Party 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.[22] This figure also marks the generally accepted upper limit for lifetime of a compound nucleus.[23]
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.[25] 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.[26]
Not all decay modes are caused by electrostatic repulsion. For example, beta decay is caused by the weak interaction.[31]
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 heaviest nuclei.[32] The first direct measurement of mass of a superheavy nucleus was reported in 2018 at LBNL.[33] 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).[34]
Spontaneous fission was discovered by Soviet physicist Georgy Flerov,[35] a leading scientist at JINR, and thus it was a "hobbyhorse" for the facility.[36] 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.[23] They thus preferred to link new isotopes to the already known ones by successive alpha decays.[35]
For instance, element 102 was mistakenly identified in 1957 at the Nobel Institute of Physics in Stockholm, Stockholm County, Sweden.[37] 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.[38] The following year, LBNL was unable to reproduce the Swedish results and announced instead their synthesis of the element; that claim was also disproved later.[38] JINR insisted that they were the first to create the element and suggested a name of their own for the new element, joliotium;[39] the Soviet name was also not accepted (JINR later referred to the naming of element 102 as "hasty").[40] The name "nobelium" remained unchanged on account of its widespread usage.[41]
Different sources give different values for half-lives; the most recently published values are listed.
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| Periodic table | |||||||||||||||||||||||||||||||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| H | He | ||||||||||||||||||||||||||||||||||||||||
| Li | Be | B | C | N | O | F | Ne | ||||||||||||||||||||||||||||||||||
| Na | Mg | Al | Si | P | S | Cl | Ar | ||||||||||||||||||||||||||||||||||
| K | Ca | Sc | Ti | V | Cr | Mn | Fe | Co | Ni | Cu | Zn | Ga | Ge | As | Se | Br | Kr | ||||||||||||||||||||||||
| Rb | Sr | Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd | Ag | Cd | In | Sn | Sb | Te | I | Xe | ||||||||||||||||||||||||
| Cs | Ba | La | Ce | Pr | Nd | Pm | Sm | Eu | Gd | Tb | Dy | Ho | Er | Tm | Yb | Lu | Hf | Ta | W | Re | Os | Ir | Pt | Au | Hg | Tl | Pb | Bi | Po | At | Rn | ||||||||||
| Fr | Ra | Ac | Th | Pa | U | Np | Pu | Am | Cm | Bk | Cf | Es | Fm | Md | No | Lr | Rf | Db | Sg | Bh | Hs | Mt | Ds | Rg | Cn | Nh | Fl | Mc | Lv | Ts | Og | ||||||||||
|
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