Copernicium

Copernicium,  ₁₁₂Cn

General properties
Name, symbol	copernicium, Cn
Pronunciation	/koʊpərˈnɪsiəm/ koe-pər-NIS-ee-əm
Copernicium in the periodic table
Hg ↑ Cn ↓ (Uhq) roentgenium ← copernicium → ununtrium
Atomic number (Z)	112
Group, block	group 12, d-block
Period	period 7
Element category	transition metal
Standard atomic weight (Ar)	[285]
Electron configuration	[Rn] 5f14 6d10 7s2 (predicted)
per shell	2, 8, 18, 32, 32, 18, 2 (predicted)
Physical properties
Phase	unknown
Boiling point	357+112 −108 K ​(84+112 −108 °C, ​183+202 −194 °F)
Density near r.t.	23.7 g/cm3 (predicted)
Atomic properties
Oxidation states	4, 2, 1, 0 ​(predicted)
Ionization energies	1st: 1154.9 kJ/mol 2nd: 2170.0 kJ/mol 3rd: 3164.7 kJ/mol (more) (all estimated)
Atomic radius	empirical: 147 pm (predicted)
Covalent radius	122 pm (predicted)
Miscellanea
Crystal structure	​hexagonal close-packed (hcp) (predicted)
CAS Number	54084-26-3
History
Naming	after Nicolaus Copernicus
Discovery	Gesellschaft für Schwerionenforschung (1996)
Most stable isotopes of copernicium
iso NA half-life DM DE (MeV) DP 285Cn syn 29 s α 9.15, 9.03? 281Ds 285mCn ? syn 8.9 min α 8.63 281mDs ? 283Cn syn 4 s 90% α 9.53, 9.32, 8.94 279Ds 10% SF 283mCn ?? syn ~7.0 min SF

Copernicium is a chemical element with symbol Cn and atomic number 112. It is an extremely radioactive synthetic element that can only be created in a laboratory. The most stable known isotope, copernicium-285, has a half-life of approximately 29 seconds, but it is possible that this copernicium isotope may have a nuclear isomer with a longer half-life, 8.9 min. Copernicium was first created in 1996 by the GSI Helmholtz Centre for Heavy Ion Research near Darmstadt, Germany. It is named after the astronomer Nicolaus Copernicus.

In the periodic table of the elements, it is a d-block transactinide element. During reactions with gold, it has been shown to be an extremely volatile metal and a group 12 element, and it may even be a gas at standard temperature and pressure. Copernicium is calculated to have several properties that differ between it and its lighter homologues, zinc, cadmium and mercury; the most notable of them is withdrawing two 6d-electrons before 7s ones due to relativistic effects, which confirm copernicium as an undisputed transition metal. Copernicium is also calculated to show a predominance of the oxidation state +4, while mercury shows it in only one compound at extreme conditions and zinc and cadmium do not show it at all. It has also been predicted to be more difficult to oxidise copernicium from its neutral state than the other group 12 elements.

In total, approximately 75 atoms of copernicium have been detected using various nuclear reactions.

History

Official discovery

Copernicium was first created on February 9, 1996, at the Gesellschaft für Schwerionenforschung (GSI) in Darmstadt, Germany, by Sigurd Hofmann, Victor Ninov et al. This element was created by firing accelerated zinc-70 nuclei at a target made of lead-208 nuclei in a heavy ion accelerator. A single atom (the second was subsequently dismissed) of copernicium was produced with a mass number of 277.

²⁰⁸
₈₂Pb + ⁷⁰
₃₀Zn → ²⁷⁸
₁₁₂Cn* → ²⁷⁷
₁₁₂Cn + ¹
₀n

In May 2000, the GSI successfully repeated the experiment to synthesize a further atom of copernicium-277. This reaction was repeated at RIKEN using the Search for a Super-Heavy Element Using a Gas-Filled Recoil Separator set-up in 2004 and 2013 to synthesize three further atoms and confirm the decay data reported by the GSI team.[1]

The IUPAC/IUPAP Joint Working Party (JWP) assessed the claim of discovery by the GSI team in 2001 and 2003. In both cases, they found that there was insufficient evidence to support their claim. This was primarily related to the contradicting decay data for the known nuclide rutherfordium-261. However, between 2001 and 2005, the GSI team studied the reaction ²⁴⁸Cm(²⁶Mg,5n)²⁶⁹Hs, and were able to confirm the decay data for hassium-269 and rutherfordium-261. It was found that the existing data on rutherfordium-261 was for an isomer, now designated rutherfordium-261m.

In May 2009, the JWP reported on the claims of discovery of element 112 again and officially recognized the GSI team as the discoverers of element 112. This decision was based on the confirmation of the decay properties of daughter nuclei as well as the confirmatory experiments at RIKEN.

Naming

Nicolaus Copernicus, who postulated the heliocentric theory that the Earth orbits around the Sun, contradicting prior belief.

Using Mendeleev's nomenclature for unnamed and undiscovered elements, copernicium should be known as eka-mercury. In 1979, IUPAC published recommendations according to which the element was to be called ununbium (with the corresponding symbol of Uub), a systematic element name as a placeholder, until the element was discovered (and the discovery then confirmed) and a permanent name was decided on. Although widely used in the chemical community on all levels, from chemistry classrooms to advanced textbooks, the recommendations were mostly ignored among scientists in the field, who either called it "element 112", with the symbol of (112) or even simply 112.

After acknowledging the GSI team's discovery, the IUPAC asked them to suggest a permanent name for element 112. On 14 July 2009, they proposed copernicium with the element symbol Cp, after Nicolaus Copernicus "to honor an outstanding scientist, who changed our view of the world".

During the standard six-month discussion period among the scientific community about the naming, it was pointed out that the symbol Cp was previously associated with the name cassiopeium (cassiopium), now known as lutetium (Lu). For this reason, the IUPAC disallowed the use of Cp as a future symbol, prompting the GSI team to put forward the symbol Cn as an alternative. On 19 February 2010, the 537th anniversary of Copernicus' birth, IUPAC officially accepted the proposed name and symbol.

Isotopes

Main article: Isotopes of copernicium

List of copernicium isotopes

Isotope	Half-life	Decay mode	Discovery year	Reaction
277Cn	0.69 ms	α	1996	208Pb(70Zn,n)
278Cn	10? ms	α, SF ?	unknown	—
279Cn	0.2? ms	α, SF ?	unknown	—
280Cn	0.5? ms	α, SF ?	unknown	—
281Cn	97 ms	α	2010	285Fl(—,α)
282Cn	0.8 ms	SF	2004	238U(48Ca,4n)
283Cn	4 s	α, SF	2002	238U(48Ca,3n)
283bCn ?	5 min ?	α	1998	238U(48Ca,3n)
284Cn	97 ms	SF	2002	288Fl(—,α)
285Cn	29 s	α	1999	289Fl(—,α)
285bCn ?	8.9 min ?	α	1999	289Fl(—,α)

Copernicium 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. Six different isotopes have been reported with atomic masses from 281 to 285, and 277, two of which, copernicium-283 and copernicium-285, have known metastable states. Most of these decay predominantly through alpha decay, but some undergo spontaneous fission.

The isotope copernicium-283 was instrumental in the confirmation of the discoveries of the elements flerovium and livermorium.

Half-lives

All copernicium isotopes are extremely unstable and radioactive; in general, heavier isotopes are more stable than the lighter. The most stable isotope, copernicium-285, has a half-life of 29 seconds, although it is suspected that this isotope has an isomer with a half-life of 8.9 minutes, and copernicium-283 may have an isomer with a half-life of about 5 minutes. Other isotopes have half-lives shorter than 0.1 seconds. Copernicium-281 and copernicium-284 have half-life of 97 ms, and the other two isotopes have half-lives slightly under one millisecond. It is predicted that the heavy isotopes copernicium-291 and copernicium-293 may have half-lives of around 1200 years, and may have been produced in the r-process and be detectable in cosmic rays, though they would be about 10⁻¹² times as abundant as lead.

The lightest isotopes were synthesized by direct fusion between two lighter nuclei and as decay products (except for copernicium-277, which is known to be a decay product), while the heavier isotopes are only known to be produced by decay of heavier nuclei. The heaviest isotope produced by direct fusion is copernicium-283; the two heavier isotopes, copernicium-284 and copernicium-285 have only been observed as decay products of elements with larger atomic numbers. In 1999, American scientists at the University of California, Berkeley, announced that they had succeeded in synthesizing three atoms of ²⁹³118. These parent nuclei were reported to have successively emitted three alpha particles to form copernicium-281 nuclei, which were claimed to have undergone an alpha decay, emitting an alpha particle with decay energy of 10.68 MeV and half-life 0.90 ms, but their claim was retracted in 2001. The isotope, however, was produced in 2010 by the same team. The new data contradicted the previous (fabricated) data.

Predicted properties

Chemical

Copernicium is the last member of the 6d series of transition metals and the heaviest group 12 element in the periodic table, below zinc, cadmium and mercury. It is predicted to differ significantly from the lighter group 12 elements. Due to stabilization of 7s electronic orbitals and destabilization of 6d ones caused by relativistic effects, Cn²⁺ is likely to have a [Rn]5f¹⁴6d⁸7s² electronic configuration, using the 6d orbitals before the 7s one, unlike its homologues. The fact that the 6d electrons participate readily in chemical bonding mean that copernicium should behave more like a transition metal than its lighter homologues, especially in the +4 oxidation state. In water solutions, copernicium is likely to form the +2 and +4 oxidation states, with the latter one being more stable. Among the lighter group 12 members, for which the +2 oxidation state is the most common, only mercury can show the +4 oxidation state, but it is highly uncommon, existing at only one compound (mercury(IV) fluoride, HgF₄) at extreme conditions. The analogous compound for copernicium, copernicium(IV) fluoride (CnF₄), is predicted to be more stable. The diatomic ion Hg²⁺
₂, featuring mercury in +1 oxidation state is well-known, but the Cn²⁺
₂ ion is predicted to be unstable or even non-existent. Oxidation of copernicium from its neutral state is also likely to be more difficult than those of previous group 12 members. Copernicium(II) fluoride, CnF₂, should be more unstable than the analogous mercury compound, mercury(II) fluoride (HgF₂), and may even decompose spontaneously into its constituent elements. In polar solvents, copernicium is predicted to preferentially form the CnF⁻
₅ and CnF⁻
₃ anions rather than the analogous neutral fluorides (CnF₄ and CnF₂, respectively), although the analogous bromide or iodide ions may be more stable towards hydrolysis in aqueous solution. The anions CnCl²⁻
₄ and CnBr²⁻
₄ should also be able to exist in aqueous solution.

The valence s-subshells of the group 12 elements and period 7 elements are expected to be relativistically contracted most strongly at copernicium. This and the closed-shell configuration of copernicium result in it probably being a very noble metal. Its metallic bonds should also be very weak, possibly making it extremely volatile, like the noble gases, and potentially making it gaseous at room temperature. However, it should be able to form metal–metal bonds with copper, palladium, platinum, silver, and gold; these bonds are predicted to be only about 15–20 kJ/mol weaker than the analogous bonds with mercury.

Physical and atomic

Copernicium should be a very heavy metal with a density of around 23.7 g/cm³ in the solid state; in comparison, the most dense known element that has had its density measured, osmium, has a density of only 22.61 g/cm³. This results from copernicium's high atomic weight, the lanthanide and actinide contractions, and relativistic effects, although production of enough copernicium to measure this quantity would be impractical, and the sample would quickly decay. However, some calculations predict copernicium to be a gas at room temperature, the first gaseous metal in the periodic table (the second being flerovium), due to the closed-shell electron configurations of copernicium and flerovium. The atomic radius of copernicium is expected to be around 147 pm. Due to the relativistic stabilization of the 7s orbital and destabilization of the 6d orbital, the Cn⁺ and Cn²⁺ ions are predicted to give up 6d electrons instead of 7s electrons, which is the opposite of the behavior of its lighter homologues.

In addition to the relativistic contraction and binding of the 7s subshell, the 6d_5/2 orbital is expected to be destabilized due to spin-orbit coupling, making it behave similarly to the 7s orbital in terms of size, shape, and energy. Hence copernicium may not be a noble transition metal, but rather a semiconductor with a band gap of around 0.2 eV. Copernicium is expected to crystallize in the hexagonal close-packed crystal structure, with lattice parameters a = 332 pm and c = 540 pm. The ^c/_a ratio of 1.63 is the ideal value, establishing a kinship between solid copernicium and the solid noble gases, though its cohesive energy (enthalpy of crystallization) should be on the order of that of mercury rather than be near the lower value of the noble gases.

Experimental atomic gas phase chemistry

Interest in copernicium's chemistry was sparked by predictions that it would have the largest relativistic effects in the whole of period 7 and group 12. Copernicium has the ground state electron configuration [Rn]5f¹⁴6d¹⁰7s² and thus should belong to group 12 of the periodic table, according to the Aufbau principle. As such, it should behave as the heavier homologue of mercury and form strong binary compounds with noble metals like gold. Experiments probing the reactivity of copernicium have focused on the adsorption of atoms of element 112 onto a gold surface held at varying temperatures, in order to calculate an adsorption enthalpy. Owing to relativistic stabilization of the 7s electrons, copernicium shows radon-like properties. Experiments were performed with the simultaneous formation of mercury and radon radioisotopes, allowing a comparison of adsorption characteristics.

The first experiments were conducted using the ²³⁸U(⁴⁸Ca,3n)²⁸³Cn reaction. Detection was by spontaneous fission of the claimed parent isotope with half-life of 5 minutes. Analysis of the data indicated that copernicium was more volatile than mercury and had noble gas properties. However, the confusion regarding the synthesis of copernicium-283 has cast some doubt on these experimental results. Given this uncertainty, between April–May 2006 at the JINR, a FLNR–PSI team conducted experiments probing the synthesis of this isotope as a daughter in the nuclear reaction ²⁴²Pu(⁴⁸Ca,3n)²⁸⁷Fl. In this experiment, two atoms of copernicium-283 were unambiguously identified and the adsorption properties indicated that copernicium is a more volatile homologue of mercury, due to formation of a weak metal-metal bond with gold, placing it firmly in group 12.

In April 2007, this experiment was repeated and a further three atoms of copernicium-283 were positively identified. The adsorption property was confirmed and indicated that copernicium has adsorption properties completely in agreement with being the heaviest member of group 12. These experiments also allowed the first experimental estimation of copernicium's boiling point: 84⁺¹¹²
₋₁₀₈ °C.

See also

• Island of stability

External links

• Copernicium at The Periodic Table of Videos (University of Nottingham)