Flerovium
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Flerovium | ||||||||||||||||||||||||||||||||||||||||||||||||||||
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114Fl
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Appearance | ||||||||||||||||||||||||||||||||||||||||||||||||||||
unknown | ||||||||||||||||||||||||||||||||||||||||||||||||||||
General properties | ||||||||||||||||||||||||||||||||||||||||||||||||||||
Name, symbol, number | flerovium, Fl, 114 | |||||||||||||||||||||||||||||||||||||||||||||||||||
Pronunciation | / f l ɨ ˈ r oʊ v i ə m / fli-ROH-vee-əm |
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Element category | unknown | |||||||||||||||||||||||||||||||||||||||||||||||||||
Group, period, block | 14, 7, p | |||||||||||||||||||||||||||||||||||||||||||||||||||
Standard atomic weight | [289] | |||||||||||||||||||||||||||||||||||||||||||||||||||
Electron configuration | [Rn] 5f14 6d10 7s2 7p2 (predicted) 2, 8, 18, 32, 32, 18, 4 (predicted) |
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History | ||||||||||||||||||||||||||||||||||||||||||||||||||||
Discovery | Joint Institute for Nuclear Research and Lawrence Livermore National Laboratory (1999) | |||||||||||||||||||||||||||||||||||||||||||||||||||
Physical properties | ||||||||||||||||||||||||||||||||||||||||||||||||||||
Phase | solid (predicted) | |||||||||||||||||||||||||||||||||||||||||||||||||||
Density (near r.t.) | 22 (predicted) g·cm−3 | |||||||||||||||||||||||||||||||||||||||||||||||||||
Melting point | 340 K, 70 °C, 160 (predicted) °F | |||||||||||||||||||||||||||||||||||||||||||||||||||
Boiling point | 420 K, 150 °C, 300 (predicted) °F | |||||||||||||||||||||||||||||||||||||||||||||||||||
Atomic properties | ||||||||||||||||||||||||||||||||||||||||||||||||||||
Oxidation states | 2, 4 (prediction) | |||||||||||||||||||||||||||||||||||||||||||||||||||
Ionization energies | 1st: 823.9 (prediction) kJ·mol−1 | |||||||||||||||||||||||||||||||||||||||||||||||||||
2nd: 1621.0 (prediction) kJ·mol−1 | ||||||||||||||||||||||||||||||||||||||||||||||||||||
Atomic radius | 160 (estimated) pm | |||||||||||||||||||||||||||||||||||||||||||||||||||
Covalent radius | 143 (estimated) pm | |||||||||||||||||||||||||||||||||||||||||||||||||||
Miscellanea | ||||||||||||||||||||||||||||||||||||||||||||||||||||
CAS registry number | 54085-16-4 | |||||||||||||||||||||||||||||||||||||||||||||||||||
Most stable isotopes | ||||||||||||||||||||||||||||||||||||||||||||||||||||
Main article: Isotopes of flerovium | ||||||||||||||||||||||||||||||||||||||||||||||||||||
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Flerovium is the radioactive chemical element with the symbol "Fl" and atomic number 114. The element is named after the Flerov Laboratory of Nuclear Reactions of the Joint Institute for Nuclear Research in Dubna, Russia, where the element was discovered. The name of the laboratory, in turn, honours the Russian physicist Georgy Flyorov. The name was adopted by IUPAC on May 30, 2012.
About 80 decays of atoms of flerovium have been observed to date, 50 directly and 30 from the decay of the heavier elements livermorium and ununoctium. All decays have been assigned to the five neighbouring isotopes with mass numbers 285–289. The longest-lived isotope currently known is 289Fl with a half-life of ~2.6 s, although there is evidence for a nuclear isomer, 289bFl, with a half-life of ~66 s, that would be one of the longest-lived nuclei in the superheavy element region.
Chemical studies performed in 2007–2008 indicate that flerovium is unexpectedly volatile for a group 14 element; in preliminary results it even seemed to exhibit noble-gas-like properties due to relativistic effects.
History
Discovery
In December 1998, scientists at Dubna ( Joint Institute for Nuclear Research) in Russia bombarded a 244Pu target with 48Ca ions. A single atom of flerovium, decaying by 9.67 MeV alpha-emission with a half-life of 30 s, was produced and assigned to 289Fl. This observation was subsequently published in January 1999. However, the decay chain observed has not been repeated and the exact identity of this activity is unknown, although it is possible that it is due to a meta-stable isomer, namely 289mFl.
In March 1999, the same team replaced the 244Pu target with a 242Pu one in order to produce other isotopes. This time two atoms of flerovium were produced, decaying by 10.29 MeV alpha-emission with a half-life of 5.5 s. They were assigned as 287Fl. Once again, this activity has not been seen again and it is unclear what nucleus was produced. It is possible that it was a meta-stable isomer, namely 287mFl.
The now-confirmed discovery of flerovium was made in June 1999 when the Dubna team repeated the 244Pu reaction. This time, two atoms of element 114 were produced decaying by emission of 9.82 MeV alpha particles with a half-life of 2.6 s.
This activity was initially assigned to 288Fl in error, due to the confusion regarding the above observations. Further work in Dec 2002 has allowed a positive reassignment to 289Fl.
- 244
94Pu + 48
20Ca → 292
114Fl → 289
114Fl + 3 1
0n
In May 2009, the Joint Working Party (JWP) of IUPAC published a report on the discovery of copernicium in which they acknowledged the discovery of the isotope 283Cn. This therefore implies the de facto discovery of flerovium, from the acknowledgment of the data for the synthesis of 287Fl and 291Lv (see below), relating to 283Cn. In 2011, IUPAC evaluated the Dubna team experiments of 1999–2007. Whereas they found the early data inconclusive, the results of 2004–2007 were accepted as identification of element 114.
The discovery of flerovium, as 287Fl and 286Fl, was confirmed in January 2009 at Berkeley. This was followed by confirmation of 288Fl and 289Fl in July 2009 at the GSI (see section 2.1.3).
Naming
Ununquadium (Uuq) was the temporary IUPAC systematic element name. The element is often referred to as element 114, for its atomic number.
According to IUPAC recommendations, the discoverer(s) of a new element has the right to suggest a name. The discovery of ununquadium was recognized by JWG of IUPAC on 1 June 2011, along with that of ununhexium. According to the vice-director of JINR, the Dubna team chose to name element 114 flerovium (symbol Fl), after the founder of the Russian institute, Flerov Laboratory of Nuclear Reactions, the Soviet physicist Georgy Flyorov (also spelled Flerov). However, IUPAC officially named flerovium after the Flerov Laboratory of Nuclear Reactions, not after Flerov himself. Flerov is known for writing to Stalin in April 1942 and pointing out the conspicuous silence in scientific journals within the field of nuclear fission in the United States, Great Britain, and Germany. Flyorov deduced that this research must have become classified information in those countries. Flyorov's work and urgings led to the eventual development of the USSR's own atomic bomb project.
Future experiments
The team at RIKEN have indicated plans to study the cold fusion reaction:
- 208
82Pb + 76
32Ge → 284
114Fl → ?
The FLNR have future plans to study light isotopes of flerovium, formed in the reaction between 239Pu and 48Ca.
Nucleosynthesis
- Target-projectile combinations leading to Z=114 compound nuclei
The following table contains various combinations of targets and projectiles that could be used to form compound nuclei with an atomic number of 114.
Target | Projectile | CN | Attempt result |
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208Pb | 76Ge | 284Fl | Failure to date |
232Th | 54Cr | 286Fl | Reaction yet to be attempted |
238U | 50Ti | 288Fl | Reaction yet to be attempted |
244Pu | 48Ca | 292Fl | Successful reaction |
242Pu | 48Ca | 290Fl | Successful reaction |
239Pu | 48Ca | 287Fl | Reaction yet to be attempted |
248Cm | 40Ar | 288Fl | Reaction yet to be attempted |
249Cf | 36S | 285Fl | Reaction yet to be attempted |
Cold fusion
This section deals with the synthesis of nuclei of flerovium by so-called "cold" fusion reactions. These processes create compound nuclei at low excitation energy (~10–20 MeV, hence "cold"), leading to a higher probability of survival from fission. The excited nucleus then decays to the ground state via the emission of one or two neutrons only.
- 208Pb(76Ge,xn)284−xFl
The first attempt to synthesise flerovium in cold fusion reactions was performed at Grand accélérateur national d'ions lourds (GANIL), France in 2003. No atoms were detected providing a yield limit of 1.2 pb.
Hot fusion
This section deals with the synthesis of nuclei of flerovium by so-called "hot" fusion reactions. These processes create compound nuclei at high excitation energy (~40–50 MeV, hence "hot"), leading to a reduced probability of survival from fission. The excited nucleus then decays to the ground state via the emission of 3–5 neutrons. Fusion reactions utilizing 48Ca nuclei usually produce compound nuclei with intermediate excitation energies (~30–35 MeV) and are sometimes referred to as "warm" fusion reactions. This leads, in part, to relatively high yields from these reactions.
- 244Pu(48Ca,xn)292−xFl (x=3,4,5)
The first experiments on the synthesis of flerovium were performed by the team in Dubna in November 1998. They were able to detect a single, long decay chain, assigned to 289Fl. The reaction was repeated in 1999 and a further two atoms of flerovium were detected. The products were assigned to 288Fl. The team further studied the reaction in 2002. During the measurement of the 3n, 4n, and 5n neutron evaporation excitation functions they were able to detect three atoms of 289Fl, twelve atoms of the new isotope 288Fl, and one atom of the new isotope 287Fl. Based on these results, the first atom to be detected was tentatively reassigned to 290Fl or 289mFl, whilst the two subsequent atoms were reassigned to 289Fl and therefore belong to the unofficial discovery experiment. In an attempt to study the chemistry of copernicium as the isotope 285Cn, this reaction was repeated in April 2007. Surprisingly, a PSI-FLNR directly detected two atoms of 288Fl forming the basis for the first chemical studies of flerovium.
In June 2008, the experiment was repeated to further assess the chemistry of the element using the 289Fl isotope. A single atom was detected seeming to confirm the noble-gas-like properties of the element.
During May–July 2009, the team at GSI studied this reaction for the first time, as a first step towards the synthesis of ununseptium. The team were able to confirm the synthesis and decay data for 288Fl and 289Fl, producing nine atoms of the former isotope and four atoms of the latter.
- 242Pu(48Ca,xn)290−x114 (x=2,3,4,5)
The team at Dubna first studied this reaction in March–April 1999 and detected two atoms of flerovium, assigned to 287Fl. The reaction was repeated in September 2003 to attempt to confirm the decay data for 287Fl and 283Cn since conflicting data for 283Cn had been collected (see copernicium). The Russian scientists were able to measure decay data for 288Fl, 287Fl and the new isotope 286Fl from the measurement of the 2n, 3n, and 4n excitation functions.
In April 2006, a PSI-FLNR collaboration used the reaction to determine the first chemical properties of copernicium by producing 283Cn as an overshoot product. In a confirmatory experiment in April 2007, the team were able to detect 287Fl directly and therefore measure some initial data on the atomic chemical properties of flerovium.
The team at Berkeley, using the Berkeley gas-filled separator (BGS), continued their studies using newly acquired 242Pu targets by attempting the synthesis of flerovium in January 2009 using the above reaction. In September 2009, they reported that they had succeeded in detecting two atoms of flerovium, as 287Fl and 286Fl, confirming the decay properties reported at the FLNR, although the measured cross sections were slightly lower; however the statistics were of lower quality.
In April 2009, the collaboration of Paul Scherrer Institute (PSI) and Flerov Laboratory of Nuclear Reactions (FLNR) of JINR carried out another study of the chemistry of flerovium using this reaction. A single atom of 283Cn was detected.
In December 2010, the team at the LBNL announced the synthesis of a single atom of the new isotope 285Fl with the consequent observation of 5 new isotopes of daughter elements.
As a decay product
The isotopes of flerovium have also been observed in the decay chains of livermorium and ununoctium.
Evaporation residue | Observed Fl isotope |
---|---|
293Lv | 289Fl |
292Lv | 288Fl |
291Lv | 287Fl |
294Uuo, 290Lv | 286Fl |
Isotopes and nuclear properties
- Chronology of isotope discovery
Isotope | Year discovered | Discovery reaction |
---|---|---|
285Fl | 2010 | 242Pu (48Ca, 5n) |
286Fl | 2002 | 249Cf (48Ca, 3n) |
287aFl | 2002 | 244Pu (48Ca, 5n) |
287bFl ?? | 1999 | 242Pu (48Ca, 3n) |
288Fl | 2002 | 244Pu (48Ca, 4n) |
289aFl | 1999 | 244Pu (48Ca, 3n) |
289bFl ? | 1998 | 244Pu (48Ca, 3n) |
Retracted isotopes
- 285Fl
In the claimed synthesis of 293Uuo in 1999, the isotope 285Fl was identified as decaying by 11.35 MeV alpha emission with a half-life of 0.58 ms. The claim was retracted in 2001 after it was discovered that the data has been fabricated. This isotope was finally created in 2010 and its decay properties did not match the retracted decay data.
Fission of compound nuclei with an atomic number of 114
Several experiments have been performed between 2000 and 2004 at the Flerov Laboratory of Nuclear Reactions in Dubna studying the fission characteristics of the compound nucleus 292Fl. The nuclear reaction used is 244
94Pu + 48
20Ca. The results have revealed how nuclei such as this fission predominantly by expelling closed shell nuclei such as 132Sn (Z=50, N=82). It was also found that the yield for the fusion-fission pathway was similar between 48Ca and 58Fe projectiles, indicating a possible future use of 58Fe projectiles in superheavy element formation.
Nuclear isomerism
- 289Fl
In the first claimed synthesis of flerovium, an isotope assigned as 289Fl decayed by emitting a 9.71 MeV alpha particle with a lifetime of 30 seconds. This activity was not observed in repetitions of the direct synthesis of this isotope. However, in a single case from the synthesis of 293Lv, a decay chain was measured starting with the emission of a 9.63 MeV alpha particle with a lifetime of 2.7 minutes. All subsequent decays were very similar to that observed from 289Fl, presuming that the parent decay was missed. This strongly suggests that the activity should be assigned to an isomeric level. The absence of the activity in recent experiments indicates that the yield of the isomer is ~20% compared to the supposed ground state and that the observation in the first experiment was a fortunate (or not as the case history indicates). Further research is required to resolve these issues.
- 287Fl
In a manner similar to those for 289Fl, first experiments with a 242Pu target identified an isotope 287Fl decaying by emission of a 10.29 MeV alpha particle with a lifetime of 5.5 seconds. The daughter spontaneously fissioned with a lifetime in accord with the previous synthesis of 283Cn. Both these activities have not been observed since (see copernicium). However, the correlation suggests that the results are not random and are possible due to the formation of isomers whose yield is obviously dependent on production methods. Further research is required to unravel these discrepancies.
Decay characteristics
Theoretical estimation of the alpha decay half-lives of the isotopes of the flerovium supports the experimental data. The fission-survived isotope 298Fl is predicted to have alpha decay half-life around 17 days.
In search for the island of stability: 298Fl
According to macroscopic-microscopic (MM) theory, Z=114 is the next spherical magic number. This means that such nuclei are spherical in their ground state and should have high, wide fission barriers to deformation and hence long SF partial half-lives.
In the region of Z=114, MM theory indicates that N=184 is the next spherical neutron magic number and puts forward the nucleus 298Fl as a strong candidate for the next spherical doubly magic nucleus, after 208Pb (Z=82, N=126). 298Fl is taken to be at the centre of a hypothetical " island of stability". However, other calculations using relativistic mean field (RMF) theory propose Z=120, 122, and 126 as alternative proton magic numbers depending upon the chosen set of parameters. It is possible that rather than a peak at a specific proton shell, there exists a plateau of proton shell effects from Z=114–126.
It should be noted that calculations suggest that the minimum of the shell-correction energy and hence the highest fission barrier exists for 297Uup, caused by pairing effects. Due to the expected high fission barriers, any nucleus within this island of stability exclusively decays by alpha-particle emission and, as such, the nucleus with the longest half-life is predicted to be 298Fl. The expected half-life is unlikely to reach values higher than about 10 minutes, unless the N=184 neutron shell proves to be more stabilising than predicted, for which there exists some evidence. In addition, 297Fl may have an even-longer half-life due to the effect of the odd neutron, creating transitions between similar Nilsson levels with lower Qalpha values.
In either case, an island of stability does not represent nuclei with the longest half-lives, but those that are significantly stabilized against fission by closed-shell effects.
Evidence for Z=114 closed proton shell
While evidence for closed neutron shells can be deemed directly from the systematic variation of Qalpha values for ground-state to ground-state transitions, evidence for closed proton shells comes from (partial) spontaneous fission half-lives. Such data can sometimes be difficult to extract due to low production rates and weak SF branching. In the case of Z=114, evidence for the effect of this proposed closed shell comes from the comparison between the nuclei pairings 282Cn (TSF1/2 = 0.8 ms) and 286Fl (TSF1/2 = 130 ms), and 284Cn (TSF = 97 ms) and 288Fl (TSF > 800 ms). Further evidence would come from the measurement of partial SF half-lives of nuclei with Z>114, such as 290Lv and 292Uuo (both N=174 isotones). The extraction of Z=114 effects is complicated by the presence of a dominating N=184 effect in this region.
Difficulty of synthesis of 298Fl
The direct synthesis of the nucleus 298Fl by a fusion–evaporation pathway is impossible since no known combination of target and projectile can provide 184 neutrons in the compound nucleus.
It has been suggested that such a neutron-rich isotope can be formed by the quasifission (partial fusion followed by fission) of a massive nucleus. Such nuclei tend to fission with the formation of isotopes close to the closed shells Z=20/N=20 (40Ca), Z=50/N=82 (132Sn) or Z=82/N=126 (208Pb/209Bi). If Z=114 does represent a closed shell, then the hypothetical reaction below may represent a method of synthesis:
- 204
80Hg + 136
54Xe → 298
114Fl + 40
20Ca + 2 1
0n
Recently it has been shown that the multi-nucleon transfer reactions in collisions of actinide nuclei (such as uranium and curium) might be used to synthesize the neutron rich superheavy nuclei located at the island of stability.
It is also possible that 298Fl can be synthesized by the alpha decay of a massive nucleus. Such a method would depend highly on the SF stability of such nuclei, since the alpha half-lives are expected to be very short. The yields for such reactions will also most likely be extremely small. One such reaction is:
- 244
94Pu ( 96
40Zr, 2n) → 338
134Utq → → 298
114Fl + 10 4
2He
Chemical properties
Extrapolated chemical properties
Oxidation states
Flerovium is projected to be the second member of the 7p series of chemical elements and the heaviest member of group 14 (IVA) in the Periodic Table, below lead. Each of the members of this group show the group oxidation state of +IV and the latter members have an increasing +II chemistry due to the onset of the inert pair effect. Tin represents the point at which the stability of the +II and +IV states are similar. Lead, the heaviest member, portrays a switch from the +IV state to the +II state. Flerovium should therefore follow this trend and a possess an oxidising +IV state and a stable +II state.
Chemistry
Flerovium should portray eka-lead chemical properties and should therefore form a monoxide, FlO, and dihalides, FlF2, FlCl2, FlBr2, and FlI2. If the +IV state is accessible, it is likely that it is only possible in the oxide, FlO2, and fluoride, FlF4. It may also show a mixed oxide, Fl3O4, analogous to Pb3O4.
Some studies also suggest that the chemical behaviour of flerovium might in fact be closer to that of the noble gas radon, than to that of lead.
Calculations suggest that flerovium will not form a tetrafluoride, FlF4, but will form a difluoride (FlF2) that is soluble in water.
Experimental chemistry
Atomic gas phase
Two experiments were performed in April–May 2007 in a joint FLNR-PSI collaboration aiming to study the chemistry of copernicium. The first experiment involved the reaction 242Pu(48Ca,3n)287Fl and the second the reaction 244Pu(48Ca,4n)288Fl. The adsorption properties of the resultant atoms on a gold surface were compared with those of radon. The first experiment allowed detection of 3 atoms of 283Cn but also seemingly detected 1 atom of 287Fl. This result was a surprise given the transport time of the product atoms is ~2 s, so flerovium atoms should decay before adsorption. In the second reaction, 2 atoms of 288Fl and possibly 1 atom of 289Fl were detected. Two of the three atoms portrayed adsorption characteristics associated with a volatile, noble-gas-like element, which has been suggested but is not predicted by more recent calculations. These experiments did however provide independent confirmation for the discovery of copernicium, flerovium, and livermorium via comparison with published decay data. Further experiments in 2008 to confirm this important result detected a single atom of 289Fl—which provided data that agreed with previous data that supported flerovium having a noble-gas-like interaction with gold.
In April 2009, the FLNR-PSI collaboration synthesized a further atom of flerovium.