Chemistry:Roentgenium

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Roentgenium, 111Rg
Roentgenium
Pronunciation
Appearancesilvery (predicted)[1]
Mass number[282] (unconfirmed: 286)
Roentgenium 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
Au

Rg

(Uhp)
darmstadtiumroentgeniumcopernicium
Atomic number (Z)111
Groupgroup 11
Periodperiod 7
Block  d-block
Element category  d-block, but probably a transition metal
Electron configuration[Rn] 5f14 6d9 7s2 (predicted)[1][2]
Electrons per shell2, 8, 18, 32, 32, 17, 2 (predicted)
Physical properties
Phase at STPsolid (predicted)[3]
Density (near r.t.)28.7 g/cm3 (predicted)[2]
Atomic properties
Oxidation states(−1), (+1), (+3), (+5), (+7) (predicted)[2][4][5]
Ionization energies
  • 1st: 1020 kJ/mol
  • 2nd: 2070 kJ/mol
  • 3rd: 3080 kJ/mol
  • (more) (all estimated)[2]
Atomic radiusempirical: 138 pm (predicted)[2][6]
Covalent radius121 pm (estimated)[7]
Other properties
Natural occurrencesynthetic
Crystal structurebody-centered cubic (bcc)
Body-centered cubic crystal structure for roentgenium

(predicted)[3]
CAS Number54386-24-2
History
Namingafter Wilhelm Röntgen
DiscoveryGesellschaft für Schwerionenforschung (1994)
Main isotopes of roentgenium
Iso­tope Abun­dance Physics:Half-life (t1/2) Decay mode Pro­duct
272Rg syn 2 ms α 268Mt
274Rg syn 12 ms α 272Mt


278Rg syn 4 ms α 274Mt
279Rg syn 0.09 s α 275Mt
280Rg syn 4.6 s α 276Mt
281Rg[8][9] syn 17 s SF (90%)
α (10%) 277Mt
282Rg[10] syn 100 s α 278Mt
283Rg[11] syn 5.1 min? SF
286Rg[12] syn 10.7 min? α 282Mt
Category Category: Roentgenium
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Check temperatures Rg: no input for C, K, F.

Check temperatures Rg: no input for C, K, F.

Roentgenium (German: [ʁœntˈɡeːni̯ʊm] (About this soundlisten)) is a synthetic chemical element; it has symbol Rg and atomic number 111. It is extremely radioactive and can only be created in a laboratory. The most stable known isotope, roentgenium-282, has a half-life of 120 seconds, although the unconfirmed roentgenium-286 may have a longer half-life of about 10.7 minutes. Roentgenium was first created in 1994 by the GSI Helmholtz Centre for Heavy Ion Research near Darmstadt, Germany. It is named after the physicist Wilhelm Röntgen (also spelled Roentgen), who discovered X-rays. Only a few roentgenium atoms have ever been synthesized, and they have no practical application.

In the periodic table, it is a d-block transactinide element. It is a member of the 7th period and is placed in the group 11 elements, although no chemical experiments have been carried out to confirm that it behaves as the heavier homologue to gold in group 11 as the ninth member of the 6d series of transition metals. Roentgenium is calculated to have similar properties to its lighter homologues, copper, silver, and gold, although it may show some differences from them. Roentgenium is thought to be a solid at room temperature and to have a metallic appearance in its regular state.

Introduction

History

Roentgenium was named after the physicist Wilhelm Röntgen, the discoverer of X-rays.

Official discovery

Roentgenium was first synthesized by an international team led by Sigurd Hofmann at the Gesellschaft für Schwerionenforschung (GSI) in Darmstadt, Germany , on December 8, 1994.[13] The team bombarded a target of bismuth-209 with accelerated nuclei of nickel-64 and detected three nuclei of the isotope roentgenium-272:

20983Bi + 6428Ni272111Rg + 10neutron

This reaction had previously been conducted at the Joint Institute for Nuclear Research in Dubna (then in the Soviet Union) in 1986, but no atoms of 272Rg had then been observed.[14] In 2001, the IUPAC/IUPAP Joint Working Party (JWP) concluded that there was insufficient evidence for the discovery at that time.[15] The GSI team repeated their experiment in 2002 and detected three more atoms.[16][17] In their 2003 report, the JWP decided that the GSI team should be acknowledged for the discovery of this element.[18]

Backdrop for presentation of the discovery and recognition of roentgenium at GSI Darmstadt

Naming

Using Mendeleev's nomenclature for unnamed and undiscovered elements, roentgenium should be known as eka-gold. In 1979, IUPAC published recommendations according to which the element was to be called unununium (with the corresponding symbol of Uuu),[19] 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 called it element 111, with the symbol of E111, (111) or even simply 111.[2]

The name roentgenium (Rg) was suggested by the GSI team[20] in 2004, to honor the German physicist Wilhelm Conrad Röntgen, the discoverer of X-rays.[20] This name was accepted by IUPAC on November 1, 2004.[20]

Isotopes

Main page: Physics:Isotopes of roentgenium
List of roentgenium isotopes
Isotope Half-life[lower-alpha 1] Decay
mode
Discovery
year[21]
Discovery
reaction[22]
Value Ref
272Rg 0000045 4.5 ms [21] α 1994 209Bi(64Ni,n)
274Rg 000029 29 ms [21] α 2004 278Nh(—,α)
278Rg 0000046 4.6 ms [23] α 2006 282Nh(—,α)
279Rg 000090 90 ms [23] α, SF 2003 287Mc(—,2α)
280Rg 0039 3.9 s [23] α, EC 2003 288Mc(—,2α)
281Rg 011 11 s [23] SF, α 2010 293Ts(—,3α)
282Rg 100 1.7 min [24] α 2010 294Ts(—,3α)
283Rg[lower-alpha 2] 306 5.1 min [25] SF 1999 283Cn(ee)
286Rg[lower-alpha 2] 640 10.7 min [26] α 1998 290Fl(eeα)


Roentgenium has no stable or naturally occurring isotopes. Several radioactive isotopes have been synthesized in the laboratory, either by fusion of the nuclei of lighter elements or as intermediate decay products of heavier elements. Nine different isotopes of roentgenium have been reported with atomic masses 272, 274, 278–283, and 286 (283 and 286 unconfirmed), two of which, roentgenium-272 and roentgenium-274, have known but unconfirmed metastable states. All of these decay through alpha decay or spontaneous fission,[27] though 280Rg may also have an electron capture branch.[28]

Stability and half-lives

All roentgenium isotopes are extremely unstable and radioactive; in general, the heavier isotopes are more stable than the lighter. The most stable known roentgenium isotope, 282Rg, is also the heaviest known roentgenium isotope; it has a half-life of 100 seconds. The unconfirmed 286Rg is even heavier and appears to have an even longer half-life of about 10.7 minutes, which would make it one of the longest-lived superheavy nuclides known; likewise, the unconfirmed 283Rg appears to have a long half-life of about 5.1 minutes. The isotopes 280Rg and 281Rg have also been reported to have half-lives over a second. The remaining isotopes have half-lives in the millisecond range.[27]

Predicted properties

Other than nuclear properties, no properties of roentgenium or its compounds have been measured; this is due to its extremely limited and expensive production[29] and the fact that roentgenium (and its parents) decays very quickly. Properties of roentgenium metal remain unknown and only predictions are available.

Chemical

Roentgenium is the ninth member of the 6d series of transition metals.[30] Calculations on its ionization potentials and atomic and ionic radii are similar to that of its lighter homologue gold, thus implying that roentgenium's basic properties will resemble those of the other group 11 elements, copper, silver, and gold; however, it is also predicted to show several differences from its lighter homologues.[2]

Roentgenium is predicted to be a noble metal. The standard electrode potential of 1.9 V for the Rg3+/Rg couple is greater than that of 1.5 V for the Au3+/Au couple. Roentgenium's predicted first ionisation energy of 1020 kJ/mol almost matches that of the noble gas radon at 1037 kJ/mol.[2] Based on the most stable oxidation states of the lighter group 11 elements, roentgenium is predicted to show stable +5 and +3 oxidation states, with a less stable +1 state. The +3 state is predicted to be the most stable. Roentgenium(III) is expected to be of comparable reactivity to gold(III), but should be more stable and form a larger variety of compounds. Gold also forms a somewhat stable −1 state due to relativistic effects, and it has been suggested roentgenium may do so as well:[2] nevertheless, the electron affinity of roentgenium is expected to be around 1.6 eV (37 kcal/mol), significantly lower than gold's value of 2.3 eV (53 kcal/mol), so roentgenides may not be stable or even possible.[4] The 6d orbitals are destabilized by relativistic effects and spin–orbit interactions near the end of the fourth transition metal series, thus making the high oxidation state roentgenium(V) more stable than its lighter homologue gold(V) (known only in gold pentafluoride, Au2F10) as the 6d electrons participate in bonding to a greater extent. The spin-orbit interactions stabilize molecular roentgenium compounds with more bonding 6d electrons; for example, RgF6 is expected to be more stable than RgF4, which is expected to be more stable than RgF2.[2] The stability of RgF6 is homologous to that of AuF6; the silver analogue AgF6 is unknown and is expected to be only marginally stable to decomposition to AgF4 and F2. Moreover, Rg2F10 is expected to be stable to decomposition, exactly analogous to the Au2F10, whereas Ag2F10 should be unstable to decomposition to Ag2F6 and F2. Gold heptafluoride, AuF7, is known as a gold(V) difluorine complex AuF5·F2, which is lower in energy than a true gold(VII) heptafluoride would be; RgF7 is instead calculated to be more stable as a true roentgenium(VII) heptafluoride, although it would be somewhat unstable, its decomposition to Rg2F10 and F2 releasing a small amount of energy at room temperature.[5] Roentgenium(I) is expected to be difficult to obtain.[2][31][32] Gold readily forms the cyanide complex Au(CN)2, which is used in its extraction from ore through the process of gold cyanidation; roentgenium is expected to follow suit and form Rg(CN)2.[33]

The probable chemistry of roentgenium has received more interest than that of the two previous elements, meitnerium and darmstadtium, as the valence s-subshells of the group 11 elements are expected to be relativistically contracted most strongly at roentgenium.[2] Calculations on the molecular compound RgH show that relativistic effects double the strength of the roentgenium–hydrogen bond, even though spin–orbit interactions also weaken it by 0.7 eV (16 kcal/mol). The compounds AuX and RgX, where X = F, Cl, Br, O, Au, or Rg, were also studied.[2][34] Rg+ is predicted to be the softest metal ion, even softer than Au+, although there is disagreement on whether it would behave as an acid or a base.[35][36] In aqueous solution, Rg+ would form the aqua ion [Rg(H2O)2]+, with an Rg–O bond distance of 207.1 pm. It is also expected to form Rg(I) complexes with ammonia, phosphine, and hydrogen sulfide.[36]

Physical and atomic

Roentgenium is expected to be a solid under normal conditions and to crystallize in the body-centered cubic structure, unlike its lighter congeners which crystallize in the face-centered cubic structure, due to its being expected to have different electron charge densities from them.[3] It should be a very heavy metal with a density of around 22–24 g/cm3; in comparison, the densest known element that has had its density measured, osmium, has a density of 22.61 g/cm3.[37][38] The atomic radius of roentgenium is expected to be around 138 pm.[2]

Experimental chemistry

Unambiguous determination of the chemical characteristics of roentgenium has yet to have been established[39] due to the low yields of reactions that produce roentgenium isotopes.[2] For chemical studies to be carried out on a transactinide, at least four atoms must be produced, the half-life of the isotope used must be at least 1 second, and the rate of production must be at least one atom per week.[30] Even though the half-life of 282Rg, the most stable confirmed roentgenium isotope, is 100 seconds, long enough to perform chemical studies, another obstacle is the need to increase the rate of production of roentgenium isotopes and allow experiments to carry on for weeks or months so that statistically significant results can be obtained. Separation and detection must be carried out continuously to separate out the roentgenium isotopes and allow automated systems to experiment on the gas-phase and solution chemistry of roentgenium, as the yields for heavier elements are predicted to be smaller than those for lighter elements. However, the experimental chemistry of roentgenium has not received as much attention as that of the heavier elements from copernicium to livermorium,[2][39][40] despite early interest in theoretical predictions due to relativistic effects on the ns subshell in group 11 reaching a maximum at roentgenium.[2] The isotopes 280Rg and 281Rg are promising for chemical experimentation and may be produced as the granddaughters of the moscovium isotopes 288Mc and 289Mc respectively;[41] their parents are the nihonium isotopes 284Nh and 285Nh, which have already received preliminary chemical investigations.[42]

See also

Explanatory notes

  1. Different sources give different values for half-lives; the most recently published values are listed.
  2. 2.0 2.1 This isotope is unconfirmed

Citations

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  2. 2.00 2.01 2.02 2.03 2.04 2.05 2.06 2.07 2.08 2.09 2.10 2.11 2.12 2.13 2.14 2.15 2.16 Hoffman, Darleane C.; Lee, Diana M.; Pershina, Valeria (2006). "Transactinides and the future elements". in Morss; Edelstein, Norman M.; Fuger, Jean. The Chemistry of the Actinide and Transactinide Elements (3rd ed.). Dordrecht, The Netherlands: Springer Science+Business Media. ISBN 978-1-4020-3555-5. 
  3. 3.0 3.1 3.2 Östlin, A.; Vitos, L. (2011). "First-principles calculation of the structural stability of 6d transition metals". Physical Review B 84 (11). doi:10.1103/PhysRevB.84.113104. Bibcode2011PhRvB..84k3104O. 
  4. 4.0 4.1 Fricke, Burkhard (1975). "Superheavy elements: a prediction of their chemical and physical properties". Recent Impact of Physics on Inorganic Chemistry. Structure and Bonding 21: 89–144. doi:10.1007/BFb0116498. ISBN 978-3-540-07109-9. https://www.researchgate.net/publication/225672062. Retrieved 4 October 2013. 
  5. 5.0 5.1 Conradie, Jeanet; Ghosh, Abhik (15 June 2019). "Theoretical Search for the Highest Valence States of the Coinage Metals: Roentgenium Heptafluoride May Exist". Inorganic Chemistry 2019 (58): 8735–8738. doi:10.1021/acs.inorgchem.9b01139. PMID 31203606. 
  6. Fricke, Burkhard (1975). "Superheavy elements: a prediction of their chemical and physical properties". Recent Impact of Physics on Inorganic Chemistry 21: 89–144. doi:10.1007/BFb0116498. https://www.researchgate.net/publication/225672062_Superheavy_elements_a_prediction_of_their_chemical_and_physical_properties. Retrieved 4 October 2013. 
  7. Chemical Data. Roentgenium - Rg, Royal Chemical Society
  8. Oganessian, Yuri Ts.; Abdullin, F. Sh.; Alexander, C. et al. (2013-05-30). "Experimental studies of the 249Bk + 48Ca reaction including decay properties and excitation function for isotopes of element 117, and discovery of the new isotope 277Mt". Physical Review C (American Physical Society) 87 (054621). doi:10.1103/PhysRevC.87.054621. Bibcode2013PhRvC..87e4621O. 
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  14. Barber, R. C.; Greenwood, N. N.; Hrynkiewicz, A. Z.; Jeannin, Y. P.; Lefort, M.; Sakai, M.; Ulehla, I.; Wapstra, A. P. et al. (1993). "Discovery of the transfermium elements. Part II: Introduction to discovery profiles. Part III: Discovery profiles of the transfermium elements". Pure and Applied Chemistry 65 (8): 1757. doi:10.1351/pac199365081757.  (Note: for Part I see Pure Appl. Chem., Vol. 63, No. 6, pp. 879–886, 1991)
  15. Karol; Nakahara, H.; Petley, B. W.; Vogt, E. (2001). "On the discovery of the elements 110–112". Pure Appl. Chem. 73 (6): 959–967. doi:10.1351/pac200173060959. http://iupac.org/publications/pac/2001/pdf/7306x0959.pdf. 
  16. Hofmann, S.; Heßberger, F. P.; Ackermann, D.; Münzenberg, G.; Antalic, S.; Cagarda, P.; Kindler, B.; Kojouharova, J. et al. (2002). "New results on elements 111 and 112". European Physical Journal A 14 (2): 147–157. doi:10.1140/epja/i2001-10119-x. Bibcode2002EPJA...14..147H. 
  17. Hofmann. "New results on element 111 and 112". GSI report 2000. pp. 1–2. https://repository.gsi.de/record/53531/files/GSI-Report-2001-1.pdf. 
  18. Karol, P. J.; Nakahara, H.; Petley, B. W.; Vogt, E. (2003). "On the claims for discovery of elements 110, 111, 112, 114, 116, and 118". Pure Appl. Chem. 75 (10): 1601–1611. doi:10.1351/pac200375101601. http://iupac.org/publications/pac/2003/pdf/7510x1601.pdf. 
  19. Chatt, J. (1979). "Recommendations for the naming of elements of atomic numbers greater than 100". Pure and Applied Chemistry 51 (2): 381–384. doi:10.1351/pac197951020381. 
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  21. 21.0 21.1 21.2 Audi, G.; Kondev, F. G.; Wang, M.; Huang, W. J.; Naimi, S. (2017). "The NUBASE2016 evaluation of nuclear properties". Chinese Physics C 41 (3): 030001. doi:10.1088/1674-1137/41/3/030001. Bibcode2017ChPhC..41c0001A. https://www-nds.iaea.org/amdc/ame2016/NUBASE2016.pdf. 
  22. Thoennessen, M. (2016). The Discovery of Isotopes: A Complete Compilation. Springer. pp. 229, 234, 238. doi:10.1007/978-3-319-31763-2. ISBN 978-3-319-31761-8. 
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  35. Thayer, John S. (2010). "Relativistic Effects and the Chemistry of the Heavier Main Group Elements". Relativistic Methods for Chemists. Challenges and Advances in Computational Chemistry and Physics. 10. p. 82. doi:10.1007/978-1-4020-9975-5_2. ISBN 978-1-4020-9974-8. 
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  41. Moody, Ken (2013-11-30). "Synthesis of Superheavy Elements". in Schädel, Matthias; Shaughnessy, Dawn. The Chemistry of Superheavy Elements (2nd ed.). Springer Science & Business Media. pp. 24–8. ISBN 9783642374661. 
  42. Aksenov, Nikolay V.; Steinegger, Patrick; Abdullin, Farid Sh.; Albin, Yury V.; Bozhikov, Gospodin A.; Chepigin, Viktor I.; Eichler, Robert; Lebedev, Vyacheslav Ya. et al. (July 2017). "On the volatility of nihonium (Nh, Z = 113)". The European Physical Journal A 53 (158): 158. doi:10.1140/epja/i2017-12348-8. Bibcode2017EPJA...53..158A. 

General bibliography

External links

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