Dubnium

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Dubnium, 105Db
General properties
Name, symbol dubnium, Db
Pronunciation Listeni/'du?bni?m/
doob-nee-?m
Dubnium in the periodic table
Hydrogen (diatomic nonmetal)
Helium (noble gas)
Lithium (alkali metal)
Beryllium (alkaline earth metal)
Boron (metalloid)
Carbon (polyatomic nonmetal)
Nitrogen (diatomic nonmetal)
Oxygen (diatomic nonmetal)
Fluorine (diatomic nonmetal)
Neon (noble gas)
Sodium (alkali metal)
Magnesium (alkaline earth metal)
Aluminium (post-transition metal)
Silicon (metalloid)
Phosphorus (polyatomic nonmetal)
Sulfur (polyatomic nonmetal)
Chlorine (diatomic nonmetal)
Argon (noble gas)
Potassium (alkali metal)
Calcium (alkaline earth metal)
Scandium (transition metal)
Titanium (transition metal)
Vanadium (transition metal)
Chromium (transition metal)
Manganese (transition metal)
Iron (transition metal)
Cobalt (transition metal)
Nickel (transition metal)
Copper (transition metal)
Zinc (transition metal)
Gallium (post-transition metal)
Germanium (metalloid)
Arsenic (metalloid)
Selenium (polyatomic nonmetal)
Bromine (diatomic nonmetal)
Krypton (noble gas)
Rubidium (alkali metal)
Strontium (alkaline earth metal)
Yttrium (transition metal)
Zirconium (transition metal)
Niobium (transition metal)
Molybdenum (transition metal)
Technetium (transition metal)
Ruthenium (transition metal)
Rhodium (transition metal)
Palladium (transition metal)
Silver (transition metal)
Cadmium (transition metal)
Indium (post-transition metal)
Tin (post-transition metal)
Antimony (metalloid)
Tellurium (metalloid)
Iodine (diatomic nonmetal)
Xenon (noble gas)
Caesium (alkali metal)
Barium (alkaline earth metal)
Lanthanum (lanthanide)
Cerium (lanthanide)
Praseodymium (lanthanide)
Neodymium (lanthanide)
Promethium (lanthanide)
Samarium (lanthanide)
Europium (lanthanide)
Gadolinium (lanthanide)
Terbium (lanthanide)
Dysprosium (lanthanide)
Holmium (lanthanide)
Erbium (lanthanide)
Thulium (lanthanide)
Ytterbium (lanthanide)
Lutetium (lanthanide)
Hafnium (transition metal)
Tantalum (transition metal)
Tungsten (transition metal)
Rhenium (transition metal)
Osmium (transition metal)
Iridium (transition metal)
Platinum (transition metal)
Gold (transition metal)
Mercury (transition metal)
Thallium (post-transition metal)
Lead (post-transition metal)
Bismuth (post-transition metal)
Polonium (post-transition metal)
Astatine (metalloid)
Radon (noble gas)
Francium (alkali metal)
Radium (alkaline earth metal)
Actinium (actinide)
Thorium (actinide)
Protactinium (actinide)
Uranium (actinide)
Neptunium (actinide)
Plutonium (actinide)
Americium (actinide)
Curium (actinide)
Berkelium (actinide)
Californium (actinide)
Einsteinium (actinide)
Fermium (actinide)
Mendelevium (actinide)
Nobelium (actinide)
Lawrencium (actinide)
Rutherfordium (transition metal)
Dubnium (transition metal)
Seaborgium (transition metal)
Bohrium (transition metal)
Hassium (transition metal)
Meitnerium (unknown chemical properties)
Darmstadtium (unknown chemical properties)
Roentgenium (unknown chemical properties)
Copernicium (transition metal)
Nihonium (unknown chemical properties)
Flerovium (post-transition metal)
Moscovium (unknown chemical properties)
Livermorium (unknown chemical properties)
Tennessine (unknown chemical properties)
Oganesson (unknown chemical properties)
Ta
?
Db
?
(Upe)
rutherfordium ? dubnium ? seaborgium
Atomic number (Z) 105
Group, block group 5, d-block
Period period 7
Element category transition metal
Standard atomic weight (Ar) [268]
Electron configuration [Rn] 5f14 6d3 7s2[1]
Electrons per shell
2, 8, 18, 32, 32, 11, 2
Physical properties
Phase solid (predicted)[2]
Density near r.t. 29.3 g/cm3 (predicted)[1][3]
Atomic properties
Oxidation states 5, (4), (3)[1][3] ?(parenthesized oxidation states are p
redictions)
Ionization energies 1st: 656.1 kJ/mol
2nd: 1546.7 kJ/mol
3rd: 2378.4 kJ/mol
(more) (all but first estimated)[1]
Atomic radius empirical: 139 pm (estimated)[1]
Covalent radius 149 pm (estimated)[4]
Miscellanea
Crystal structure ?body-centered cubic (bcc) (predicted)[2] Body-centered
cubic crystal structure for dubnium
CAS Number 53850-35-4
History
Naming after Dubna, Moscow Oblast, Russia, site of the Joint Institute for Nucl
ear Research
Discovery independently by the University of California and the Joint Inst
itute for Nuclear Research (1970)
Most stable isotopes of dubnium
iso NA half-life DM DE (MeV) DP
262Db syn 34 s[5][6] 67% a 8.66,
8.45 258Lr
33% SF
263Db syn 27 s[6] 56% SF
41% a 8.36 259Lr
3% e 263mRf
266Db syn 22 min[6] SF
e 266Rf
267Db syn 1 h[6] SF
268Db syn 30 h[6] SF
e 268Rf
270Db syn 1 h[7] 17% SF
83% a 266Lr
view talk edit | references | in Wikidata
Dubnium is a chemical element with symbol Db and atomic number 105. A transactin
ide element, dubnium is highly radioactive: the most stable known isotope, dubni
um-268, has a half-life of just above a day. This greatly limits the extent of p
ossible research on dubnium.
Dubnium does not occur naturally on Earth and is produced artificially. The firs
t discovery of the element was claimed by the Soviet Joint Institute for Nuclear
Research (JINR) in 1968, followed in 1970 by the American University of Califor
nia. Both teams proposed a name for the new element, and used it without formal
approval. The long-standing dispute was resolved in 1997, when the element was o
fficially named dubnium after Dubna, the site of the JINR.
In the periodic table of the elements, dubnium is located in period 7, in d-bloc
k, thus being a transactinide element. Dubnium belongs to group 5 as the third m
ember of the 6d series of transition metals. The limited investigation on chemis
try of dubnium has demonstrated that behavior of dubnium is typical for group 5,
and the element is established as the heavier homologue to tantalum in group 5;
however, some deviations, particularly those from the periodic trends, occur du
e to relativistic effects.
Contents [hide]
1 Discovery
1.1 Reports
1.2 Naming controversy
2 Isotopes
3 Predicted properties
3.1 Atomic and physical
3.2 Chemical
4 Experimental chemistry
5 Notes
6 References
7 External links
Discovery[edit]
The first discovery of an element heavier than uranium, the heaviest of the natu
rally occurring quantity elements neptunium occurred in 1940 by the University of Ca
lifornia in Berkeley, California, United States. In the coming years, the Americ
an team undoubtedly synthesized the following elements up to mendelevium, elemen
t 101. However, in 1956, the Joint Institute for Nuclear Research (JINR) in Dubn
a, Moscow Oblast, Russian SFSR, Soviet Union, was founded and became a major riv
al to the American team. Their rivalry, heated by the ideological and geopolitic
al rivalry of their countries, which itself reached its peak in the 1960s, resul
ted in a race for new elements and credit of their discoveries, later named the
Transfermium Wars.
Reports[edit]
The first report of discovery of element 105 came from the JINR in 1968. A targe
t of americium-243 was bombarded by a beam of neon-22 ions. The scientists at Du
bna reported 9.4 MeV (with the reported half-live of 0.1 3 seconds) and 9.7 MeV (t
1/2 > 0.05 s) alpha activities followed by alpha activities similar to those of
lawrencium-256 and lawrencium-257. The two activity lines were, based on predict
ed data, assigned to 261105 and 260105, accordingly:[8]
243
95Am
+ 22
10Ne
? 265-x105 + x
n
(x = 4, 5)
Investigation of the original reaction was continued; the research was aimed at
looking for fission fragments of Z=105 isotopes. In February 1970, a following p
aper was published. Two activities were found, with half-lives of 14 ms and 2.20.
5 s. The former activity was assigned to 242mfAm; the latter one was described a
s having been caused by an isotope of element 105. The idea that the latter acti
vity could come from a transfer reaction and thus not be from element 105 was sa
id to be diminished by the fact that the yield ratio for this reaction was lower
than that of the 242mfAm-producing transfer reaction. The idea that this synthe
sis reaction was indeed a (22Ne,xn) reaction was grounded on research on the rea
ction of that beam with 18O; reactions producing 256Lr and 257Lr showed very lit
tle spontaneous fission (SF) activity (matching the established data), and the r
eaction producing heavier 258Lr and 259Lr produced no SF activity at all, fallin
g in line with theory. A subsequent paper, released in May 1970, reported that t
his isotope was probably 261105, though the possibility of it being 260105 was n
ot excluded.[8]
In April 1970, a team led by Albert Ghiorso working at the University of Califor
nia stepped into the competition. They claimed to have synthesized the element b
y bombarding a californium-249 target with nitrogen-15 ions. Alpha activity with
the energy of 9.1 MeV was formed; the team attempted reaction with other nuclid
es bombardment of 249Cf with 14N, Pb with 15N, Hg with 15N and stated no such activi
ty was found in those reactions. The characteristics of the daughter nuclei corr
elated with those of lawrencium-256:[8]
249
98Cf
+ 15
7N
? 260105 + 4
n
These results by the Berkeley scientists did not confirm the JINR findings regar
ding the 9.4 MeV or 9.7 MeV alpha-decay of dubnium-260, leaving only dubnium-261
as possible produced isotope.
In May 1970, the first paper discussing chemical examination and confirmation of
the supposed element 105 was published in Dubna. That work relied on the previo
us data from Dubna: the February 1970 paper. The thermal gradient version of the
gas-chromatography method was applied to demonstrate that the chloride of what
formed the SF activity in the aforementioned work nearly agreed with that of NbC
l5, rather than HfCl4: therefore, this directed to an assignment to element 105.
The team identified a 2.2-second spontaneous fission activity contained within
a volatile chloride portraying eka-tantalum properties.[8]
In June 1970, the Dubna team made improvements on their original experiment, pro
viding a purer target and intensity of transfer reactions reduced by using a col
limator before the catcher. This time, they were able to find 9.1 MeV alpha acti
vities with daughter isotopes identifiable as either 256Lr or 257Lr; thus, the o
riginal isotope was either 260105 or 261105.[8]
Naming controversy[edit]
Main article: Element naming controversy
A photo of Niels Bohr
A photo of Otto Hahn
The element 105 was originally proposed to be named after Danish nuclear physici
st Niels Bohr (left), with name nielsbohrium (Ns) by the Soviet/Russian team. Th
e American team initially proposed the element to be named hahnium (Ha) after Ge
rman nuclear chemist Otto Hahn.
The Soviet team proposed the name nielsbohrium (Ns) in honor of the Danish nucle
ar physicist Niels Bohr, one of the founders of the theories of the atomic struc
ture and the quantum theory. The American team proposed that the new element sho
uld be named hahnium (Ha), in honor of the German chemist Otto Hahn, the "father
of nuclear chemistry". An element naming controversy rose; consequently, hahniu
m was the name that most American and Western European scientists used and appea
rs in many papers published at the time, and nielsbohrium was used in the Soviet
 Union and Eastern Bloc countries.
However, tensions in the late 1960s and 1970s simmered down somewhat. Both teams
synthesized the next element, element 106, but decided not to suggest their nam
es.[9] In 1968, the Soviet team presented a report calling recognition of discov
ery of elements 102 and 103 by other teams "hasty".[10] Afterwards, they suggest
ed establishing an international committee on elaborating the discovery criteria
. This proposal was accepted in 1974; however, the newly formed Committee never
assembled to assess the claims.[10] The conflict remained unsolved, and in 1979,
the IUPAC published a new suggested system of systematic element names (accordi
ng to which element 105 would be named unnilpentium, from the Latin roots un- an
d nil- and the Greek root pent- (meaning "one", "zero", and "five", accordingly,
referencing the atomic number) intended to be used as placeholders until perman
ent names were established; the scientists ignored it, not wishing to weaken the
ir claims by adopting a neutral naming system rather than their own.[11]
In 1981, a third major competitor joined the race for superheavy elements the Gese
llschaft fr Schwerionenforschung (English Society for Heavy Ion Research) in Darm
stadt, Hesse, West Germany. They claimed to have synthesized the element 107; th
eir report came out five years after the first report from Dubna did, but it pro
vided further details not presented in that work.[8] The German team joined with
the Soviet team in that it suggested the name nielsbohrium for the new element,
believing Bohr did deserve an element named after him, and hoping to ease the t
ension on the element 105 controversy.[10] The Soviet team did not hurry to sugg
est a new name for element 105, stating it was more fundamental to first determi
ne the discoverers of the element.[10]
Dubna is located in European Russia. DubnaDubna
Location of Dubna within European Russia
In 1985, the International Union of Pure and Applied Chemistry (IUPAC) and the I
nternational Union of Pure and Applied Physics (IUPAP) formed a Joint Working Pa
rty (JWP) aimed at assessing discoveries and establishing final names for the el
ements in question.[8] The party held numerous meetings with delegates from all
three competing institutes; in 1990, they established criteria on recognizing an
element and in 1991, they completed the work on assessing discoverer statuses a
nd the party was disbanded. These results were published in 1993. According to t
he report, the first definitely successful experiment was the April 1970 experim
ent in Berkeley, followed closely by the June 1970 Dubna experiment; thus, credi
t for discovery of the element should be shared between the two competing teams.
[8]
The American team dismissed the report. In an open response, they proclaimed tha
t the input from the Russian team was overrated by the review. In addition, they
claimed the Dubna team was able to undoubtedly demonstrate the synthesis of ele
ment 105 no earlier than a year after they did. The Russian and the German teams
endorsed the report. The scientists from the former JWP rejected criticisms fro
m Berkeley.[10]
In 1994, the IUPAC published a recommendation on naming the disputed elements fo
llowing the previous reports. For element 105, they proposed the name joliotium
(Jl), after the French physicist Frdric Joliot-Curie, a significant contributor to
the development of nuclear physics and chemistry; this name was originally prop
osed by the Soviet team for element 102, which by then had long been called nobe
lium.[12] (The name nielsbohrium for the element 107 transformed to bohrium to c
onform the practice set by all then-current elements.)[12] This recommendation p
aper was generally met with criticism from the American scientists: their recomm
endations were scrambled (i.e. the name rutherfordium, originally suggested by B
erkeley for element 104, was used for element 106); both elements 104 and 105 we
re given names suggested by the Russian team despite earlier recognition of the
Berkeley team as of an equal co-discoverer; and especially because the name seab
orgium for element 106 was rejected for honoring a living person (Glenn Seaborg
was an American nuclear chemist and a principal pioneer in the research on trans
uranium elements), a rule that had only just been approved.[13] These names were
to be accepted on a Council meeting in 1995.
After a new term of negotiations between the parties, IUPAC decided to allow the
name seaborgium for element 106 and changed the name of element 102 to fleroviu
m after Soviet nuclear physicist Georgy Flyorov following the recognition by the
1993 report that the element had been first convincingly synthesized in Dubna (
Flyorov discovered spontaneous fission and was another tremendously important pi
oneering researcher on the superheavy elements). However, this compromise was al
so rejected by the American scientists and the decision was retracted.[1]
In 1996, the IUPAC held another meeting and reconsidered all names in hand and a
nother set of recommendations was accepted on this meeting; it was finally appro
ved and published in 1997.[14] Element 105 got its final name, dubnium (Db), aft
er the Russian town of Dubna, the location of the Joint Institute for Nuclear Re
search. This decision was "reluctantly" approved by the American scientists.[15]
The IUPAC stated the Berkeley laboratory had already been recognized several ti
mes in the naming of elements (i.e., berkelium, californium, americium) and that
the acceptance of the names rutherfordium and seaborgium for elements 104 and 1
06 should be offset by recognizing the Russian team's contributions to the disco
very of elements 104, 105, and 106. (The matter of naming element 107 was transf
erred to the Royal Danish Academy of Sciences and Letters, who recommended the n
ame bohrium to be used.)[16]
Isotopes[edit]
Main article: Isotopes of dubnium
A 2D graph with rectangular cells colored in black-and-white colors, spanning fr
om the llc to the urc, with cells mostly becoming lighter closer to the latter
A chart of nuclide stability as used by the Dubna team in 2012. Characterized is
otopes are shown with borders.[17]
Dubnium, having atomic number 105, is a superheavy element, and as such is unsta
ble. The most stable known isotope of dubnium, 268Db, has a half-life of around
a day. Thus, even if it had once existed on Earth, it would have decayed complet
ely long ago and can only be produced artificially.[a]
The short half-live of dubnium limits the scope of experimentation. This is ampl
ified by the neutron-to-proton ratio of the most stable isotopes of an element g
rowing with the atomic number, a trend that is expected to continue to the super
heavy elements;[20] this complicates synthesis of the most stable isotopes as th
e isotopes in question will have more neutrons per proton than both the target a
nd beam nuclei that could be employed. (Although a different technique based on
rapid neutron capture is being considered,[21] the ones based on collision of a
big and a small nucleus dominate research in the area nowadays.)
The first nuclei of dubnium were produced by reactions of direct nuclear fusion,
in which two nuclei fused into one, possibly emitting a few neutrons. These fir
st nuclei were very unstable, lasting often less than a second. However, more st
able isotopes of dubnium heavier than those first synthesized should exist, as t
he nuclear drip line moves towards greater relative neutron-richness of nuclei w
ith the increase in atomic number. Some of those isotopes have been produced sin
ce then with other fusion reactions. However, as research on superheavy nuclei m
oved on, the heaviest isotopes of dubnium were produced only indirectly, but rat
her as the daughters of heavier nuclei that would decay via consecutive alpha de
cays to dubnium.
The most stable isotope of dubnium is 268Db. By 2016, only a few atoms were avai
lable each time, and thus the half-lives changed significantly during the proces
s. During three experiments, 23 atoms were created in total, with a resulting ha
lf-life of 28+11
-4 hours.[22] The second most stable isotope, 270Db, has been produced in even s
maller quanitites: three atoms in total, with lifetimes of 33.4 h,[23] 1.3 h, an
d 1.6 h.[24] These two are the heaviest isotopes of dubnium to date, and both we
re produced as a result of decay of heavier nuclei rather than directly. The rea
son for is that the experiments that yielded were originally designed in Dubna f
or using 48Ca beams.[25] For its mass, 48Ca has by far the greatest neutron exce
ss of all practically stable nuclei, both quantitative and relative,[26] which,
correspondingly, helps synthesize superheavy nuclei with more neutrons.
While it yet remains to be seen if there are principally more stable isotopes, t
here has not any theoretical, let alone practical, suggestion this could be the
case. In a 2012 calculation from Dubna, it was suggested that the half-lives of
all dubnium isotopes, synthesized or not, did not actually significantly exceed
a day.[17][b]
Predicted properties[edit]
According to the periodic law, dubnium should belong to group 5, under vanadium,
niobium, and tantalum. Several studies investigated the properties of element 1
05 and found a general agreement with the predictions from the periodic law. Sig
nificant deviations may nevertheless occur, due to relativistic effects, which d
ramatically change physical properties on both atomic and macroscopic scales. Th
ese properties have remained challenging to measure: only gas-phase studies have
been performed on singular atoms, and generally prove the assignment of dubnium
to the position under tantalum in the periodic table.
Atomic and physical[edit]
Relativistic effects arise when an object moves on velocities comparable to the
speed of light. For example, as velocity of an object increases, so does its mas
s, which leads to decrease of the mean distance between the electron and the nuc
leus.

Relativistic (solid line) and nonrelativistic (dashed line) radial distribution

of the 7s valence electrons in dubnium.
A direct relativistic effect is that as atomic numbers of elements increase, the
innermost electrons begin to revolve faster around the nucleus as a result of t
he increase of the electromagnetic attraction between an electron and a nucleus.
Similar effects have been found for s orbitals (and p1/2 ones, though this is n
ot quite applicable for dubnium): for example, the 7s orbital is contracted by 2
5% in size and stabilized by 2.6 eV.[1]
A more indirect effect would be that the contracted s and p1/2 orbitals shield (
take on themselves) the charge of the nucleus more effectively, leaving even les
s for the outer d and f electrons, which therefore move on larger orbitals. Dubn
ium is greatly affected by this: unlike the previous group 5 members, its 7s ele
ctrons are more difficult to extract from an atom than the 6d electrons, though
these energy levels remain close to each other.[1]

Relativistic stabilization of the ns orbitals, the destabilization of the (n-1)d

orbitals and their SO splitting for the group 5 elements.
A third effect is the spin orbit (SO) interaction, particularly, the SO splitting,
which, in application to dubnium, splits the 6d subshell the azimuthal quantum nu
mber l for a d shell is 2 into two subshells, with four of the ten orbitals having
its l lowered to 3/2 and six raised to 5/2. While all ten energy levels are act
ually raised (lowered in absolute values), making them less stable energetically
, four of them are more stable than the other six. (The three 6d electrons norma
lly assume the energy levels of lowest energy, 6d3/2.)[1]
While after a removal of a single electron from a neutral dubnium atom, the rema
ining valence electrons in a singly ionized ion (Db+) should organize themselves
in a 6d27s2 configuration, the doubly (Db2+) or triply (Db3+) ionized atoms eli
minate the 7s electrons: this is the opposite order to that of its lighter homol
ogs. Despite the changes, however, dubnium is still expected to use five electro
ns as its valence electrons; 7p energy levels have not been shown to influence d
ubnium and its properties. As the 6d orbitals are further destabilized compared
to 5d ones of tantalum, and Db3+ is expected to have two d, rather than s, elect
rons remaining, the resulting oxidation state is expected to be unstable and eve
n rarer than that of tantalum. The ionization potential of dubnium in its maximu
m oxidation state should be slightly lower than that of tantalum and the ionic r
adius of dubnium should increase compared to tantalum; this has a significant ef
fect on dubnium's chemistry (see below).[1]
Dubnium atoms, when in quantity and in a free state, should arrange themselves i
n a body-centered cubic configuration, like the previous group 5 elements.[2] Th
e predicted density of dubnium is 29 g/cm3.[1]
Chemical[edit]
Relativistic (rel) and nonrelativistic (nr) values of the effective charge (QM)
and overlap population (OP) in MCl5, where M = V, Nb, Ta, and Db
The simplest case for computational chemistry is the gas-phase chemistry, in whi
ch a substance is treated as if it was a gas to eliminate the necessity to take
interactions between molecules in account. Research by multiple authors[1] has b
een undertaken on the expected highest chloride of dubnium, DbCl5: it has been c
alculated to be consistent with the periodic laws by exhibiting properties of a
compound of a d-block element, for example, the molecular orbital levels indicat
e dubnium uses three 6d electron levels, just as it would be expected. One prope
rty DbCl5 is expected to show is its increased (compared to TaCl5) covalence: a
decrease in the effective charge on an atom and an increase in the overlap popul
ation (between orbitals of dubnium and chlorine).[1]
Calculations for solution chemistry indicate that again, the maximum oxidation s
tate, +5, will be more stable than that of niobium and tantalum, and the +3 stat
e will be less stable than those of niobium and tantalum. Hydrolysis of cations
of +5 is expected to continue to decrease within group 5; however, it is still e
xpected to be quite rapid. Complexation of dubnium is expected to follow group 5
trends in its richness; calculations for hydroxo-chlorido- complexes have been
conducted; they show reversal in the trend in the complex formation and extracti
on of group 5 elements, with dubnium being more prone to do so than tantalum.[1]
Experimental chemistry[edit]
Early experimental results of studies of the chemistry of dubnium date back to 1
974 and 1976. Dubna researchers used a thermochromatographic system, and conclud
ed that the volatility of dubnium bromide was less than that of niobium bromide
and about the same as that of hafnium bromide. It is not certain, however, that
the detected fission products confirmed that the parent was indeed element 105.
This may imply that the new element behaved more like hafnium than niobium.[1]
Further studies of the chemistry of dubnium were reported over a decade later, i
n 1988. Studies at Berkeley examined whether the most stable oxidation state of
dubnium in aqueous solution is 5+. Sorption of dubnium on glass cover slips afte
r fuming twice and washing with concentrated nitric acid, was compared with that
of tracers of the group 5 elements niobium and tantalum and the group 4 element
s zirconium and hafnium produced on-line under similar conditions. The group 5 e
lements are known to sorb on glass surfaces while the group 4 elements do not. D
ubnium was confirmed as a group 5 member. However, it was surprising that extrac
tion behavior into methyl isobutyl ketone from mixed HNO3/HF solutions differed
between dubnium, tantalum, and niobium. Element 105 did not extract and its beha
vior resembled niobium more closely than tantalum, indicating that details of co
mplexing behavior cannot be predicted based only on simple extrapolations of tre
nds within a group in the periodic table.[1]
This prompted further exploration of the chemical behavior of complexes of dubni
um. Thousand of repetitive chromatographic experiments were performed jointly in
various labs in the period 1988 93. All group 5 elements and protactinium were ex
tracted from concentrated hydrochloric acid; at lower concentrations of HCl, sma
ll amounts of HF were added to start selective re-extraction. Element 105 showed
a behavior unlike tantanum at concentrations of HCl below 12 M, following the b
ehavior of niobium and the pseudohomolog protactinium. Because of this similarit
y to these two elements, the research suggested that the formed complex was eith
er DbOX-
4 or [Db(OH)
2X
4]-
. After extraction experiments of Db from HBr into diisobutyl carbinol (2,6-dime
thylheptan-4-ol), a specific extractant for protactinium, with subsequent elutio
ns with mixed HCl/HF and HCl, the obtained extraction sequence Pa > Nb > Db was
determined. It was explained as an increasing tendency to form non-extractable c
omplexes of multiple negative charges. Further experiments in 1992 confirmed the
stability of the +5 state: Db(V) was shown to be extractable from cation-exchan
ge columns with a-hydroxyisobutyrate, similarly to other group 5 elements and pr
otactinium; Db(III) and Db(IV) were not. In 1998 and 1999, new predictions yield
ed the sequence Pa >> Nb = Db > Ta for extraction from halide solutions, which w
as later confirmed.[1]
The first isothermal gas chromatography experiments were performed in 1992 with
262Db (t1/2 = 35 s). The volatilities for niobium and tantalum were similar with
in error limits, but dubnium appeared to be significantly less volatile. It was
postulated that traces of oxygen in the system might have led to formation of Db
OBr
3, which was predicted to be less volatile than DbBr
5. Later experiments in 1996 showed that group 5 chlorides were more volatile th
an the corresponding bromides, with the exception of tantalum, presumably due to
formation of TaOCl
3). Later volatility studies of chlorides of dubnium and niobium as a function o
f controlled partial pressures of oxygen, showed that formation of oxychlroides
and general volatility are dependent on concentrations of oxygen. The oxychlorid
es were shown to be less volatile than the chlorides.[1]
In 2004 05, researchers from Dubna and Livermore identified dubnium as a fivefold
alpha decay product of the newly created element 115 which they found to be stab
le enough to allow chemical experiments a year earlier. In the 2004 experiment,
a thin layer was removed from the surface of the target (with dubnium on it), di
ssolved in aqua regia with tracers and lanthanum carrier, from which precipitate
d various +3, +4, and +5 species on adding NH
4OH. The precipitate was washed and dissolved in HCl, in which it was converted
to nitrate form then dried on a film and counted. It mostly contained a +5 speci
es, which was immediately assigned to dubnium, but also a +4 species, and the te
am decided on need of additional chemical separation. In 2005, the experiment wa
s repeated, with the final product being hydroxide, rather than nitrate, precipi
tate, which was processed to either Livermore further experimentations (based on
reverse phase chromatography) or that of Dubna (based on anion exchange chromat
ography). The +5 species was effectively isolated; dubnium in that experiment ap
peared three times in Ta-only fractions and not even once in Nb-only fractions.
It was, however, noted that these experiments were insufficient to draw conclusi
ons about dubnium chemical profile in general.[27]
In 2009, another anion-exchange experiment was conducted in Japan at the JAEA ta
ndem accelerator. Dubnium was processed to a nitric acid/hydrofluoric acid solut
ion, with concentrations at which Nb forms NbOF-
4 and Ta forms TaF6-
. Dubnium's behavior was close to that of Nb but not Ta; thus, it was deduced it
formed DbOF-
4. It was concluded that the information available by that point lead to a concl
usion that Db often behaved like Nb, sometimes like Pa, but rarely as Ta.[28]
Notes[edit]
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