Dubnium
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Dubnium is a
synthetic Synthetic things are composed of multiple parts, often with the implication that they are artificial. In particular, 'synthetic' may refer to: Science * Synthetic chemical or compound, produced by the process of chemical synthesis * Synthetic o ...
chemical element A chemical element is a species of atoms that have a given number of protons in their nuclei, including the pure substance consisting only of that species. Unlike chemical compounds, chemical elements cannot be broken down into simpler sub ...
with the
symbol A symbol is a mark, sign, or word that indicates, signifies, or is understood as representing an idea, object, or relationship. Symbols allow people to go beyond what is known or seen by creating linkages between otherwise very different conc ...
Db and
atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of every ...
105. It is highly radioactive: the most stable known
isotope Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers (mass numbers) ...
, dubnium-268, has a
half-life Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable ato ...
of about 16 hours. This greatly limits extended research on the element. Dubnium does not occur naturally on Earth and is produced artificially. The Soviet
Joint Institute for Nuclear Research The Joint Institute for Nuclear Research (JINR, russian: Объединённый институт ядерных исследований, ОИЯИ), in Dubna, Moscow Oblast (110 km north of Moscow), Russia, is an international research cen ...
(JINR) claimed the first discovery of the element in 1968, followed by the American
Lawrence Berkeley Laboratory Lawrence Berkeley National Laboratory (LBNL), commonly referred to as the Berkeley Lab, is a United States national laboratory that is owned by, and conducts scientific research on behalf of, the United States Department of Energy. Located in ...
in 1970. Both teams proposed their names for the new element and used them without formal approval. The long-standing dispute was resolved in 1993 by an official investigation of the discovery claims by the Transfermium Working Group, formed by the
International Union of Pure and Applied Chemistry The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
and the
International Union of Pure and Applied Physics The International Union of Pure and Applied Physics (IUPAP ) is an international non-governmental organization whose mission is to assist in the worldwide development of physics, to foster international cooperation in physics, and to help in the ...
, resulting in credit for the discovery being officially shared between both teams. The element was formally named ''dubnium'' in 1997 after the town of
Dubna Dubna ( rus, Дубна́, p=dʊbˈna) is a town in Moscow Oblast, Russia. It has a status of ''naukograd'' (i.e. town of science), being home to the Joint Institute for Nuclear Research, an international nuclear physics research center and one o ...
, the site of the JINR. Theoretical research establishes dubnium as a member of
group 5 Group 5 may refer to: *Group 5 element, chemical element classification *Group 5 (racing) Group 5 was an FIA motor racing classification which was applied to four distinct categories during the years 1966 to 1982. Initially Group 5 regulations defi ...
in the 6d series of
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
s, placing it under
vanadium Vanadium is a chemical element with the symbol V and atomic number 23. It is a hard, silvery-grey, malleable transition metal. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an oxide layer ( pas ...
,
niobium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it has sim ...
, and
tantalum Tantalum is a chemical element with the symbol Ta and atomic number 73. Previously known as ''tantalium'', it is named after Tantalus, a villain in Greek mythology. Tantalum is a very hard, ductile, lustrous, blue-gray transition metal that is ...
. Dubnium should share most properties, such as its valence
electron configuration In atomic physics and quantum chemistry, the electron configuration is the distribution of electrons of an atom or molecule (or other physical structure) in atomic or molecular orbitals. For example, the electron configuration of the neon atom ...
and having a dominant +5 oxidation state, with the other group 5 elements, with a few anomalies due to
relativistic effects Relativistic quantum chemistry combines relativistic mechanics with quantum chemistry to calculate elemental properties and structure, especially for the heavier elements of the periodic table. A prominent example is an explanation for the color of ...
. A limited investigation of dubnium chemistry has confirmed this.


Introduction


Discovery


Background

Uranium Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
, element 92, is the heaviest element to occur in significant quantities in nature; heavier elements can only be practically produced by synthesis. The first synthesis of a new element—
neptunium Neptunium is a chemical element with the Symbol (chemistry), symbol Np and atomic number 93. A radioactivity, radioactive actinide metal, neptunium is the first transuranic element. Its position in the periodic table just after uranium, named after ...
, element 93—was achieved in 1940 by a team of researchers in the United States. In the following years, American scientists synthesized the elements up to
mendelevium Mendelevium is a synthetic element with the symbol Md ( formerly Mv) and atomic number 101. A metallic radioactive transuranium element in the actinide series, it is the first element by atomic number that currently cannot be produced in macroscopi ...
, element 101, which was synthesized in 1955. From element 102, the priority of discoveries was contested between American and Soviet physicists. Their rivalry resulted in a race for new elements and credit for their discoveries, later named the
Transfermium Wars The names for the chemical elements 104 to 106 were the subject of a major controversy starting in the 1960s, described by some nuclear chemists as the Transfermium Wars because it concerned the elements following fermium (element 100) on the peri ...
.


Reports

The first report of the discovery of element 105 came from the
Joint Institute for Nuclear Research The Joint Institute for Nuclear Research (JINR, russian: Объединённый институт ядерных исследований, ОИЯИ), in Dubna, Moscow Oblast (110 km north of Moscow), Russia, is an international research cen ...
(JINR) in
Dubna Dubna ( rus, Дубна́, p=dʊbˈna) is a town in Moscow Oblast, Russia. It has a status of ''naukograd'' (i.e. town of science), being home to the Joint Institute for Nuclear Research, an international nuclear physics research center and one o ...
,
Moscow Oblast Moscow Oblast ( rus, Моско́вская о́бласть, r=Moskovskaya oblast', p=mɐˈskofskəjə ˈobləsʲtʲ), or Podmoskovye ( rus, Подмоско́вье, p=pədmɐˈskovʲjə, literally "under Moscow"), is a federal subject of Rus ...
,
Soviet Union The Soviet Union,. officially the Union of Soviet Socialist Republics. (USSR),. was a transcontinental country that spanned much of Eurasia from 1922 to 1991. A flagship communist state, it was nominally a federal union of fifteen national ...
, in April 1968. The scientists bombarded 243Am with a beam of 22Ne ions, and reported 9.4 MeV (with a half-life 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 either 256103 or 257103. Based on prior theoretical predictions, the two activity lines were assigned to 261105 and 260105, respectively. : + → 265−''x''105 + ''x'' (''x'' = 4, 5) After observing the alpha decays of element 105, the researchers aimed to observe
spontaneous fission Spontaneous fission (SF) is a form of radioactive decay that is found only in very heavy chemical elements. The nuclear binding energy of the elements reaches its maximum at an atomic mass number of about 56 (e.g., iron-56); spontaneous breakdo ...
(SF) of the element and study the resulting fission fragments. They published a paper in February 1970, reporting multiple examples of two such activities, with half-lives of 14 ms and . They assigned the former activity to 242mfAm and ascribed the latter activity to an isotope of element 105. They suggested that it was unlikely that this activity could come from a transfer reaction instead of element 105, because the yield ratio for this reaction was significantly lower than that of the 242mfAm-producing transfer reaction, in accordance with theoretical predictions. To establish that this activity was not from a (22Ne,''x''n) reaction, the researchers bombarded a 243Am target with 18O ions; reactions producing 256103 and 257103 showed very little SF activity (matching the established data), and the reaction producing heavier 258103 and 259103 produced no SF activity at all, in line with theoretical data. The researchers concluded that the activities observed came from SF of element 105. In April 1970, a team at
Lawrence Berkeley Laboratory Lawrence Berkeley National Laboratory (LBNL), commonly referred to as the Berkeley Lab, is a United States national laboratory that is owned by, and conducts scientific research on behalf of, the United States Department of Energy. Located in ...
(LBL), in
Berkeley Berkeley most often refers to: *Berkeley, California, a city in the United States **University of California, Berkeley, a public university in Berkeley, California * George Berkeley (1685–1753), Anglo-Irish philosopher Berkeley may also refer ...
,
California California is a U.S. state, state in the Western United States, located along the West Coast of the United States, Pacific Coast. With nearly 39.2million residents across a total area of approximately , it is the List of states and territori ...
, United States, claimed to have synthesized element 105 by bombarding
californium-249 Californium (98Cf) is an artificial element, and thus a standard atomic weight cannot be given. Like all artificial elements, it has no stable isotopes. The first isotope to be synthesized was 245Cf in 1950. There are 20 known radioisotopes rangin ...
with
nitrogen-15 Natural nitrogen (7N) consists of two stable isotopes: the vast majority (99.6%) of naturally occurring nitrogen is nitrogen-14, with the remainder being nitrogen-15. Fourteen radioisotopes are also known, with atomic masses ranging from 10 to 25, ...
ions, with an alpha activity of 9.1 MeV. To ensure this activity was not from a different reaction, the team attempted other reactions: bombarding 249Cf with 14N, Pb with 15N, and Hg with 15N. They stated no such activity was found in those reactions. The characteristics of the daughter nuclei matched those of 256103, implying that the parent nuclei were of 260105. : + → 260105 + 4 These results did not confirm the JINR findings regarding the 9.4 MeV or 9.7 MeV alpha decay of 260105, leaving only 261105 as a possibly produced isotope. JINR then attempted another experiment to create element 105, published in a report in May 1970. They claimed that they had synthesized more nuclei of element 105 and that the experiment confirmed their previous work. According to the paper, the isotope produced by JINR was probably 261105, or possibly 260105. This report included an initial chemical examination: the thermal gradient version of the gas-chromatography method was applied to demonstrate that the chloride of what had formed from the SF activity nearly matched that of
niobium pentachloride Niobium(V) chloride, also known as niobium pentachloride, is a yellow crystalline solid. It hydrolyzes in air, and samples are often contaminated with small amounts of NbOCl3. It is often used as a precursor to other compounds of niobium. NbCl ...
, rather than
hafnium tetrachloride Hafnium(IV) chloride is the inorganic compound with the chemical formula, formula HfCl4. This colourless solid is the Precursor (chemistry), precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, m ...
. The team identified a 2.2-second SF activity in a volatile chloride portraying eka-tantalum properties, and inferred that the source of the SF activity must have been element 105. In June 1970, JINR made improvements on their first experiment, using a purer target and reducing the intensity of transfer reactions by installing a
collimator A collimator is a device which narrows a beam of particles or waves. To narrow can mean either to cause the directions of motion to become more aligned in a specific direction (i.e., make collimated light or parallel rays), or to cause the spati ...
before the catcher. This time, they were able to find 9.1 MeV alpha activities with daughter isotopes identifiable as either 256103 or 257103, implying that the original isotope was either 260105 or 261105.


Naming controversy

JINR did not propose a name after their first report claiming synthesis of element 105, which would have been the usual practice. This led LBL to believe that JINR did not have enough experimental data to back their claim. After collecting more data, JINR proposed the name ''bohrium'' (Bo) in honor of the Danish nuclear physicist
Niels Bohr Niels Henrik David Bohr (; 7 October 1885 – 18 November 1962) was a Danish physicist who made foundational contributions to understanding atomic structure and quantum theory, for which he received the Nobel Prize in Physics in 1922. B ...
, a founder of the theories of
atomic structure Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons. Every solid, liquid, gas, an ...
and
quantum theory Quantum theory may refer to: Science *Quantum mechanics, a major field of physics *Old quantum theory, predating modern quantum mechanics * Quantum field theory, an area of quantum mechanics that includes: ** Quantum electrodynamics ** Quantum ...
; they soon changed their proposal to ''nielsbohrium'' (Ns) to avoid confusion with
boron Boron is a chemical element with the symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the ''boron group'' it has th ...
. Another proposed name was ''dubnium''. When LBL first announced their synthesis of element 105, they proposed that the new element be named ''hahnium'' (Ha) after the German chemist
Otto Hahn Otto Hahn (; 8 March 1879 – 28 July 1968) was a German chemist who was a pioneer in the fields of radioactivity and radiochemistry. He is referred to as the father of nuclear chemistry and father of nuclear fission. Hahn and Lise Meitner ...
, the "father of nuclear chemistry", thus creating an
element naming controversy The currently accepted names and symbols of the chemical elements are determined by the International Union of Pure and Applied Chemistry (IUPAC), usually following recommendations by the recognized discoverers of each element. However the names o ...
. In the early 1970s, both teams reported synthesis of the next element, element 106, but did not suggest names. JINR suggested establishing an international committee to clarify the discovery criteria. This proposal was accepted in 1974 and a neutral joint group formed. Neither team showed interest in resolving the conflict through a third party, so the leading scientists of LBL—
Albert Ghiorso Albert Ghiorso (July 15, 1915 – December 26, 2010) was an American nuclear scientist and co-discoverer of a record 12 chemical elements on the periodic table. His research career spanned six decades, from the early 1940s to the late 1990s. Biog ...
and
Glenn Seaborg Glenn Theodore Seaborg (; April 19, 1912February 25, 1999) was an American chemist whose involvement in the synthesis, discovery and investigation of ten transuranium elements earned him a share of the 1951 Nobel Prize in Chemistry. His work in ...
—traveled to Dubna in 1975 and met with the leading scientists of JINR— Georgy Flerov,
Yuri Oganessian Yuri Tsolakovich Oganessian (russian: Юрий Цолакович Оганесян ; ''Yuri Ts'olaki Hovhannisyan'' . Oganessian is the Russified version of the Armenian last name Hovhannisyan. The article on Oganessian in the ''Armenian Soviet ...
, and others—to try to resolve the conflict internally and render the neutral joint group unnecessary; after two hours of discussions, this failed. The joint neutral group never assembled to assess the claims, and the conflict remained unresolved. In 1979, IUPAC suggested
systematic element name A systematic element name is the temporary name assigned to an unknown or recently synthesized chemical element. A systematic symbol is also derived from this name. In chemistry, a transuranic element receives a permanent name and symbol only af ...
s to be used as placeholders until permanent names were established; under it, element 105 would be ''unnilpentium'', from the Latin roots ''un-'' and ''nil-'' and the Greek root ''pent-'' (meaning "one", "zero", and "five", respectively, the digits of the atomic number). Both teams ignored it as they did not wish to weaken their outstanding claims. In 1981, the
Gesellschaft für Schwerionenforschung The GSI Helmholtz Centre for Heavy Ion Research (german: GSI Helmholtzzentrum für Schwerionenforschung) is a federally and state co-funded heavy ion () research center in the Wixhausen suburb of Darmstadt, Germany. It was founded in 1969 as the ...
(GSI; ''Society for Heavy Ion Research'') in
Darmstadt Darmstadt () is a city in the States of Germany, state of Hesse in Germany, located in the southern part of the Frankfurt Rhine Main Area, Rhine-Main-Area (Frankfurt Metropolitan Region). Darmstadt has around 160,000 inhabitants, making it th ...
,
Hesse Hesse (, , ) or Hessia (, ; german: Hessen ), officially the State of Hessen (german: links=no, Land Hessen), is a States of Germany, state in Germany. Its capital city is Wiesbaden, and the largest urban area is Frankfurt. Two other major histor ...
, West Germany, claimed synthesis of element 107; their report came out five years after the first report from JINR but with greater precision, making a more solid claim on discovery. GSI acknowledged JINR's efforts by suggesting the name ''nielsbohrium'' for the new element. JINR did not suggest a new name for element 105, stating it was more important to determine its discoverers first. In 1985, the
International Union of Pure and Applied Chemistry The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
(IUPAC) and the
International Union of Pure and Applied Physics The International Union of Pure and Applied Physics (IUPAP ) is an international non-governmental organization whose mission is to assist in the worldwide development of physics, to foster international cooperation in physics, and to help in the ...
(IUPAP) formed a Transfermium Working Group (TWG) to assess discoveries and establish final names for the controversial elements. The party held meetings with delegates from the three competing institutes; in 1990, they established criteria on recognition of an element, and in 1991, they finished the work on assessing discoveries and disbanded. These results were published in 1993. According to the report, the first definitely successful experiment was the April 1970 LBL experiment, closely followed by the June 1970 JINR experiment, so credit for the discovery of the element should be shared between the two teams. LBL said that the input from JINR was overrated in the review. They claimed JINR was only able to unambiguously demonstrate the synthesis of element 105 a year after they did. JINR and GSI endorsed the report. In 1994, IUPAC published a recommendation on naming the disputed elements. For element 105, they proposed ''joliotium'' (Jl) after the French physicist
Frédéric Joliot-Curie Jean Frédéric Joliot-Curie (; ; 19 March 1900 – 14 August 1958) was a French physicist and husband of Irène Joliot-Curie, with whom he was jointly awarded the Nobel Prize in Chemistry in 1935 for their discovery of Induced radioactivity. T ...
, a contributor to the development of nuclear physics and chemistry; this name was originally proposed by the Soviet team for element 102, which by then had long been called
nobelium Nobelium is a synthetic chemical element with the symbol No and atomic number 102. It is named in honor of Alfred Nobel, the inventor of dynamite and benefactor of science. A radioactive metal, it is the tenth transuranic element and is the penul ...
. This recommendation was criticized by the American scientists for several reasons. Firstly, their suggestions were scrambled: the names ''rutherfordium'' and ''hahnium'', originally suggested by Berkeley for elements 104 and 105, were respectively reassigned to elements 106 and 108. Secondly, elements 104 and 105 were given names favored by JINR, despite earlier recognition of LBL as an equal co-discoverer for both of them. Thirdly and most importantly, IUPAC rejected the name ''seaborgium'' for element 106, having just approved a rule that an element could not be named after a living person, even though the 1993 report had given the LBL team the sole credit for its discovery. In 1995, IUPAC abandoned the controversial rule and established a committee of national representatives aimed at finding a compromise. They suggested ''seaborgium'' for element 106 in exchange for the removal of all the other American proposals, except for the established name ''lawrencium'' for element 103. The equally entrenched name ''nobelium'' for element 102 was replaced by ''flerovium'' after Georgy Flerov, following the recognition by the 1993 report that that element had been first synthesized in Dubna. This was rejected by American scientists and the decision was retracted. The name ''
flerovium Flerovium is a superheavy chemical element with symbol Fl and atomic number 114. It is an extremely radioactive synthetic element. It is named after the Flerov Laboratory of Nuclear Reactions of the Joint Institute for Nuclear Research in Dubn ...
'' was later used for element 114. In 1996, IUPAC held another meeting, reconsidered all names in hand, and accepted another set of recommendations; it was approved and published in 1997. Element 105 was named ''dubnium'' (Db), after
Dubna Dubna ( rus, Дубна́, p=dʊbˈna) is a town in Moscow Oblast, Russia. It has a status of ''naukograd'' (i.e. town of science), being home to the Joint Institute for Nuclear Research, an international nuclear physics research center and one o ...
in Russia, the location of the JINR; the American suggestions were used for elements 102, 103, 104, and 106. The name ''dubnium'' had been used for element 104 in the previous IUPAC recommendation. The American scientists "reluctantly" approved this decision. IUPAC pointed out that the Berkeley laboratory had already been recognized several times, in the naming of
berkelium Berkelium is a transuranic radioactive chemical element with the symbol Bk and atomic number 97. It is a member of the actinide and transuranium element series. It is named after the city of Berkeley, California, the location of the Lawrence Berke ...
,
californium Californium is a radioactive chemical element with the symbol Cf and atomic number 98. The element was first synthesized in 1950 at Lawrence Berkeley National Laboratory (then the University of California Radiation Laboratory), by bombarding ...
, and
americium Americium is a synthetic radioactive chemical element with the symbol Am and atomic number 95. It is a transuranic member of the actinide series, in the periodic table located under the lanthanide element europium, and thus by analogy was na ...
, and that the acceptance of the names ''rutherfordium'' and ''seaborgium'' for elements 104 and 106 should be offset by recognizing JINR's contributions to the discovery of elements 104, 105, and 106. Even after 1997, LBL still sometimes used the name ''hahnium'' for element 105 in their own material, doing so as recently as 2014. However, the problem was resolved in the literature as Jens Volker Kratz, editor of ''Radiochimica Acta'', refused to accept papers not using the 1997 IUPAC nomenclature.


Isotopes

Dubnium, having an
atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of every ...
of 105, is a
superheavy element Superheavy elements, also known as transactinide elements, transactinides, or super-heavy elements, are the chemical elements with atomic number greater than 103. The superheavy elements are those beyond the actinides in the periodic table; the l ...
; like all elements with such high atomic numbers, it is very unstable. The longest-lasting known isotope of dubnium, 268Db, has a half-life of around a day. No stable isotopes have been seen, and a 2012 calculation by JINR suggested that the half-lives of all dubnium isotopes would not significantly exceed a day. Dubnium can only be obtained by artificial production. The short half-life of dubnium limits experimentation. This is exacerbated by the fact that the most stable isotopes are the hardest to synthesize. Elements with a lower atomic number have stable isotopes with a lower
neutron–proton ratio The neutron–proton ratio (N/Z ratio or nuclear ratio) of an atomic nucleus is the ratio of its number of neutrons to its number of protons. Among stable nuclei and naturally occurring nuclei, this ratio generally increases with increasing atomi ...
than those with higher atomic number, meaning that the target and beam nuclei that could be employed to create the superheavy element have fewer neutrons than needed to form these most stable isotopes. (Different techniques based on rapid neutron capture and transfer reactions are being considered as of the 2010s, but those based on the collision of a large and small nucleus still dominate research in the area.) Only a few atoms of 268Db can be produced in each experiment, and thus the measured lifetimes vary significantly during the process. As of 2022, following additional experiments performed at the JINR's Superheavy Element Factory (which started operations in 2019), the half-life of 268Db is measured to be hours. The second most stable isotope, 270Db, has been produced in even smaller quantities: three atoms in total, with lifetimes of 33.4 h, 1.3 h, and 1.6 h. These two are the heaviest isotopes of dubnium to date, and both were produced as a result of decay of the heavier nuclei 288 Mc and 294 Ts rather than directly, because the experiments that yielded them were originally designed in Dubna for 48Ca beams. For its mass, 48Ca has by far the greatest neutron excess of all practically stable nuclei, both quantitative and relative, which correspondingly helps synthesize superheavy nuclei with more neutrons, but this gain is compensated by the decreased likelihood of fusion for high atomic numbers.


Predicted properties

According to the
periodic law Periodic trends are specific patterns that are present in the periodic table that illustrate different aspects of a certain element. They were discovered by the Russian chemist Dmitri Mendeleev in the year 1863. Major periodic trends include atom ...
, dubnium should belong to group 5, with
vanadium Vanadium is a chemical element with the symbol V and atomic number 23. It is a hard, silvery-grey, malleable transition metal. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an oxide layer ( pas ...
,
niobium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it has sim ...
, and
tantalum Tantalum is a chemical element with the symbol Ta and atomic number 73. Previously known as ''tantalium'', it is named after Tantalus, a villain in Greek mythology. Tantalum is a very hard, ductile, lustrous, blue-gray transition metal that is ...
. Several studies have investigated the properties of element 105 and found that they generally agreed with the predictions of the periodic law. Significant deviations may nevertheless occur, due to
relativistic effects Relativistic quantum chemistry combines relativistic mechanics with quantum chemistry to calculate elemental properties and structure, especially for the heavier elements of the periodic table. A prominent example is an explanation for the color of ...
, which dramatically change physical properties on both atomic and macroscopic scales. These properties have remained challenging to measure for several reasons: the difficulties of production of superheavy atoms, the low rates of production, which only allows for microscopic scales, requirements for a radiochemistry laboratory to test the atoms, short half-lives of those atoms, and the presence of many unwanted activities apart from those of synthesis of superheavy atoms. So far, studies have only been performed on single atoms.


Atomic and physical

A direct relativistic effect is that as the atomic numbers of elements increase, the innermost electrons begin to revolve faster around the nucleus as a result of an increase of
electromagnetic attraction In physics, electromagnetism is an interaction that occurs between particles with electric charge. It is the second-strongest of the four fundamental interactions, after the strong force, and it is the dominant force in the interactions of a ...
between an electron and a nucleus. Similar effects have been found for the outermost s orbitals (and p1/2 ones, though in dubnium they are not occupied): for example, the 7s orbital contracts by 25% in size and is stabilized by 2.6  eV. A more indirect effect is that the contracted s and p1/2 orbitals
shield A shield is a piece of personal armour held in the hand, which may or may not be strapped to the wrist or forearm. Shields are used to intercept specific attacks, whether from close-ranged weaponry or projectiles such as arrows, by means of a ...
the charge of the nucleus more effectively, leaving less for the outer d and f electrons, which therefore move in larger orbitals. Dubnium is greatly affected by this: unlike the previous group 5 members, its 7s electrons are slightly more difficult to extract than its 6d electrons. Another effect is the
spin–orbit interaction In quantum physics, the spin–orbit interaction (also called spin–orbit effect or spin–orbit coupling) is a relativistic interaction of a particle's spin with its motion inside a potential. A key example of this phenomenon is the spin–orbi ...
, particularly spin–orbit splitting, which splits the 6d subshell—the
azimuthal quantum number The azimuthal quantum number is a quantum number for an atomic orbital that determines its orbital angular momentum and describes the shape of the orbital. The azimuthal quantum number is the second of a set of quantum numbers that describe t ...
ℓ of a d shell is 2—into two subshells, with four of the ten orbitals having their ℓ lowered to 3/2 and six raised to 5/2. All ten energy levels are raised; four of them are lower than the other six. (The three 6d electrons normally occupy the lowest energy levels, 6d3/2.) A singly ionized atom of dubnium (Db+) should lose a 6d electron compared to a neutral atom; the doubly (Db2+) or triply (Db3+) ionized atoms of dubnium should eliminate 7s electrons, unlike its lighter homologs. Despite the changes, dubnium is still expected to have five valence electrons; 7p energy levels have not been shown to influence dubnium and its properties. As the 6d orbitals of dubnium are more destabilized than the 5d ones of tantalum, and Db3+ is expected to have two 6d, rather than 7s, electrons remaining, the resulting +3 oxidation state is expected to be unstable and even rarer than that of tantalum. The ionization potential of dubnium in its maximum +5 oxidation state should be slightly lower than that of tantalum and the ionic radius of dubnium should increase compared to tantalum; this has a significant effect on dubnium's chemistry. Atoms of dubnium in the solid state should arrange themselves in a
body-centered cubic In crystallography, the cubic (or isometric) crystal system is a crystal system where the unit cell is in the shape of a cube. This is one of the most common and simplest shapes found in crystals and minerals. There are three main varieties of ...
configuration, like the previous group 5 elements. The predicted density of dubnium is 21.6 g/cm3.


Chemical

Computational chemistry is simplest in gas-phase chemistry, in which interactions between molecules may be ignored as negligible. Multiple authors have researched dubnium pentachloride; calculations show it to be consistent with the periodic laws by exhibiting the properties of a compound of a group 5 element. For example, the
molecular orbital In chemistry, a molecular orbital is a mathematical function describing the location and wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of finding ...
levels indicate that dubnium uses three 6d electron levels as expected. Compared to its tantalum analog, dubnium pentachloride is expected to show increased
covalent A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms ...
character: a decrease in the effective charge on an atom and an increase in the overlap population (between orbitals of dubnium and chlorine). Calculations of
solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Soluti ...
chemistry indicate that the maximum oxidation state of dubnium, +5, will be more stable than those of niobium and tantalum and the +3 and +4 states will be less stable. The tendency towards
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
of cations with the highest oxidation state should continue to decrease within group 5 but is still expected to be quite rapid.
Complexation A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many m ...
of dubnium is expected to follow group 5 trends in its richness. Calculations for hydroxo-chlorido- complexes have shown a reversal in the trends of complex formation and extraction of group 5 elements, with dubnium being more prone to do so than tantalum.


Experimental chemistry

Experimental results of the chemistry of dubnium date back to 1974 and 1976. JINR researchers used a thermochromatographic system and concluded 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 that the detected fission products confirmed that the parent was indeed element 105. These results may imply that dubnium behaves more like
hafnium Hafnium is a chemical element with the symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dmitri M ...
than niobium. The next studies on the chemistry of dubnium were conducted in 1988, in Berkeley. They examined whether the most stable oxidation state of dubnium in aqueous solution was +5. Dubnium was fumed twice and washed with concentrated
nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitri ...
;
sorption Sorption is a physical and chemical process by which one substance becomes attached to another. Specific cases of sorption are treated in the following articles: ; Absorption: "the incorporation of a substance in one state into another of a dif ...
of dubnium on glass
cover slip A microscope slide is a thin flat piece of glass, typically 75 by 26 mm (3 by 1 inches) and about 1 mm thick, used to hold objects for examination under a microscope. Typically the object is mounted (secured) on the slide, and then b ...
s was then compared with that of the group 5 elements niobium and tantalum and the group 4 elements zirconium and hafnium produced under similar conditions. The group 5 elements are known to sorb on glass surfaces; the group 4 elements do not. Dubnium was confirmed as a group 5 member. Surprisingly, the behavior on extraction from mixed nitric and
hydrofluoric acid Hydrofluoric acid is a Solution (chemistry), solution of hydrogen fluoride (HF) in water. Solutions of HF are colourless, acidic and highly Corrosive substance, corrosive. It is used to make most fluorine-containing compounds; examples include th ...
solution into
methyl isobutyl ketone Methyl isobutyl ketone (MIBK) is the common name for the organic compound 4-methylpentan-2-one, condensed chemical formula (CH3)2CHCH2C(O)CH3. This colourless liquid, a ketone, is used as a solvent for gums, resins, paints, varnishes, lacquers, and ...
differed between dubnium, tantalum, and niobium. Dubnium did not extract and its behavior resembled niobium more closely than tantalum, indicating that complexing behavior could not be predicted purely from simple extrapolations of trends within a group in the periodic table. This prompted further exploration of the chemical behavior of complexes of dubnium. Various labs jointly conducted thousands of repetitive chromatographic experiments between 1988 and 1993. All group 5 elements and
protactinium Protactinium (formerly protoactinium) is a chemical element with the symbol Pa and atomic number 91. It is a dense, silvery-gray actinide metal which readily reacts with oxygen, water vapor and inorganic acids. It forms various chemical compounds ...
were extracted from concentrated
hydrochloric acid Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid Acid strength is the tendency of an acid, symbol ...
; after mixing with lower concentrations of hydrogen chloride, small amounts of hydrogen fluoride were added to start selective re-extraction. Dubnium showed behavior different from that of tantalum but similar to that of niobium and its pseudohomolog protactinium at concentrations of hydrogen chloride below 12 moles per liter. This similarity to the two elements suggested that the formed complex was either or . After extraction experiments of dubnium from
hydrogen bromide Hydrogen bromide is the inorganic compound with the formula . It is a hydrogen halide consisting of hydrogen and bromine. A colorless gas, it dissolves in water, forming hydrobromic acid, which is saturated at 68.85% HBr by weight at room temper ...
into diisobutyl carbinol (2,6-dimethylheptan-4-ol), a specific extractant for protactinium, with subsequent elutions with the hydrogen chloride/hydrogen fluoride mix as well as hydrogen chloride, dubnium was found to be less prone to extraction than either protactinium or niobium. This was explained as an increasing tendency to form non‐extractable complexes of multiple negative charges. Further experiments in 1992 confirmed the stability of the +5 state: Db(V) was shown to be extractable from cation‐exchange columns with α‐hydroxyisobutyrate, like the group 5 elements and protactinium; Db(III) and Db(IV) were not. In 1998 and 1999, new predictions suggested that dubnium would extract nearly as well as niobium and better than tantalum from halide solutions, which was later confirmed. The first isothermal gas chromatography experiments were performed in 1992 with 262Db (half-life 35 seconds). The volatilities for niobium and tantalum were similar within 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 , which was predicted to be less volatile than . Later experiments in 1996 showed that group 5 chlorides were more volatile than the corresponding bromides, with the exception of tantalum, presumably due to formation of . Later volatility studies of chlorides of dubnium and niobium as a function of controlled partial pressures of oxygen showed that formation of oxychlorides and general volatility are dependent on concentrations of oxygen. The oxychlorides were shown to be less volatile than the chlorides. In 2004–05, researchers from Dubna and Livermore identified a new dubnium isotope, 268Db, as a fivefold alpha decay product of the newly created element 115. This new isotope proved to be long-lived enough to allow further chemical experimentation, with a half-life of over a day. In the 2004 experiment, a thin layer with dubnium was removed from the surface of the target and dissolved in aqua regia with tracers and a
lanthanum Lanthanum is a chemical element with the symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air. It is the eponym of the lanthanide series, a group of 15 similar elements between lantha ...
carrier, from which various +3, +4, and +5 species were precipitated on adding
ammonium hydroxide Ammonia solution, also known as ammonia water, ammonium hydroxide, ammoniacal liquor, ammonia liquor, aqua ammonia, aqueous ammonia, or (inaccurately) ammonia, is a solution of ammonia in water. It can be denoted by the symbols NH3(aq). Although ...
. The precipitate was washed and dissolved in hydrochloric acid, where it converted to nitrate form and was then dried on a film and counted. Mostly containing a +5 species, which was immediately assigned to dubnium, it also had a +4 species; based on that result, the team decided that additional chemical separation was needed. In 2005, the experiment was repeated, with the final product being hydroxide rather than nitrate precipitate, which was processed further in both Livermore (based on reverse phase chromatography) and Dubna (based on anion exchange chromatography). The +5 species was effectively isolated; dubnium appeared three times in tantalum-only fractions and never in niobium-only fractions. It was noted that these experiments were insufficient to draw conclusions about the general chemical profile of dubnium. In 2009, at the JAEA tandem accelerator in Japan, dubnium was processed in nitric and hydrofluoric acid solution, at concentrations where niobium forms and tantalum forms . Dubnium's behavior was close to that of niobium but not tantalum; it was thus deduced that dubnium formed . From the available information, it was concluded that dubnium often behaved like niobium, sometimes like protactinium, but rarely like tantalum. In 2021, the volatile heavy group 5 oxychlorides MOCl3 (M = Nb, Ta, Db) were experimentally studied at the JAEA tandem accelerator. The trend in volatilities was found to be NbOCl3 > TaOCl3 ≥ DbOCl3, so that dubnium behaves in line with periodic trends.


Notes


References


Bibliography

* * * * * {{Authority control Chemical elements Transition metals Synthetic elements Chemical elements with body-centered cubic structure