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Neptunium is a
chemical element A chemical element is a species of atoms that have a given number of protons in their atomic nucleus, nuclei, including the pure Chemical substance, substance consisting only of that species. Unlike chemical compounds, chemical elements canno ...
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 ...
Np 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 ever ...
93. A
radioactive Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is consi ...
actinide The actinide () or actinoid () series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium. The actinide series derives its name from the first element in the series, actinium. The info ...
metal, neptunium is the first transuranic element. Its position in the
periodic table The periodic table, also known as the periodic table of the (chemical) elements, is a rows and columns arrangement of the chemical elements. It is widely used in chemistry, physics, and other sciences, and is generally seen as an icon of ch ...
just after
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 ...
, named after the planet
Uranus Uranus is the seventh planet from the Sun. Its name is a reference to the Greek god of the sky, Uranus ( Caelus), who, according to Greek mythology, was the great-grandfather of Ares (Mars), grandfather of Zeus (Jupiter) and father of ...
, led to it being named after Neptune, the next planet beyond Uranus. A neptunium atom has 93
proton A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
s and 93 electrons, of which seven are valence electrons. Neptunium metal is silvery and tarnishes when exposed to air. The element occurs in three allotropic forms and it normally exhibits five
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s, ranging from +3 to +7. It is
radioactive Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is consi ...
, poisonous,
pyrophoric A substance is pyrophoric (from grc-gre, πυροφόρος, , 'fire-bearing') if it ignites spontaneously in air at or below (for gases) or within 5 minutes after coming into contact with air (for liquids and solids). Examples are organolith ...
, and capable of accumulating in
bone A bone is a rigid organ that constitutes part of the skeleton in most vertebrate animals. Bones protect the various other organs of the body, produce red and white blood cells, store minerals, provide structure and support for the body, ...
s, which makes the handling of neptunium dangerous. Although many false claims of its discovery were made over the years, the element was first synthesized by Edwin McMillan and Philip H. Abelson at the Berkeley Radiation Laboratory in 1940. Since then, most neptunium has been and still is produced by neutron irradiation of uranium in nuclear reactors. The vast majority is generated as a by-product in conventional
nuclear power Nuclear power is the use of nuclear reactions to produce electricity. Nuclear power can be obtained from nuclear fission, nuclear decay and nuclear fusion reactions. Presently, the vast majority of electricity from nuclear power is produced b ...
reactors. While neptunium itself has no commercial uses at present, it is used as a precursor for the formation of
plutonium-238 Plutonium-238 (238Pu or Pu-238) is a fissile, radioactive isotope of plutonium that has a half-life of 87.7 years. Plutonium-238 is a very powerful alpha emitter; as alpha particles are easily blocked, this makes the plutonium-238 isotope suit ...
, and in
radioisotope thermal generator A radioisotope thermoelectric generator (RTG, RITEG), sometimes referred to as a radioisotope power system (RPS), is a type of nuclear battery that uses an array of thermocouples to convert the heat released by the decay of a suitable radioact ...
s to provide electricity for
spacecraft A spacecraft is a vehicle or machine designed to fly in outer space. A type of artificial satellite, spacecraft are used for a variety of purposes, including communications, Earth observation, meteorology, navigation, space colonization, ...
. Neptunium has also been used in detectors of high-energy
neutron The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the atomic nucleus, nuclei of atoms. Since protons and ...
s. The longest-lived
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 num ...
of neptunium, neptunium-237, is a by-product of
nuclear reactor A nuclear reactor is a device used to initiate and control a fission nuclear chain reaction or nuclear fusion reactions. Nuclear reactors are used at nuclear power plants for electricity generation and in nuclear marine propulsion. Heat fr ...
s and
plutonium Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exh ...
production. It, and the isotope neptunium-239, are also found in trace amounts in
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 ...
ores due to neutron capture reactions and
beta decay In nuclear physics, beta decay (β-decay) is a type of radioactive decay in which a beta particle (fast energetic electron or positron) is emitted from an atomic nucleus, transforming the original nuclide to an isobar of that nuclide. For ...
. __TOC__


Characteristics


Physical

Neptunium is a hard, silvery, ductile,
radioactive Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is consi ...
actinide
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
. In the
periodic table The periodic table, also known as the periodic table of the (chemical) elements, is a rows and columns arrangement of the chemical elements. It is widely used in chemistry, physics, and other sciences, and is generally seen as an icon of ch ...
, it is located to the right of the actinide
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 ...
, to the left of the actinide
plutonium Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exh ...
and below the
lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yt ...
promethium Promethium is a chemical element with the symbol Pm and atomic number 61. All of its isotopes are radioactive; it is extremely rare, with only about 500–600 grams naturally occurring in Earth's crust at any given time. Promethium is one of onl ...
. Neptunium is a hard metal, having a bulk modulus of 118  GPa, comparable to that of
manganese Manganese is a chemical element with the Symbol (chemistry), symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of ...
. Neptunium metal is similar to uranium in terms of physical workability. When exposed to air at normal temperatures, it forms a thin oxide layer. This reaction proceeds more rapidly as the temperature increases. Neptunium melts at 639±3 °C: this low melting point, a property the metal shares with the neighboring element plutonium (which has melting point 639.4 °C), is due to the
hybridization Hybridization (or hybridisation) may refer to: *Hybridization (biology), the process of combining different varieties of organisms to create a hybrid *Orbital hybridization, in chemistry, the mixing of atomic orbitals into new hybrid orbitals *Nu ...
of the 5f and 6d orbitals and the formation of directional bonds in the metal. The boiling point of neptunium is not empirically known and the usually given value of 4174 °C is extrapolated from the
vapor pressure Vapor pressure (or vapour pressure in English-speaking countries other than the US; see spelling differences) or equilibrium vapor pressure is defined as the pressure exerted by a vapor in thermodynamic equilibrium with its condensed pha ...
of the element. If accurate, this would give neptunium the largest liquid range of any element (3535 K passes between its melting and boiling points). Neptunium is found in at least three allotropes. Some claims of a fourth allotrope have been made, but they are so far not proven.Yoshida et al., p. 718. This multiplicity of allotropes is common among the actinides. The
crystal structure In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric pattern ...
s of neptunium, protactinium, uranium, and plutonium do not have clear analogs among the lanthanides and are more similar to those of the 3d 
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. α-neptunium takes on an orthorhombic structure, resembling a highly distorted body-centered cubic structure.Lemire, R. J. et al.,''Chemical Thermodynamics of Neptunium and Plutonium'', Elsevier, Amsterdam, 2001. Each neptunium atom is coordinated to four others and the Np–Np bond lengths are 260 pm.Yoshida et al., p. 719. It is the densest of all the actinides and the fifth-densest of all naturally occurring elements, behind only rhenium,
platinum Platinum is a chemical element with the symbol Pt and atomic number 78. It is a dense, malleable, ductile, highly unreactive, precious, silverish-white transition metal. Its name originates from Spanish , a diminutive of "silver". Pla ...
,
iridium Iridium is a chemical element with the symbol Ir and atomic number 77. A very hard, brittle, silvery-white transition metal of the platinum group, it is considered the second-densest naturally occurring metal (after osmium) with a density o ...
, and
osmium Osmium (from Greek grc, ὀσμή, osme, smell, label=none) is a chemical element with the symbol Os and atomic number 76. It is a hard, brittle, bluish-white transition metal in the platinum group that is found as a trace element in alloys, ...
.Theodore Gray. ''The Elements''. Page 215. α-neptunium has semimetallic properties, such as strong
covalent bond 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 ato ...
ing and a high electrical resistivity, and its metallic physical properties are closer to those of the metalloids than the true metals. Some allotropes of the other actinides also exhibit similar behaviour, though to a lesser degree. The densities of different isotopes of neptunium in the alpha phase are expected to be observably different: α-235Np should have density 20.303 g/cm3; α-236Np, density 20.389 g/cm3; α-237Np, density 20.476 g/cm3. β-neptunium takes on a distorted tetragonal close-packed structure. Four atoms of neptunium make up a unit cell, and the Np–Np bond lengths are 276 pm. γ-neptunium has a body-centered cubic structure and has Np–Np bond length of 297 pm. The γ form becomes less stable with increased pressure, though the melting point of neptunium also increases with pressure. The β-Np/γ-Np/liquid
triple point In thermodynamics, the triple point of a substance is the temperature and pressure at which the three phases (gas, liquid, and solid) of that substance coexist in thermodynamic equilibrium.. It is that temperature and pressure at which the ...
occurs at 725 °C and 3200  MPa.


Alloys

Due to the presence of valence 5f electrons, neptunium and its alloys exhibit very interesting magnetic behavior, like many other actinides. These can range from the itinerant band-like character characteristic of the
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 to the local moment behavior typical of
scandium Scandium is a chemical element with the symbol Sc and atomic number 21. It is a silvery-white metallic d-block element. Historically, it has been classified as a rare-earth element, together with yttrium and the Lanthanides. It was discovered in ...
, yttrium, and the
lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yt ...
s. This stems from 5f-orbital hybridization with the orbitals of the metal
ligand In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's elect ...
s, and the fact that the 5f orbital is relativistically destabilized and extends outwards.Yoshida et al., pp. 719–20. For example, pure neptunium is paramagnetic, Np Al3 is ferromagnetic, Np Ge3 has no magnetic ordering, and Np Sn3 behaves fermionically. Investigations are underway regarding alloys of neptunium with uranium,
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 n ...
,
plutonium Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exh ...
, zirconium, and
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in ...
, so as to recycle long-lived waste isotopes such as neptunium-237 into shorter-lived isotopes more useful as nuclear fuel. One neptunium-based superconductor alloy has been discovered with formula Np Pd5Al2. This occurrence in neptunium compounds is somewhat surprising because they often exhibit strong magnetism, which usually destroys superconductivity. The alloy has a tetragonal structure with a superconductivity transition temperature of −268.3 °C (4.9 K).


Chemical

Neptunium has five ionic
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s ranging from +3 to +7 when forming chemical compounds, which can be simultaneously observed in solutions. It is the heaviest actinide that can lose all its valence electrons in a stable compound. The most stable state in solution is +5, but the valence +4 is preferred in solid neptunium compounds. Neptunium metal is very reactive. Ions of neptunium are prone to hydrolysis and formation of
coordination compound 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. Man ...
s.


Atomic

A neptunium atom has 93 electrons, arranged in the configuration Rn.html" ;"title="Radon.html" ;"title="/nowiki>Radon">Rn">Radon.html" ;"title="/nowiki>Radon">Rn/nowiki> 5f4 6d1 7s2. This differs from the configuration expected by the Aufbau principle in that one electron is in the 6d Electron shell#Subshells, subshell instead of being as expected in the 5f subshell. This is because of the similarity of the electron energies of the 5f, 6d, and 7s subshells. In forming compounds and ions, all the valence electrons may be lost, leaving behind an inert core of inner electrons with the electron configuration of the noble gas radon; more commonly, only some of the valence electrons will be lost. The electron configuration for the tripositive ion Np3+ is nnbsp;5f4, with the outermost 7s and 6d electrons lost first: this is exactly analogous to neptunium's lanthanide homolog promethium, and conforms to the trend set by the other actinides with their nnbsp;5f''n'' electron configurations in the tripositive state. The first ionization potential of neptunium was measured to be at most in 1974, based on the assumption that the 7s electrons would ionize before 5f and 6d; more recent measurements have refined this to 6.2657 eV.


Isotopes

24 neptunium radioisotopes have been characterized with the most stable being 237Np with 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 ...
of 2.14 million years, 236Np with a half-life of 154,000 years, and 235Np with a half-life of 396.1 days. All of the remaining
radioactive Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is consi ...
isotopes have half-lives that are less than 4.5 days, and the majority of these have half-lives that are less than 50 minutes. This element also has at least four meta states, with the most stable being 236mNp with a half-life of 22.5 hours. . The isotopes of neptunium range in atomic weight from 219.032 u (219Np) to 244.068 u (244Np), though 221Np and 222Np have not yet been reported. Most of the isotopes that are lighter than the most stable one, 237Np, decay primarily by
electron capture Electron capture (K-electron capture, also K-capture, or L-electron capture, L-capture) is a process in which the proton-rich nucleus of an electrically neutral atom absorbs an inner atomic electron, usually from the K or L electron shells. ...
although a sizable number, most notably 229Np and 230Np, also exhibit various levels of decay via alpha emission to become protactinium. 237Np itself, being the beta-stable isobar of mass number 237, decays almost exclusively by alpha emission into 233 Pa, with very rare (occurring only about once in trillions of decays) spontaneous fission and cluster decay (emission of 30Mg to form 207Tl). All of the known isotopes except one that are heavier than this decay exclusively via beta emission. The lone exception, 240mNp, exhibits a rare (>0.12%) decay by isomeric transition in addition to beta emission. 237Np eventually decays to form bismuth-209 and
thallium Thallium is a chemical element with the symbol Tl and atomic number 81. It is a gray post-transition metal that is not found free in nature. When isolated, thallium resembles tin, but discolors when exposed to air. Chemists William Crookes an ...
-205, unlike most other common heavy nuclei which decay into isotopes of lead. This decay chain is known as the neptunium series. This decay chain had long been extinct on Earth due to the short half-lives of all of its isotopes above bismuth-209, but is now being resurrected thanks to artificial production of neptunium on the tonne scale. The isotopes neptunium-235, -236, and -237 are predicted to be fissile; only neptunium-237's fissionability has been experimentally shown, with the
critical mass In nuclear engineering, a critical mass is the smallest amount of fissile material needed for a sustained nuclear chain reaction. The critical mass of a fissionable material depends upon its nuclear properties (specifically, its nuclear fi ...
being about 60 kg, only about 10 kg more than that of the commonly used
uranium-235 Uranium-235 (235U or U-235) is an isotope of uranium making up about 0.72% of natural uranium. Unlike the predominant isotope uranium-238, it is fissile, i.e., it can sustain a nuclear chain reaction. It is the only fissile isotope that exi ...
. Calculated values of the critical masses of neptunium-235, -236, and -237 respectively are 66.2 kg, 6.79 kg, and 63.6 kg: the neptunium-236 value is even lower than that of plutonium-239. In particular, 236Np also has a low neutron cross section. Despite this, a neptunium
atomic bomb A nuclear weapon is an explosive device that derives its destructive force from nuclear reactions, either fission (fission bomb) or a combination of fission and fusion reactions ( thermonuclear bomb), producing a nuclear explosion. Both bomb ...
has never been built: uranium and plutonium have lower critical masses than 235Np and 237Np, and 236Np is difficult to purify as it is not found in quantity in spent nuclear fuel and is nearly impossible to separate in any significant quantities from its parent 237Np.


Occurrence

Since all isotopes of neptunium have half-lives that are many times shorter than the age of the Earth, any primordial neptunium should have decayed by now. After only about 80 million years, the concentration of even the longest-lived isotope, 237Np, would have been reduced to less than one-trillionth (10−12) of its original amount.Yoshida et al., pp. 703–4. Thus neptunium is present in nature only in negligible amounts produced as intermediate decay products of other isotopes. Trace amounts of the neptunium isotopes neptunium-237 and -239 are found naturally as
decay product In nuclear physics, a decay product (also known as a daughter product, daughter isotope, radio-daughter, or daughter nuclide) is the remaining nuclide left over from radioactive decay. Radioactive decay often proceeds via a sequence of steps ( ...
s from transmutation reactions in uranium ores.Emsley, pp. 345–347. In particular, 239Np and 237Np are the most common of these isotopes; they are directly formed from
neutron capture Neutron capture is a nuclear reaction in which an atomic nucleus and one or more neutrons collide and merge to form a heavier nucleus. Since neutrons have no electric charge, they can enter a nucleus more easily than positively charged protons ...
by uranium-238 atoms. These neutrons come from the spontaneous fission of uranium-238, naturally neutron-induced fission of uranium-235, cosmic ray spallation of nuclei, and light elements absorbing
alpha particle Alpha particles, also called alpha rays or alpha radiation, consist of two protons and two neutrons bound together into a particle identical to a helium-4 nucleus. They are generally produced in the process of alpha decay, but may also be prod ...
s and emitting a neutron. The half-life of 239Np is very short, although the detection of its much longer-lived
daughter A daughter is a female offspring; a girl or a woman in relation to her parents. Daughterhood is the state of being someone's daughter. The male counterpart is a son. Analogously the name is used in several areas to show relations between groups ...
239Pu in nature in 1951 definitively established its natural occurrence. In 1952, 237Np was identified and isolated from concentrates of uranium ore from the
Belgian Congo The Belgian Congo (french: Congo belge, ; nl, Belgisch-Congo) was a Belgian colony in Central Africa from 1908 until independence in 1960. The former colony adopted its present name, the Democratic Republic of the Congo (DRC), in 1964. Colo ...
: in these minerals, the ratio of neptunium-237 to uranium is less than or equal to about 10−12 to 1. Most neptunium (and plutonium) now encountered in the environment is due to atmospheric nuclear explosions that took place between the detonation of the
first atomic bomb Trinity was the code name of the first detonation of a nuclear weapon. It was conducted by the United States Army at 5:29 a.m. on July 16, 1945, as part of the Manhattan Project. The test was conducted in the Jornada del Muerto desert abo ...
in 1945 and the ratification of the Partial Nuclear Test Ban Treaty in 1963. The total amount of neptunium released by these explosions and the few atmospheric tests that have been carried out since 1963 is estimated to be around 2500 kg. The overwhelming majority of this is composed of the long-lived isotopes 236Np and 237Np since even the moderately long-lived 235Np (half-life 396 days) would have decayed to less than one-billionth (10−9) its original concentration over the intervening decades. An additional very small amount of neptunium, created by neutron irradiation of natural uranium in nuclear reactor cooling water, is released when the water is discharged into rivers or lakes. The concentration of 237Np in seawater is approximately 6.5 × 10−5  millibecquerels per liter: this concentration is between 0.1% and 1% that of plutonium. Once in the environment, neptunium generally
oxidizes Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
fairly quickly, usually to the +4 or +5 state. Regardless of its oxidation state, the element exhibits much greater mobility than the other actinides, largely due to its ability to readily form aqueous solutions with various other elements. In one study comparing the diffusion rates of neptunium(V), plutonium(IV), and americium(III) in sandstone and limestone, neptunium penetrated more than ten times as well as the other elements. Np(V) will also react efficiently in pH levels greater than 5.5 if there are no
carbonate A carbonate is a salt of carbonic acid (H2CO3), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word ''carbonate'' may also refer to a carbonate ester, an organic compound containing the carbonate ...
s present and in these conditions it has also been observed to readily bond with
quartz Quartz is a hard, crystalline mineral composed of silica ( silicon dioxide). The atoms are linked in a continuous framework of SiO4 silicon-oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall chemical f ...
. It has also been observed to bond well with goethite,
ferric oxide Iron(III) oxide or ferric oxide is the inorganic compound with the formula Fe2O3. It is one of the three main oxides of iron, the other two being iron(II) oxide (FeO), which is rare; and iron(II,III) oxide (Fe3O4), which also occurs naturall ...
colloids, and several clays including
kaolinite Kaolinite ( ) is a clay mineral, with the chemical composition Al2 Si2 O5( OH)4. It is an important industrial mineral. It is a layered silicate mineral, with one tetrahedral sheet of silica () linked through oxygen atoms to one octahed ...
and smectite. Np(V) does not bond as readily to soil particles in mildly acidic conditions as its fellow actinides americium and curium by nearly an order of magnitude. This behavior enables it to migrate rapidly through the soil while in solution without becoming fixed in place, contributing further to its mobility.Atwood, section 4. Np(V) is also readily absorbed by concrete, which because of the element's radioactivity is a consideration that must be addressed when building nuclear waste storage facilities. When absorbed in concrete, it is reduced to Np(IV) in a relatively short period of time. Np(V) is also reduced by humic acid if it is present on the surface of goethite,
hematite Hematite (), also spelled as haematite, is a common iron oxide compound with the formula, Fe2O3 and is widely found in rocks and soils. Hematite crystals belong to the rhombohedral lattice system which is designated the alpha polymorph of . ...
, and
magnetite Magnetite is a mineral and one of the main iron ores, with the chemical formula Fe2+Fe3+2O4. It is one of the oxides of iron, and is ferrimagnetic; it is attracted to a magnet and can be magnetized to become a permanent magnet itself. With ...
. Np(IV) is absorbed efficiently by
tuff Tuff is a type of rock made of volcanic ash ejected from a vent during a volcanic eruption. Following ejection and deposition, the ash is lithified into a solid rock. Rock that contains greater than 75% ash is considered tuff, while rock ...
, granodiorite, and bentonite; although uptake by the latter is most pronounced in mildly acidic conditions. It also exhibits a strong tendency to bind to colloidal particulates, an effect that is enhanced when in soil with high clay content. The behavior provides an additional aid in the element's observed high mobility.Atwood, section 1.


History


Background and early claims

When the first
periodic table The periodic table, also known as the periodic table of the (chemical) elements, is a rows and columns arrangement of the chemical elements. It is widely used in chemistry, physics, and other sciences, and is generally seen as an icon of ch ...
of the elements was published by
Dmitri Mendeleev Dmitri Ivanovich Mendeleev (sometimes transliterated as Mendeleyev or Mendeleef) ( ; russian: links=no, Дмитрий Иванович Менделеев, tr. , ; 8 February Old_Style_and_New_Style_dates">O.S._27_January.html" ;"title="O ...
in the early 1870s, it showed a " — " in place after uranium similar to several other places for then-undiscovered elements. Other subsequent tables of known elements, including a 1913 publication of the known radioactive isotopes by Kasimir Fajans, also show an empty place after uranium, element 92. Up to and after the discovery of the final component of the atomic nucleus, the
neutron The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the atomic nucleus, nuclei of atoms. Since protons and ...
in 1932, most scientists did not seriously consider the possibility of elements heavier than uranium. While nuclear theory at the time did not explicitly prohibit their existence, there was little evidence to suggest that they did. However, the discovery of induced radioactivity by Irène and
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 ...
in late 1933 opened up an entirely new method of researching the elements and inspired a small group of Italian scientists led by
Enrico Fermi Enrico Fermi (; 29 September 1901 – 28 November 1954) was an Italian (later naturalized American) physicist and the creator of the world's first nuclear reactor, the Chicago Pile-1. He has been called the "architect of the nuclear age" an ...
to begin a series of experiments involving neutron bombardment. Although the Joliot-Curies' experiment involved bombarding a sample of 27 Al with
alpha particle Alpha particles, also called alpha rays or alpha radiation, consist of two protons and two neutrons bound together into a particle identical to a helium-4 nucleus. They are generally produced in the process of alpha decay, but may also be prod ...
s to produce the radioactive 30 P, Fermi realized that using neutrons, which have no electrical charge, would most likely produce even better results than the positively charged alpha particles. Accordingly, in March 1934 he began systematically subjecting all of the then-known elements to neutron bombardment to determine whether others could also be induced to radioactivity. After several months of work, Fermi's group had tentatively determined that lighter elements would disperse the energy of the captured neutron by emitting a
proton A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
or
alpha particle Alpha particles, also called alpha rays or alpha radiation, consist of two protons and two neutrons bound together into a particle identical to a helium-4 nucleus. They are generally produced in the process of alpha decay, but may also be prod ...
and heavier elements would generally accomplish the same by emitting a
gamma ray A gamma ray, also known as gamma radiation (symbol γ or \gamma), is a penetrating form of electromagnetic radiation arising from the radioactive decay of atomic nuclei. It consists of the shortest wavelength electromagnetic waves, typically ...
. This latter behavior would later result in the
beta decay In nuclear physics, beta decay (β-decay) is a type of radioactive decay in which a beta particle (fast energetic electron or positron) is emitted from an atomic nucleus, transforming the original nuclide to an isobar of that nuclide. For ...
of a neutron into a proton, thus moving the resulting isotope one place up the periodic table. When Fermi's team bombarded uranium, they observed this behavior as well, which strongly suggested that the resulting isotope had 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 ever ...
of 93. Fermi was initially reluctant to publicize such a claim, but after his team observed several unknown half-lives in the uranium bombardment products that did not match those of any known isotope, he published a paper entitled ''Possible Production of Elements of Atomic Number Higher than 92'' in June 1934. In it he proposed the name ausonium (atomic symbol Ao) for element 93, after the Greek name ''Ausonia'' (Italy). Several theoretical objections to the claims of Fermi's paper were quickly raised; in particular, the exact process that took place when an atom captured a neutron was not well understood at the time. This and Fermi's accidental discovery three months later that nuclear reactions could be induced by slow neutrons cast further doubt in the minds of many scientists, notably Aristid von Grosse and
Ida Noddack Ida Noddack (25 February 1896 – 24 September 1978), ''née'' Tacke, was a German chemist and physicist. In 1934 she was the first to mention the idea later named nuclear fission. With her husband - Walter Noddack - and Otto Berg she discov ...
, that the experiment was creating element 93. While von Grosse's claim that Fermi was actually producing protactinium (element 91) was quickly tested and disproved, Noddack's proposal that the uranium had been shattered into two or more much smaller fragments was simply ignored by most because existing nuclear theory did not include a way for this to be possible. Fermi and his team maintained that they were in fact synthesizing a new element, but the issue remained unresolved for several years. Although the many different and unknown radioactive half-lives in the experiment's results showed that several nuclear reactions were occurring, Fermi's group could not prove that element 93 was being created unless they could isolate it chemically. They and many other scientists attempted to accomplish this, including Otto Hahn and Lise Meitner who were among the best radiochemists in the world at the time and supporters of Fermi's claim, but they all failed. Much later, it was determined that the main reason for this failure was because the predictions of element 93's chemical properties were based on a periodic table which lacked the actinide series. This arrangement placed protactinium below tantalum, uranium below tungsten, and further suggested that element 93, at that point referred to as eka-rhenium, should be similar to the
group 7 element Group 7, numbered by IUPAC nomenclature, is a group of elements in the periodic table. They are manganese (Mn), technetium (Tc), rhenium (Re), and bohrium (Bh). All known elements of group 7 are transition metals. Like other groups, the member ...
s, including manganese and rhenium. Thorium, protactinium, and uranium, with their dominant oxidation states of +4, +5, and +6 respectively, fooled scientists into thinking they belonged below hafnium, tantalum, and tungsten, rather than below the lanthanide series, which was at the time viewed as a fluke, and whose members all have dominant +3 states; neptunium, on the other hand, has a much rarer, more unstable +7 state, with +4 and +5 being the most stable. Upon finding that
plutonium Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exh ...
and the other transuranic elements also have dominant +3 and +4 states, along with the discovery of the
f-block A block of the periodic table is a set of elements unified by the atomic orbitals their valence electrons or vacancies lie in. The term appears to have been first used by Charles Janet. Each block is named after its characteristic orbital: s-bl ...
, the actinide series was firmly established. While the question of whether Fermi's experiment had produced element 93 was stalemated, two additional claims of the discovery of the element appeared, although unlike Fermi, they both claimed to have observed it in nature. The first of these claims was by Czech engineer Odolen Koblic in 1934 when he extracted a small amount of material from the wash water of heated pitchblende. He proposed the name
bohemium Bohemium was the name assigned to the element with atomic number 93, now known as neptunium, when its discovery was first incorrectly alleged. It was named after Bohemia. The alleged discovery took place in 1934 and it was published shortly afte ...
for the element, but after being analyzed it turned out that the sample was a mixture of
tungsten Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isol ...
and vanadium. The other claim, in 1938 by Romanian physicist Horia Hulubei and French chemist Yvette Cauchois, claimed to have discovered the new element via
spectroscopy Spectroscopy is the field of study that measures and interprets the electromagnetic spectra that result from the interaction between electromagnetic radiation and matter as a function of the wavelength or frequency of the radiation. Matter ...
in minerals. They named their element sequanium, but the claim was discounted because the prevailing theory at the time was that if it existed at all, element 93 would not exist naturally. However, as neptunium does in fact occur in nature in trace amounts, as demonstrated when it was found in uranium ore in 1952, it is possible that Hulubei and Cauchois did in fact observe neptunium. Although by 1938 some scientists, including Niels Bohr, were still reluctant to accept that Fermi had actually produced a new element, he was nevertheless awarded the
Nobel Prize in Physics ) , image = Nobel Prize.png , alt = A golden medallion with an embossed image of a bearded man facing left in profile. To the left of the man is the text "ALFR•" then "NOBEL", and on the right, the text (smaller) "NAT•" then " ...
in November 1938 "''for his demonstrations of the existence of new radioactive elements produced by neutron irradiation, and for his related discovery of nuclear reactions brought about by slow neutrons''". A month later, the almost totally unexpected discovery of
nuclear fission Nuclear fission is a reaction in which the nucleus of an atom splits into two or more smaller nuclei. The fission process often produces gamma photons, and releases a very large amount of energy even by the energetic standards of radio ...
by Hahn, Meitner, and Otto Frisch put an end to the possibility that Fermi had discovered element 93 because most of the unknown half-lives that had been observed by Fermi's team were rapidly identified as those of fission products. Perhaps the closest of all attempts to produce the missing element 93 was that conducted by the Japanese physicist Yoshio Nishina working with chemist Kenjiro Kimura in 1940, just before the outbreak of the
Pacific War The Pacific War, sometimes called the Asia–Pacific War, was the theater of World War II that was fought in Asia, the Pacific Ocean, the Indian Ocean, and Oceania. It was geographically the largest theater of the war, including the vas ...
in 1941: they bombarded 238U with fast neutrons. However, while slow neutrons tend to induce neutron capture through a (n, γ) reaction, fast neutrons tend to induce a "knock-out" (n, 2n) reaction, where one neutron is added and two more are removed, resulting in the net loss of a neutron. Nishina and Kimura, having tested this technique on 232 Th and successfully produced the known 231Th and its long-lived beta decay daughter 231 Pa (both occurring in the natural decay chain of 235U), therefore correctly assigned the new 6.75-day half-life activity they observed to the new isotope 237U. They confirmed that this isotope was also a beta emitter and must hence decay to the unknown nuclide 23793. They attempted to isolate this nuclide by carrying it with its supposed lighter congener rhenium, but no beta or alpha decay was observed from the rhenium-containing fraction: Nishina and Kimura thus correctly speculated that the half-life of 23793, like that of 231Pa, was very long and hence its activity would be so weak as to be unmeasurable by their equipment, thus concluding the last and closest unsuccessful search for transuranic elements.


Discovery

As research on nuclear fission progressed in early 1939, Edwin McMillan at the Berkeley Radiation Laboratory of the
University of California, Berkeley The University of California, Berkeley (UC Berkeley, Berkeley, Cal, or California) is a public land-grant research university in Berkeley, California. Established in 1868 as the University of California, it is the state's first land-grant un ...
decided to run an experiment bombarding uranium using the powerful 60-inch (1.52 m) cyclotron that had recently been built at the university. The purpose was to separate the various fission products produced by the bombardment by exploiting the enormous force that the fragments gain from their mutual electrical repulsion after fissioning. Although he did not discover anything of note from this, McMillan did observe two new beta decay half-lives in the uranium trioxide target itself, which meant that whatever was producing the radioactivity had not violently repelled each other like normal fission products. He quickly realized that one of the half-lives closely matched the known 23-minute decay period of uranium-239, but the other half-life of 2.3 days was unknown. McMillan took the results of his experiment to chemist and fellow Berkeley professor Emilio Segrè to attempt to isolate the source of the radioactivity. Both scientists began their work using the prevailing theory that element 93 would have similar chemistry to rhenium, but Segrè rapidly determined that McMillan's sample was not at all similar to rhenium. Instead, when he reacted it with
hydrogen fluoride Hydrogen fluoride (fluorane) is an inorganic compound with the chemical formula . This colorless gas or liquid is the principal industrial source of fluorine, often as an aqueous solution called hydrofluoric acid. It is an important feedstock ...
(HF) with a strong
oxidizing agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or " accepts"/"receives" an electron from a (called the , , or ). In other words, an oxi ...
present, it behaved much like members of the rare earths. Since these elements comprise a large percentage of fission products, Segrè and McMillan decided that the half-life must have been simply another fission product, titling the paper "An Unsuccessful Search for Transuranium Elements". However, as more information about fission became available, the possibility that the fragments of nuclear fission could still have been present in the target became more remote. McMillan and several scientists, including Philip H. Abelson, attempted again to determine what was producing the unknown half-life. In early 1940, McMillan realized that his 1939 experiment with Segrè had failed to test the chemical reactions of the radioactive source with sufficient rigor. In a new experiment, McMillan tried subjecting the unknown substance to HF in the presence of a
reducing agent In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are commonly reducing agents include the Earth met ...
, something he had not done before. This reaction resulted in the sample precipitating with the HF, an action that definitively ruled out the possibility that the unknown substance was a rare-earth metal. Shortly after this, Abelson, who had received his graduate degree from the university, visited Berkeley for a short vacation and McMillan asked the more able chemist to assist with the separation of the experiment's results. Abelson very quickly observed that whatever was producing the 2.3-day half-life did not have chemistry like any known element and was actually more similar to uranium than a rare-earth metal. This discovery finally allowed the source to be isolated and later, in 1945, led to the classification of the actinide series. As a final step, McMillan and Abelson prepared a much larger sample of bombarded uranium that had a prominent 23-minute half-life from 239U and demonstrated conclusively that the unknown 2.3-day half-life increased in strength in concert with a decrease in the 23-minute activity through the following reaction: : + -> -> beta^-23\ \ce] -> beta^-2.355\ \ce] ''(The times are half-life, half-lives.)'' This proved that the unknown radioactive source originated from the decay of uranium and, coupled with the previous observation that the source was different chemically from all known elements, proved beyond all doubt that a new element had been discovered. McMillan and Abelson published their results in a paper entitled ''Radioactive Element 93'' in the ''
Physical Review ''Physical Review'' is a peer-reviewed scientific journal established in 1893 by Edward Nichols. It publishes original research as well as scientific and literature reviews on all aspects of physics. It is published by the American Physical ...
'' on May 27, 1940. They did not propose a name for the element in the paper, but they soon decided on the name ''neptunium'' since Neptune is the next planet beyond
Uranus Uranus is the seventh planet from the Sun. Its name is a reference to the Greek god of the sky, Uranus ( Caelus), who, according to Greek mythology, was the great-grandfather of Ares (Mars), grandfather of Zeus (Jupiter) and father of ...
in our solar system. McMillan and Abelson's success compared to Nishina and Kimura's near miss can be attributed to the favorable half-life of 239Np for radiochemical analysis and quick decay of 239U, in contrast to the slower decay of 237U and extremely long half-life of 237Np.


Subsequent developments

It was also realized that the beta decay of 239Np must produce an isotope of element 94 (now called
plutonium Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exh ...
), but the quantities involved in McMillan and Abelson's original experiment were too small to isolate and identify plutonium along with neptunium. The discovery of plutonium had to wait until the end of 1940, when Glenn T. Seaborg and his team identified the isotope
plutonium-238 Plutonium-238 (238Pu or Pu-238) is a fissile, radioactive isotope of plutonium that has a half-life of 87.7 years. Plutonium-238 is a very powerful alpha emitter; as alpha particles are easily blocked, this makes the plutonium-238 isotope suit ...
. In 1942, Hahn and Fritz Strassmann, and independently
Kurt Starke Kurt Starke (1911 in Berlin – 19 January 2000) was a German radiochemist. During World War II, he worked on the German nuclear energy project, also known as the Uranium Club. He independently discovered the transuranic element neptunium. From ...
, reported the confirmation of element 93 in Berlin. Hahn's group did not pursue element 94, likely because they were discouraged by McMillan and Abelson's lack of success in isolating it. Since they had access to the stronger cyclotron at Paris at this point, Hahn's group would likely have been able to detect element 94 had they tried, albeit in tiny quantities (a few
becquerels The becquerel (; symbol: Bq) is the unit of radioactivity in the International System of Units (SI). One becquerel is defined as the activity of a quantity of radioactive material in which one nucleus decays per second. For applications relatin ...
). Neptunium's unique radioactive characteristics allowed it to be traced as it moved through various compounds in chemical reactions, at first this was the only method available to prove that its chemistry was different from other elements. As the first isotope of neptunium to be discovered has such a short half-life, McMillan and Abelson were unable to prepare a sample that was large enough to perform chemical analysis of the new element using the technology that was then available. However, after the discovery of the long-lived 237Np isotope in 1942 by Glenn Seaborg and Arthur Wahl, forming weighable amounts of neptunium became a realistic endeavor. Its half-life was initially determined to be about 3 million years (later revised to 2.144 million years), confirming the predictions of Nishina and Kimura of a very long half-life. Early research into the element was somewhat limited because most of the nuclear physicists and chemists in the United States at the time were focused on the massive effort to research the properties of plutonium as part of the
Manhattan Project The Manhattan Project was a research and development undertaking during World War II that produced the first nuclear weapons. It was led by the United States with the support of the United Kingdom and Canada. From 1942 to 1946, the project w ...
. Research into the element did continue as a minor part of the project and the first bulk sample of neptunium was isolated in 1944. Much of the research into the properties of neptunium since then has been focused on understanding how to confine it as a portion of nuclear waste. Because it has isotopes with very long half-lives, it is of particular concern in the context of designing confinement facilities that can last for thousands of years. It has found some limited uses as a radioactive tracer and a precursor for various nuclear reactions to produce useful plutonium isotopes. However, most of the neptunium that is produced as a reaction byproduct in nuclear power stations is considered to be a waste product.


Production


Synthesis

The vast majority of the neptunium that currently exists on Earth was produced artificially in nuclear reactions. Neptunium-237 is the most commonly synthesized isotope due to it being the only one that both can be created via
neutron capture Neutron capture is a nuclear reaction in which an atomic nucleus and one or more neutrons collide and merge to form a heavier nucleus. Since neutrons have no electric charge, they can enter a nucleus more easily than positively charged protons ...
and also has a half-life long enough to allow weighable quantities to be easily isolated. As such, it is by far the most common isotope to be utilized in chemical studies of the element.Yoshida et al., p. 700–2. * When an 235U atom captures a neutron, it is converted to an excited state of 236U. About 81% of the excited 236U nuclei undergo fission, but the remainder decay to the ground state of 236U by emitting
gamma radiation A gamma ray, also known as gamma radiation (symbol γ or \gamma), is a penetrating form of electromagnetic radiation arising from the radioactive decay of atomic nuclei. It consists of the shortest wavelength electromagnetic waves, typically s ...
. Further neutron capture creates 237U which has a half-life of 7 days and quickly decays to 237Np through
beta decay In nuclear physics, beta decay (β-decay) is a type of radioactive decay in which a beta particle (fast energetic electron or positron) is emitted from an atomic nucleus, transforming the original nuclide to an isobar of that nuclide. For ...
. During beta decay, the excited 237U emits an electron, while the atomic weak interaction converts a
neutron The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the atomic nucleus, nuclei of atoms. Since protons and ...
to a
proton A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
, thus creating 237Np. ::\begin \ce\\ \ce \end * 237U is also produced via an ( n,2n) reaction with 238U. This only happens with very energetic neutrons. * 237Np is the product of
alpha decay Alpha decay or α-decay is a type of radioactive decay in which an atomic nucleus emits an alpha particle (helium nucleus) and thereby transforms or 'decays' into a different atomic nucleus, with a mass number that is reduced by four and an at ...
of 241Am, which is produced through neutron irradiation of uranium-238. Heavier isotopes of neptunium decay quickly, and lighter isotopes of neptunium cannot be produced by neutron capture, so chemical separation of neptunium from cooled spent nuclear fuel gives nearly pure 237Np. The short-lived heavier isotopes 238Np and 239Np, useful as
radioactive tracer A radioactive tracer, radiotracer, or radioactive label is a chemical compound in which one or more atoms have been replaced by a radionuclide so by virtue of its radioactive decay it can be used to explore the mechanism of chemical reactions by ...
s, are produced through neutron irradiation of 237Np and 238U respectively, while the longer-lived lighter isotopes 235Np and 236Np are produced through irradiation of 235U with
proton A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
s and deuterons in a cyclotron. Artificial 237Np metal is usually isolated through a reaction of 237NpF3 with liquid
barium Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Th ...
or
lithium Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense soli ...
at around 1200 ° C and is most often extracted from spent
nuclear fuel rod Nuclear fuel is material used in nuclear power stations to produce heat to power turbines. Heat is created when nuclear fuel undergoes nuclear fission. Most nuclear fuels contain heavy fissile actinide elements that are capable of undergoing ...
s in kilogram amounts as a by-product in
plutonium Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exh ...
production. :2 NpF3 + 3 Ba → 2 Np + 3 BaF2 By weight, neptunium-237 discharges are about 5% as great as plutonium discharges and about 0.05% of spent nuclear fuel discharges. However, even this fraction still amounts to more than fifty tons per year globally.


Purification methods

Recovering uranium and plutonium from spent nuclear fuel for reuse is one of the major processes of the nuclear fuel cycle. As it has a long half-life of just over 2 million years, the
alpha emitter Alpha particles, also called alpha rays or alpha radiation, consist of two protons and two neutrons bound together into a particle identical to a helium-4 nucleus. They are generally produced in the process of alpha decay, but may also be produce ...
237Np is one of the major isotopes of the
minor actinide The minor actinides are the actinide elements in used nuclear fuel other than uranium and plutonium, which are termed the major actinides. The minor actinides include neptunium (element 93), americium (element 95), curium (element 96), berkeliu ...
s separated from spent nuclear fuel.Yodshida et al., pp. 704–5. Many separation methods have been used to separate out the neptunium, operating on small and large scales. The small-scale purification operations have the goals of preparing pure neptunium as a
precursor Precursor or Precursors may refer to: * Precursor (religion), a forerunner, predecessor ** The Precursor, John the Baptist Science and technology * Precursor (bird), a hypothesized genus of fossil birds that was composed of fossilized parts of u ...
of metallic neptunium and its compounds, and also to isolate and preconcentrate neptunium in samples for analysis. Most methods that separate neptunium ions exploit the differing chemical behaviour of the differing oxidation states of neptunium (from +3 to +6 or sometimes even +7) in solution. Among the methods that are or have been used are: solvent
extraction Extraction may refer to: Science and technology Biology and medicine * Comedo extraction, a method of acne treatment * Dental extraction, the surgical removal of a tooth from the mouth Computing and information science * Data extraction, the pr ...
(using various extractants, usually multidentate β-diketone derivatives, organophosphorus compounds, and
amine In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent ...
compounds), chromatography using various
ion-exchange Ion exchange is a reversible interchange of one kind of ion present in an insoluble solid with another of like charge present in a solution surrounding the solid with the reaction being used especially for softening or making water demineralised, ...
or chelating resins, coprecipitation (possible matrices include LaF3, BiPO4, BaSO4, Fe(OH)3, and MnO2), electrodeposition, and biotechnological methods.Yoshida et al., pp. 705–17. Currently, commercial reprocessing plants use the Purex process, involving the solvent extraction of uranium and plutonium with tributyl phosphate.Yoshida et al., p. 710.


Chemistry and compounds


Solution chemistry

When it is in an aqueous solution, neptunium can exist in any of its five possible oxidation states (+3 to +7) and each of these show a characteristic color. The stability of each oxidation state is strongly dependent on various factors, such as the presence of oxidizing or
reducing agent In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are commonly reducing agents include the Earth met ...
s, pH of the solution, presence of
coordination complex 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. M ...
-forming
ligand In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's elect ...
s, and even the concentration of neptunium in the solution.Yoshida et al., pp. 752–4. In acidic solutions, the neptunium(III) to neptunium(VII) ions exist as Np3+, Np4+, , , and . In basic solutions, they exist as the oxides and hydroxides Np(OH)3, NpO2, NpO2OH, NpO2(OH)2, and . Not as much work has been done to characterize neptunium in basic solutions. Np3+ and Np4+ can easily be reduced and oxidized to each other, as can and .Yoshida et al., p. 759. ;Neptunium(III) Np(III) or Np3+ exists as hydrated complexes in acidic solutions, . It is a dark blue-purple and is analogous to its lighter congener, the pink rare-earth ion Pm3+. In the presence of
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...
, it is quickly oxidized to Np(IV) unless strong reducing agents are also present. Nevertheless, it is the second-least easily
hydrolyzed Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution, elimination, and solvation reactions in which water is the nucleophile. Biological hydrolysis ...
neptunium ion in water, forming the NpOH2+ ion. Np3+ is the predominant neptunium ion in solutions of pH 4–5.Yoshida et al., p. 766–70. ;Neptunium(IV) Np(IV) or Np4+ is pale yellow-green in acidic solutions, where it exists as hydrated complexes (). It is quite unstable to hydrolysis in acidic aqueous solutions at pH 1 and above, forming NpOH3+. In basic solutions, Np4+ tends to hydrolyze to form the neutral neptunium(IV) hydroxide (Np(OH)4) and neptunium(IV) oxide (NpO2). ;Neptunium(V) Np(V) or is green-blue in aqueous solution, in which it behaves as a strong Lewis acid. It is a stable ion and is the most common form of neptunium in aqueous solutions. Unlike its neighboring homologues and , does not spontaneously
disproportionate In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can ...
except at very low pH and high concentration: :2 + 4 H+ ⇌ Np4+ + + 2 H2O It hydrolyzes in basic solutions to form NpO2OH and . ;Neptunium(VI) Np(VI) or , the neptunyl ion, shows a light pink or reddish color in an acidic solution and yellow-green otherwise. It is a strong Lewis acid and is the main neptunium ion encountered in solutions of pH 3–4. Though stable in acidic solutions, it is quite easily reduced to the Np(V) ion, and it is not as stable as the homologous hexavalent ions of its neighbours uranium and plutonium (the
uranyl The uranyl ion is an oxycation of uranium in the oxidation state +6, with the chemical formula . It has a linear structure with short U–O bonds, indicative of the presence of multiple bonds between uranium and oxygen. Four or more ligands may ...
and plutonyl ions). It hydrolyzes in basic solutions to form the oxo and hydroxo ions NpO2OH+, , and . ;Neptunium(VII) Np(VII) is dark green in a strongly basic solution. Though its
chemical formula In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, ...
in basic solution is frequently cited as , this is a simplification and the real structure is probably closer to a hydroxo species like . Np(VII) was first prepared in basic solution in 1967. In strongly acidic solution, Np(VII) is found as ; water quickly reduces this to Np(VI). Its hydrolysis products are uncharacterized.


Hydroxides

The oxides and hydroxides of neptunium are closely related to its ions. In general, Np hydroxides at various oxidation levels are less stable than the actinides before it on the periodic table such as
thorium Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high ...
and uranium and more stable than those after it such as plutonium and americium. This phenomenon is because the stability of an ion increases as the ratio of atomic number to the radius of the ion increases. Thus actinides higher on the periodic table will more readily undergo
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, elimination, and solvation reactions in which water is the nucleophile. Biological hydrolysi ...
. Neptunium(III) hydroxide is quite stable in acidic solutions and in environments that lack oxygen, but it will rapidly oxidize to the IV state in the presence of air. It is not soluble in water. Np(IV) hydroxides exist mainly as the electrically neutral Np(OH)4 and its mild solubility in water is not affected at all by the pH of the solution. This suggests that the other Np(IV) hydroxide, , does not have a significant presence. Because the Np(V) ion is very stable, it can only form a hydroxide in high acidity levels. When placed in a 0.1  M
sodium perchlorate Sodium perchlorate is the inorganic compound with the chemical formula Na ClO4. It is a white crystalline, hygroscopic solid that is highly soluble in water and in alcohol. It is usually encountered as the monohydrate. The compound is noteworthy ...
solution, it does not react significantly for a period of months, although a higher molar concentration of 3.0 M will result in it reacting to the solid hydroxide NpO2OH almost immediately. Np(VI) hydroxide is more reactive but it is still fairly stable in acidic solutions. It will form the compound NpO3· H2O in the presence of
ozone Ozone (), or trioxygen, is an inorganic molecule with the chemical formula . It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope , breaking down in the l ...
under various
carbon dioxide Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is t ...
pressures. Np(VII) has not been well-studied and no neutral hydroxides have been reported. It probably exists mostly as .


Oxides

Three anhydrous neptunium oxides have been reported, NpO2, Np2O5, and Np3O8, though some studies have stated that only the first two of these exist, suggesting that claims of Np3O8 are actually the result of mistaken analysis of Np2O5. However, as the full extent of the reactions that occur between neptunium and oxygen has yet to be researched, it is not certain which of these claims is accurate. Although neptunium oxides have not been produced with neptunium in oxidation states as high as those possible with the adjacent actinide uranium, neptunium oxides are more stable at lower oxidation states. This behavior is illustrated by the fact that NpO2 can be produced by simply burning neptunium salts of oxyacids in air.Yoshida et al., 724–726. The greenish-brown NpO2 is very stable over a large range of pressures and temperatures and does not undergo phase transitions at low temperatures. It does show a phase transition from face-centered cubic to orthorhombic at around 33-37GPa, although it returns to is original phase when pressure is released. It remains stable under oxygen pressures up to 2.84 MPa and temperatures up to 400 °C. Np2O5 is black-brown in color and
monoclinic In crystallography, the monoclinic crystal system is one of the seven crystal systems. A crystal system is described by three vectors. In the monoclinic system, the crystal is described by vectors of unequal lengths, as in the orthorhombic ...
with a lattice size of 418×658×409 picometres. It is relatively unstable and decomposes to NpO2 and O2 at 420-695 °C. Although Np2O5 was initially subject to several studies that claimed to produce it with mutually contradictory methods, it was eventually prepared successfully by heating neptunium
peroxide In chemistry, peroxides are a group of compounds with the structure , where R = any element. The group in a peroxide is called the peroxide group or peroxo group. The nomenclature is somewhat variable. The most common peroxide is hydrogen p ...
to 300-350 °C for 2–3 hours or by heating it under a layer of water in an ampoule at 180 °C. Neptunium also forms a large number of oxide compounds with a wide variety of elements, although the neptunate oxides formed with
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
s and alkaline earth metals have been by far the most studied. Ternary neptunium oxides are generally formed by reacting NpO2 with the oxide of another element or by precipitating from an alkaline solution. Li5NpO6 has been prepared by reacting Li2O and NpO2 at 400 °C for 16 hours or by reacting Li2O2 with NpO3 · H2O at 400 °C for 16 hours in a quartz tube and flowing oxygen. Alkali neptunate compounds K3NpO5, Cs3NpO5, and Rb3NpO5 are all created by a similar reaction: :NpO2 + 3 MO2 → M3NpO5 (M = K, Cs, Rb) The oxide compounds KNpO4, CsNpO4, and RbNpO4 are formed by reacting Np(VII) () with a compound of the alkali metal nitrate and
ozone Ozone (), or trioxygen, is an inorganic molecule with the chemical formula . It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope , breaking down in the l ...
. Additional compounds have been produced by reacting NpO3 and water with solid alkali and alkaline
peroxide In chemistry, peroxides are a group of compounds with the structure , where R = any element. The group in a peroxide is called the peroxide group or peroxo group. The nomenclature is somewhat variable. The most common peroxide is hydrogen p ...
s at temperatures of 400 - 600 °C for 15–30 hours. Some of these include Ba3(NpO5)2, Ba2 NaNpO6, and Ba2LiNpO6. Also, a considerable number of hexavalent neptunium oxides are formed by reacting solid-state NpO2 with various alkali or alkaline earth oxides in an environment of flowing oxygen. Many of the resulting compounds also have an equivalent compound that substitutes uranium for neptunium. Some compounds that have been characterized include Na2Np2O7, Na4NpO5, Na6NpO6, and Na2NpO4. These can be obtained by heating different combinations of NpO2 and Na2O to various temperature thresholds and further heating will also cause these compounds to exhibit different neptunium allotropes. The lithium neptunate oxides Li6NpO6 and Li4NpO5 can be obtained with similar reactions of NpO2 and Li2O.Yoshida et al, pp. 728–730. A large number of additional alkali and alkaline neptunium oxide compounds such as Cs4Np5O17 and Cs2Np3O10 have been characterized with various production methods. Neptunium has also been observed to form ternary oxides with many additional elements in groups 3 through 7, although these compounds are much less well studied.


Halides

Although neptunium
halide In chemistry, a halide (rarely halogenide) is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a flu ...
compounds have not been nearly as well studied as its oxides, a fairly large number have been successfully characterized. Of these, neptunium fluorides have been the most extensively researched, largely because of their potential use in separating the element from nuclear waste products. Four binary neptunium fluoride compounds, Np F3, NpF4, NpF5, and NpF6, have been reported. The first two are fairly stable and were first prepared in 1947 through the following reactions: :NpO2 + H2 + 3 HF → NpF3 + 2 H2O   (400°C) :NpF3 + O2 + HF → NpF4 + H2O  (400°C) Later, NpF4 was obtained directly by heating NpO2 to various temperatures in mixtures of either
hydrogen fluoride Hydrogen fluoride (fluorane) is an inorganic compound with the chemical formula . This colorless gas or liquid is the principal industrial source of fluorine, often as an aqueous solution called hydrofluoric acid. It is an important feedstock ...
or pure fluorine gas. NpF5 is much more difficult to create and most known preparation methods involve reacting NpF4 or NpF6 compounds with various other fluoride compounds. NpF5 will decompose into NpF4 and NpF6 when heated to around 320 °C.Yoshida et al, pp. 730–736. NpF6 or neptunium hexafluoride is extremely volatile, as are its adjacent actinide compounds uranium hexafluoride (UF6) and plutonium hexafluoride (PuF6). This volatility has attracted a large amount of interest to the compound in an attempt to devise a simple method for extracting neptunium from spent nuclear power station fuel rods. NpF6 was first prepared in 1943 by reacting NpF3 and gaseous fluorine at very high temperatures and the first bulk quantities were obtained in 1958 by heating NpF4 and dripping pure fluorine on it in a specially prepared apparatus. Additional methods that have successfully produced neptunium hexafluoride include reacting BrF3 and BrF5 with NpF4 and by reacting several different neptunium oxide and fluoride compounds with anhydrous hydrogen fluorides. Four neptunium
oxyfluoride In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula , where X = fluorine (F), chlor ...
compounds, NpO2F, NpOF3, NpO2F2, and NpOF4, have been reported, although none of them have been extensively studied. NpO2F2 is a pinkish solid and can be prepared by reacting NpO3 · H2O and Np2F5 with pure fluorine at around 330 °C. NpOF3 and NpOF4 can be produced by reacting neptunium oxides with anhydrous hydrogen fluoride at various temperatures. Neptunium also forms a wide variety of fluoride compounds with various elements. Some of these that have been characterized include CsNpF6, Rb2NpF7, Na3NpF8, and K3NpO2F5. Two neptunium
chloride The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride s ...
s, Np Cl3 and NpCl4, have been characterized. Although several attempts to create NpCl5 have been made, they have not been successful. NpCl3 is created by reducing neptunium dioxide with hydrogen and carbon tetrachloride ( CCl4) and NpCl4 by reacting a neptunium oxide with CCl4 at around 500 °C. Other neptunium chloride compounds have also been reported, including NpOCl2, Cs2NpCl6, Cs3NpO2Cl4, and Cs2NaNpCl6. Neptunium bromides Np Br3 and NpBr4 have also been created; the latter by reacting aluminium bromide with NpO2 at 350 °C and the former in an almost identical procedure but with
zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
present. The neptunium iodide Np I3 has also been prepared by the same method as NpBr3.Yoshida et al, pp. 736–738.


Chalcogenides, pnictides, and carbides

Neptunium chalcogen and pnictogen compounds have been well studied primarily as part of research into their electronic and magnetic properties and their interactions in the natural environment. Pnictide and
carbide In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece. Interstitial / Metallic carbides The carbides of t ...
compounds have also attracted interest because of their presence in the fuel of several advanced nuclear reactor designs, although the latter group has not had nearly as much research as the former.Yoshida et al, pp. 739–742. ;Chalcogenides A wide variety of neptunium
sulfide Sulfide (British English also sulphide) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to chemical compounds la ...
compounds have been characterized, including the pure sulfide compounds Np S, NpS3, Np2S5, Np3S5, Np2S3, and Np3S4. Of these, Np2S3, prepared by reacting NpO2 with
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The under ...
and carbon disulfide at around 1000 °C, is the most well-studied and three allotropic forms are known. The α form exists up to around 1230 °C, the β up to 1530 °C, and the γ form, which can also exist as Np3S4, at higher temperatures. NpS can be created by reacting Np2S3 and neptunium metal at 1600 °C and Np3S5 can be prepared by the decomposition of Np2S3 at 500 °C or by reacting sulfur and neptunium hydride at 650 °C. Np2S5 is made by heating a mixture of Np3S5 and pure sulfur to 500 °C. All of the neptunium sulfides except for the β and γ forms of Np2S3 are isostructural with the equivalent uranium sulfide and several, including NpS, α−Np2S3, and β−Np2S3 are also isostructural with the equivalent plutonium sulfide. The oxysulfides NpOS, Np4O4S, and Np2O2S have also been created, although the latter three have not been well studied. NpOS was first prepared in 1985 by vacuum sealing NpO2, Np3S5, and pure sulfur in a quartz tube and heating it to 900 °C for one week. Neptunium selenide compounds that have been reported include Np Se, NpSe3, Np2Se3, Np2Se5, Np3Se4, and Np3Se5. All of these have only been obtained by heating neptunium hydride and selenium metal to various temperatures in a vacuum for an extended period of time and Np2Se3 is only known to exist in the γ allotrope at relatively high temperatures. Two neptunium oxyselenide compounds are known, NpOSe and Np2O2Se, are formed with similar methods by replacing the neptunium hydride with neptunium dioxide. The known neptunium telluride compounds Np Te, NpTe3, Np3Te4, Np2Te3, and Np2O2Te are formed by similar procedures to the selenides and Np2O2Te is isostructural to the equivalent uranium and plutonium compounds. No neptunium− polonium compounds have been reported. ;Pnictides and carbides Neptunium nitride (Np N) was first prepared in 1953 by reacting neptunium hydride and
ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous ...
gas at around 750 °C in a quartz capillary tube. Later, it was produced by reacting different mixtures of nitrogen and hydrogen with neptunium metal at various temperatures. It has also been created by the reduction of neptunium dioxide with diatomic nitrogen gas at 1550 °C. NpN is isomorphous with uranium mononitride (UN) and plutonium mononitride (PuN) and has a melting point of 2830 °C under a nitrogen pressure of around 1 MPa. Two neptunium phosphide compounds have been reported, Np P and Np3P4. The first has a face centered cubic structure and is prepared by converting neptunium metal to a powder and then reacting it with
phosphine Phosphine (IUPAC name: phosphane) is a colorless, flammable, highly toxic compound with the chemical formula , classed as a pnictogen hydride. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like rotting ...
gas at 350 °C. Np3P4 can be created by reacting neptunium metal with
red phosphorus Elemental phosphorus can exist in several allotropes, the most common of which are white and red solids. Solid violet and black allotropes are also known. Gaseous phosphorus exists as diphosphorus and atomic phosphorus. White phosphorus Whit ...
at 740 °C in a vacuum and then allowing any extra phosphorus to sublimate away. The compound is non-reactive with water but will react with
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 ni ...
to produce Np(IV) solution.Yoshida et al, pp. 742–744. Three neptunium arsenide compounds have been prepared, Np As, NpAs2, and Np3As4. The first two were first created by heating arsenic and neptunium hydride in a vacuum-sealed tube for about a week. Later, NpAs was also made by confining neptunium metal and arsenic in a vacuum tube, separating them with a quartz membrane, and heating them to just below neptunium's melting point of 639 °C, which is slightly higher than the arsenic's sublimation point of 615 °C. Np3As4 is prepared by a similar procedure using iodine as a transporting agent. NpAs2 crystals are brownish gold and Np3As4 is black. The neptunium antimonide compound Np Sb was created in 1971 by placing equal quantities of both elements in a vacuum tube, heating them to the melting point of antimony, and then heating it further to 1000 °C for sixteen days. This procedure also created trace amounts of an additional antimonide compound Np3Sb4. One neptunium- bismuth compound, NpBi, has also been reported. The neptunium
carbide In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece. Interstitial / Metallic carbides The carbides of t ...
s Np C, Np2C3, and NpC2 (tentative) have been reported, but have not characterized in detail despite the high importance and utility of actinide carbides as advanced nuclear reactor fuel. NpC is a non-stoichiometric compound, and could be better labelled as NpC''x'' (0.82 ≤ ''x'' ≤ 0.96). It may be obtained from the reaction of neptunium hydride with
graphite Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on la ...
at 1400 °C or by heating the constituent elements together in an electric arc furnace using a
tungsten Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isol ...
electrode. It reacts with excess carbon to form pure Np2C3. NpC2 is formed from heating NpO2 in a graphite crucible at 2660–2800 °C.


Other inorganic

;Hydrides Neptunium reacts with
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-to ...
in a similar manner to its neighbor plutonium, forming the
hydride In chemistry, a hydride is formally the anion of hydrogen( H−). The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride ...
s NpH2+''x'' ( face-centered cubic) and NpH3 (
hexagonal In geometry, a hexagon (from Greek , , meaning "six", and , , meaning "corner, angle") is a six-sided polygon. The total of the internal angles of any simple (non-self-intersecting) hexagon is 720°. Regular hexagon A '' regular hexagon'' has ...
). These are isostructural with the corresponding plutonium hydrides, although unlike PuH2+''x'', the lattice parameters of NpH2+''x'' become greater as the hydrogen content (''x'') increases. The hydrides require extreme care in handling as they decompose in a vacuum at 300 °C to form finely divided neptunium metal, which is
pyrophoric A substance is pyrophoric (from grc-gre, πυροφόρος, , 'fire-bearing') if it ignites spontaneously in air at or below (for gases) or within 5 minutes after coming into contact with air (for liquids and solids). Examples are organolith ...
.Yoshida et al., pp. 722–4. ;Phosphates, sulfates, and carbonates Being chemically stable, neptunium
phosphate In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid . The phosphate or orthophosphate ion is derived from phosph ...
s have been investigated for potential use in immobilizing nuclear waste. Neptunium pyrophosphate (α-NpP2O7), a green solid, has been produced in the reaction between neptunium dioxide and boron phosphate at 1100 °C, though neptunium(IV) phosphate has so far remained elusive. The series of compounds NpM2(PO4)3, where M is an
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
( Li, Na, K, Rb, or Cs), are all known. Some neptunium sulfates have been characterized, both aqueous and solid and at various oxidation states of neptunium (IV through VI have been observed). Additionally, neptunium
carbonate A carbonate is a salt of carbonic acid (H2CO3), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word ''carbonate'' may also refer to a carbonate ester, an organic compound containing the carbonate ...
s have been investigated to achieve a better understanding of the behavior of neptunium in geological repositories and the environment, where it may come into contact with carbonate and
bicarbonate In inorganic chemistry, bicarbonate (IUPAC-recommended nomenclature: hydrogencarbonate) is an intermediate form in the deprotonation of carbonic acid. It is a polyatomic anion with the chemical formula . Bicarbonate serves a crucial biochemi ...
aqueous solutions and form soluble complexes.Yoshida et al., pp. 744–5.


Organometallic

A few organoneptunium compounds are known and chemically characterized, although not as many as for
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 ...
due to neptunium's scarcity and radioactivity. The most well known organoneptunium compounds are the cyclopentadienyl and cyclooctatetraenyl compounds and their derivatives.Yoshida et al., pp. 750–2. The trivalent cyclopentadienyl compound Np(C5H5)3·
THF Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water-miscible organic liquid with low viscosity. It is ma ...
was obtained in 1972 from reacting Np(C5H5)3Cl with
sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable ...
, although the simpler Np(C5H5) could not be obtained. Tetravalent neptunium cyclopentadienyl, a reddish-brown complex, was synthesized in 1968 by reacting neptunium(IV) chloride with potassium cyclopentadienide: :NpCl4 + 4 KC5H5 → Np(C5H5)4 + 4 KCl It is soluble in
benzene Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms ...
and
THF Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water-miscible organic liquid with low viscosity. It is ma ...
, and is less sensitive to
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...
and water than Pu(C5H5)3 and Am(C5H5)3. Other Np(IV) cyclopentadienyl compounds are known for many
ligand In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's elect ...
s: they have the general formula (C5H5)3NpL, where L represents a ligand.
Neptunocene Neptunocene, Np(C8H8)2, is an organoneptunium compound composed of a neptunium atom sandwiched between two cyclooctatetraenide (COT2-) rings. As a solid it has a dark brown/red colour but it appears yellow when dissolved in chlorocarbons, in whic ...
, Np(C8H8)2, was synthesized in 1970 by reacting neptunium(IV) chloride with K2(C8H8). It is isomorphous to uranocene and
plutonocene Plutonocene, Pu(C8H8)2, is an organoplutonium compound composed of a plutonium atom sandwiched between two cyclooctatetraenide (COT2-) rings. It is a dark red, very air-sensitive solid that is sparingly soluble in toluene and chlorocarbons. Plu ...
, and they behave chemically identically: all three compounds are insensitive to water or dilute bases but are sensitive to air, reacting quickly to form oxides, and are only slightly soluble in benzene and
toluene Toluene (), also known as toluol (), is a substituted aromatic hydrocarbon. It is a colorless, water-insoluble liquid with the smell associated with paint thinners. It is a mono-substituted benzene derivative, consisting of a methyl group (CH3) ...
. Other known neptunium cyclooctatetraenyl derivatives include Np(RC8H7)2 (R =
ethanol Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an alcohol with the chemical formula . Its formula can be also written as or (an ethyl group linked to a ...
, butanol) and KNp(C8H8)·2THF, which is isostructural to the corresponding plutonium compound. In addition, neptunium
hydrocarbyl In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or e ...
s have been prepared, and solvated triiodide complexes of neptunium are a precursor to many organoneptunium and inorganic neptunium compounds.


Coordination complexes

There is much interest in the
coordination chemistry 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. Man ...
of neptunium, because its five oxidation states all exhibit their own distinctive chemical behavior, and the coordination chemistry of the actinides is heavily influenced by the actinide contraction (the greater-than-expected decrease in
ionic radii Ionic radius, ''r''ion, is the radius of a monatomic ion in an ionic crystal structure. Although neither atoms nor ions have sharp boundaries, they are treated as if they were hard spheres with radii such that the sum of ionic radii of the cation ...
across the actinide series, analogous to the lanthanide contraction).Yoshida et al., pp. 745–750.


Solid state

Few neptunium(III) coordination compounds are known, because Np(III) is readily oxidized by atmospheric oxygen while in aqueous solution. However, sodium formaldehyde sulfoxylate can reduce Np(IV) to Np(III), stabilizing the lower oxidation state and forming various sparingly soluble Np(III) coordination complexes, such as ·11H2O, ·H2O, and . Many neptunium(IV) coordination compounds have been reported, the first one being , which is isostructural with the analogous uranium(IV) coordination compound. Other Np(IV) coordination compounds are known, some involving other metals such as
cobalt Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, p ...
(·8H2O, formed at 400 K) and
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
(·6H2O, formed at 600 K). Complex nitrate compounds are also known: the experimenters who produced them in 1986 and 1987 produced single crystals by slow evaporation of the Np(IV) solution at ambient temperature in 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 ni ...
and excess 2,2′- pyrimidine. The coordination chemistry of neptunium(V) has been extensively researched due to the presence of cation–cation interactions in the solid state, which had been already known for actinyl ions. Some known such compounds include the neptunyl
dimer Dimer may refer to: * Dimer (chemistry), a chemical structure formed from two similar sub-units ** Protein dimer, a protein quaternary structure ** d-dimer * Dimer model, an item in statistical mechanics, based on ''domino tiling'' * Julius Dimer ( ...
·8H2O and neptunium glycolate, both of which form green crystals. Neptunium(VI) compounds range from the simple oxalate (which is unstable, usually becoming Np(IV)) to such complicated compounds as the green . Extensive study has been performed on compounds of the form , where M represents a monovalent cation and An is either uranium, neptunium, or plutonium. Since 1967, when neptunium(VII) was discovered, some coordination compounds with neptunium in the +7 oxidation state have been prepared and studied. The first reported such compound was initially characterized as ·''n''H2O in 1968, but was suggested in 1973 to actually have the formula ·2H2O based on the fact that Np(VII) occurs as in aqueous solution. This compound forms dark green prismatic crystals with maximum edge length 0.15–0.4  mm.


In aqueous solution

Most neptunium
coordination complex 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. M ...
es known in solution involve the element in the +4, +5, and +6 oxidation states: only a few studies have been done on neptunium(III) and (VII) coordination complexes.Yoshida et al., pp. 771–82. For the former, NpX2+ and (X = Cl, Br) were obtained in 1966 in concentrated LiCl and LiBr solutions, respectively: for the latter, 1970 experiments discovered that the ion could form sulfate complexes in acidic solutions, such as and ; these were found to have higher stability constants than the neptunyl ion (). A great many complexes for the other neptunium oxidation states are known: the inorganic ligands involved are the
halide In chemistry, a halide (rarely halogenide) is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a flu ...
s, iodate,
azide In chemistry, azide is a linear, polyatomic anion with the formula and structure . It is the conjugate base of hydrazoic acid . Organic azides are organic compounds with the formula , containing the azide functional group. The dominant appli ...
, nitride, nitrate, thiocyanate, sulfate,
carbonate A carbonate is a salt of carbonic acid (H2CO3), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word ''carbonate'' may also refer to a carbonate ester, an organic compound containing the carbonate ...
, chromate, and
phosphate In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid . The phosphate or orthophosphate ion is derived from phosph ...
. Many organic ligands are known to be able to be used in neptunium coordination complexes: they include acetate, propionate, glycolate,
lactate Lactate may refer to: * Lactation, the secretion of milk from the mammary glands * Lactate, the conjugate base of lactic acid Lactic acid is an organic acid. It has a molecular formula . It is white in the solid state and it is miscible with w ...
, oxalate, malonate, phthalate, mellitate, and citrate. Analogously to its neighbours, uranium and plutonium, the order of the neptunium ions in terms of complex formation ability is Np4+ > ≥ Np3+ > . (The relative order of the middle two neptunium ions depends on the
ligand In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's elect ...
s and solvents used.) The stability sequence for Np(IV), Np(V), and Np(VI) complexes with monovalent inorganic ligands is F > > SCN > > Cl > ; the order for divalent inorganic ligands is > > . These follow the strengths of the corresponding acids. The divalent ligands are more strongly complexing than the monovalent ones. can also form the complex ions [] (M = Al, gallium, Ga, scandium, Sc, indium, In, iron, Fe, chromium, Cr, rhodium, Rh) in perchloric acid solution: the strength of interaction between the two cations follows the order Fe > In > Sc > Ga > Al. The neptunyl and uranyl ions can also form a complex together.


Applications


Precursor in plutonium production

An important use of 237Np is as a precursor in plutonium production, where it is irradiated with neutrons to create Plutonium-238, 238Pu, an
alpha emitter Alpha particles, also called alpha rays or alpha radiation, consist of two protons and two neutrons bound together into a particle identical to a helium-4 nucleus. They are generally produced in the process of alpha decay, but may also be produce ...
for
radioisotope thermal generator A radioisotope thermoelectric generator (RTG, RITEG), sometimes referred to as a radioisotope power system (RPS), is a type of nuclear battery that uses an array of thermocouples to convert the heat released by the decay of a suitable radioact ...
s for spacecraft and military applications. 237Np will capture a neutron to form 238Np and
beta decay In nuclear physics, beta decay (β-decay) is a type of radioactive decay in which a beta particle (fast energetic electron or positron) is emitted from an atomic nucleus, transforming the original nuclide to an isobar of that nuclide. For ...
with a half-life of just over two days to 238Pu. :^_Np + ^_n -> ^_Np -> beta^-2.117 \ \ce] ^_Pu 238Pu also exists in sizable quantities in spent nuclear fuel but would have to be separated from other isotopes of plutonium.Yoshida et al., pp. 702–3. Irradiating neptunium-237 with electron beams, provoking
bremsstrahlung ''Bremsstrahlung'' (), from "to brake" and "radiation"; i.e., "braking radiation" or "deceleration radiation", is electromagnetic radiation produced by the deceleration of a charged particle when deflected by another charged particle, typical ...
, also produces quite pure samples of the isotope
plutonium-236 Plutonium (94Pu) is an artificial element, except for trace quantities resulting from neutron capture by uranium, and thus a standard atomic weight cannot be given. Like all artificial elements, it has no stable isotopes. It was synthesized long b ...
, useful as a tracer to determine plutonium concentration in the environment.


Weapons

Neptunium is fissionable, and could theoretically be used as fuel in a fast-neutron reactor or a
nuclear weapon A nuclear weapon is an explosive device that derives its destructive force from nuclear reactions, either fission (fission bomb) or a combination of fission and fusion reactions ( thermonuclear bomb), producing a nuclear explosion. Both bomb ...
, with a
critical mass In nuclear engineering, a critical mass is the smallest amount of fissile material needed for a sustained nuclear chain reaction. The critical mass of a fissionable material depends upon its nuclear properties (specifically, its nuclear fi ...
of around 60 kilograms. In 1992, the U.S. Department of Energy declassified the statement that neptunium-237 "can be used for a nuclear explosive device"."Restricted Data Declassification Decisions from 1946 until Present"
accessed Sept 23, 2006.
It is not believed that an actual weapon has ever been constructed using neptunium. As of 2009, the world production of neptunium-237 by commercial power reactors was over 1000 critical masses a year, but to extract the isotope from irradiated fuel elements would be a major industrial undertaking. In September 2002, researchers at the
Los Alamos National Laboratory Los Alamos National Laboratory (often shortened as Los Alamos and LANL) is one of the sixteen research and development laboratories of the United States Department of Energy (DOE), located a short distance northwest of Santa Fe, New Mexico, ...
briefly created the first known nuclear
critical mass In nuclear engineering, a critical mass is the smallest amount of fissile material needed for a sustained nuclear chain reaction. The critical mass of a fissionable material depends upon its nuclear properties (specifically, its nuclear fi ...
using neptunium in combination with shells of enriched uranium (
uranium-235 Uranium-235 (235U or U-235) is an isotope of uranium making up about 0.72% of natural uranium. Unlike the predominant isotope uranium-238, it is fissile, i.e., it can sustain a nuclear chain reaction. It is the only fissile isotope that exi ...
), discovering that the critical mass of a bare sphere of neptunium-237 "ranges from kilogram weights in the high fifties to low sixties," showing that it "is about as good a bomb material as ranium-235" The United States Federal government made plans in March 2004 to move America's supply of separated neptunium to a nuclear-waste disposal site in
Nevada Nevada ( ; ) is a U.S. state, state in the Western United States, Western region of the United States. It is bordered by Oregon to the northwest, Idaho to the northeast, California to the west, Arizona to the southeast, and Utah to the east. N ...
.


Physics

237Np is used in devices for detecting high-energy (MeV) neutrons.


Role in nuclear waste

Neptunium accumulates in commercial household ionization-chamber
smoke detector A smoke detector is a device that senses smoke, typically as an indicator of fire. Smoke detectors are usually housed in plastic enclosures, typically shaped like a disk about in diameter and thick, but shape and size vary. Smoke can be detecte ...
s from decay of the (typically) 0.2 microgram of americium-241 initially present as a source of
ionizing radiation Ionizing radiation (or ionising radiation), including nuclear radiation, consists of subatomic particles or electromagnetic waves that have sufficient energy to ionize atoms or molecules by detaching electrons from them. Some particles can travel ...
. With a half-life of 432 years, the americium-241 in an ionization smoke detector includes about 3% neptunium after 20 years, and about 15% after 100 years. Neptunium-237 is the most mobile
actinide The actinide () or actinoid () series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium. The actinide series derives its name from the first element in the series, actinium. The info ...
in the
deep geological repository A deep geological repository is a way of storing hazardous or radioactive waste within a stable geologic environment (typically 200–1000 m deep). It entails a combination of waste form, waste package, engineered seals and geology that is suite ...
environment. This makes it and its predecessors such as americium-241 candidates of interest for destruction by
nuclear transmutation Nuclear transmutation is the conversion of one chemical element or an isotope into another chemical element. Nuclear transmutation occurs in any process where the number of protons or neutrons in the nucleus of an atom is changed. A transmutatio ...
. Due to its long half-life, neptunium will become the major contributor of the total
radiotoxicity Ionizing radiation (or ionising radiation), including nuclear radiation, consists of subatomic particles or electromagnetic waves that have sufficient energy to ionize atoms or molecules by detaching electrons from them. Some particles can travel ...
in 10,000 years. As it is unclear what happens to the containment in that long time span, an extraction of the neptunium would minimize the contamination of the environment if the nuclear waste could be mobilized after several thousand years.


Biological role and precautions

Neptunium does not have a biological role, as it has a short half-life and occurs only in small traces naturally. Animal tests showed that it is not absorbed via the digestive tract. When injected it concentrates in the bones, from which it is slowly released. Finely divided neptunium metal presents a fire hazard because neptunium is
pyrophoric A substance is pyrophoric (from grc-gre, πυροφόρος, , 'fire-bearing') if it ignites spontaneously in air at or below (for gases) or within 5 minutes after coming into contact with air (for liquids and solids). Examples are organolith ...
; small grains will ignite spontaneously in air at room temperature.


References


Bibliography

* * * * * *


Literature

* ''Guide to the Elements – Revised Edition'', Albert Stwertka, (Oxford University Press; 1998) * Lester R. Morss, Norman M. Edelstein, Jean Fuger (Hrsg.): ''The Chemistry of the Actinide and Transactinide Elements'', Springer-Verlag, Dordrecht 2006, . * * Eric Scerri, A Very Short Introduction to the Periodic Table, Oxford University Press, Oxford, 2011, .


External links


Neptunium
at '' The Periodic Table of Videos'' (University of Nottingham)
Lab builds world's first neptunium sphere
U.S. Department of Energy Research News
NLM Hazardous Substances Databank – Neptunium, Radioactive

Neptunium: Human Health Fact Sheet


{{Authority control Chemical elements Actinides Synthetic elements Nuclear materials