Neptunium is a chemical element; it has the chemical symbol Np and atomic number 93. A radioactive actinide metal, neptunium is the first transuranic element. It is named after Neptune, the planet beyond Uranus in the Solar System, which uranium is named after. A neptunium atom has 93 protons 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 states, ranging from +3 to +7. Like all actinides, it is radioactive, poisonous, pyrophoric, and capable of accumulating in bones, 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 reactors. While neptunium itself has no commercial uses at present, it is used as a precursor for the formation of plutonium-238, which is in turn used in radioisotope thermal generators to provide electricity for spacecraft. Neptunium has also been used in detectors of high-energy neutrons.
The longest-lived isotope of neptunium, neptunium-237, is a by-product of nuclear reactors and plutonium production. This isotope, and the isotope neptunium-239, are also found in trace amounts in uranium ores due to neutron capture reactions and beta decay. __TOC__
Characteristics
Physical Neptunium is a hard, silvery, ductile, radioactive actinide metal (all actinides are metals). In the periodic table, it is located to the right of the actinide uranium, to the left of the actinide plutonium and below the lanthanide promethium. Neptunium is a hard metal, having a bulk modulus of 118 GPa, comparable to that of manganese. 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 : 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 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 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 structures of neptunium, protactinium, uranium, and plutonium do not have clear analogs among the lanthanides and are more similar to those of the 3d transition metals.
+ Allotropes of neptuniumAllotropeα (measured at 20 °C)β (measured at 313 °C)γ (measured at 600 °C)Transition temperature(α→β) 280 °C(β→γ) 576 °C(γ→liquid) 639 °CCrystal structureOrthorhombicTetragonalBody-centered cubicPearson symboloP8tP4cI2Space groupPnmaP4212ImmDensity (g/cm3, 237Np)20.4519.3618.08Lattice parameters (pm)a = 472.3b = 488.7c = 666.3a = 489.5c = 338.9a = 351.8
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, iridium, and osmium.Theodore Gray. The Elements. Page 215. α-neptunium has semimetallic properties, such as strong covalent bonding 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.Hindman J. C. 1968, "Neptunium", in C. A. Hampel (ed.), The encyclopedia of the chemical elements, Reinhold, New York, pp. 434. 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 occurs at 725 °C and 3200 MPa.
Alloys Due to the presence of valence 5f electrons, neptunium and its alloys exhibit a very interesting magnetic behavior, like many other actinides. These can range from the itinerant band-like character characteristic of the transition metals to the local moment behavior typical of scandium, yttrium, and the lanthanides. This stems from 5f-orbital hybridization with the orbitals of the metal ligands, 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, NpAl3 is ferromagnetic, NpGe3 has no magnetic ordering, and NpSn3 may be a heavy fermion material. Investigations are underway regarding alloys of neptunium with uranium, americium, plutonium, zirconium, and iron, 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 NpPd5Al2. 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 states 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 compounds.
Atomic A neptunium atom has 93 electrons, arranged in the configuration [Rn] 5f4 6d1 7s2. This differs from the configuration expected by the Aufbau principle in that one electron is in the 6d 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 [Rn] 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 [Rn] 5fn 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.David R. Lide (ed), CRC Handbook of Chemistry and Physics, 84th Edition. CRC Press. Boca Raton, Florida, 2003; Section 10, Atomic, Molecular, and Optical Physics; Ionization Potentials of Atoms and Atomic Ions.
Isotopes
All nuclear data not otherwise stated is from the standard source: Twenty-four neptunium radioisotopes have been characterized, with the most stable being 237Np with a half-life of 2.144 million years, 236Np with a half-life of 153,000 years, and 235Np with a half-life of 396.1 days. All of the remaining radioactive isotopes have half-lives that are less than 5 days.
Isotopes lighter than the most stable one, 237Np, decay primarily by electron capture, although some also decay by alpha emission to become protactinium. 237Np itself, being the beta-stable isobar of mass number 237, decays by alpha to 233Pa, with very rare spontaneous fission. Heavier isotopes generally decay by beta emission.
The decay of 237Np eventually yields bismuth-209 and thallium-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 was virtually absent 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 (and uranium-233) on the tonne scale.
The isotopes neptunium-235, -236, and -237 are predicted to be fissile; although only neptunium-237's fissionability has been experimentally shown. Its critical mass is about 60 kg, only about 10 kg more than that of the commonly used uranium-235. 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 and 236Np also has a low neutron cross section. However, a neptunium atomic bomb has never been built because 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 237Np.
Occurrence The longest-lived isotope of neptunium, 237Np, has a half-life of 2.14 million years, which is more than 2,000 times shorter than the age of the Earth. Therefore, any primordial neptunium would have decayed in the distant past. 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 products from transmutation reactions in uranium ores.Emsley, pp. 345–347. 239Np and 237Np are the most common of these isotopes; they are directly formed from neutron capture 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 particles and emitting a neutron. The half-life of 239Np is very short, although the detection of its much longer-lived daughter 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: in these minerals, the ratio of neptunium-237 to uranium is less than or equal to about 10−12 to 1. Additionally, 240Np must also occur as an intermediate decay product of 244Pu, which has been detected in meteorite dust in marine sediments on Earth.