Niels Bohr

Neptunium is a chemical element with the symbol Np and atomic number 93. A radioactive actinide metal, neptunium is the first transuranic element. Its position in the periodic table just after uranium, named after the planet Uranus, led to its being named after Neptune, the next planet beyond Uranus. 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. It occurs in three allotropic forms. The element normally exhibits five oxidation states, ranging from +3 to +7.

In the 1870s, Dmitri Mendeleev first predicted the existence of neptunium, and 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. Most neptunium is produced by bombarding uranium with neutrons in nuclear reactors; neptunium is also generated as a by-product in conventional nuclear reactors. Though neptunium has no commercial uses at present, it is widely used as a precursor for the formation of plutonium-238, used in radioisotope thermal generators which are used to power some spacecraft. Neptunium itself can be used in detectors of high-energy neutrons.

The most stable isotope of neptunium, neptunium-237, is a by-product of nuclear reactors and plutonium production, and it can be used as a component in neutron detection equipment. The isotopes neptunium-237 and neptunium-239 are also found in trace amounts in uranium ores due to neutron capture reactions and beta decay.

History

Pre-discovery

Even before its discovery, the existence of neptunium had been predicted several times. The periodic table of Dmitri Mendeleev published in the 1870s showed a " — " in place after uranium similar to several other places for at that point undiscovered elements. Also, a 1913 publication of the known radioactive isotopes by Kasimir Fajans shows the empty place after uranium.

The search for element 93 in minerals was encumbered by the fact that the predictions on the chemical properties of element 93 were based on a periodic table which lacked the actinide series, and therefore placed thorium below hafnium, protactinium below tantalum, and uranium below tungsten. This periodic table suggested that element 93, at that point often named eka-rhenium, should be similar to manganese or rhenium. With this misconception it was impossible to isolate element 93 from minerals, although neptunium was later found in uranium ore, in 1952.

In 1934, Odolen Koblic extracted a small amount of material from the wash water of roasted pitchblende. He assumed the sample was element 93, and called it bohemium, but after being analyzed, it turned out that the sample was a mixture of tungsten and vanadium.

In 1938, Horia Hulubei, a Romanian physicist; and Yvette Cauchois, a French chemist; claimed to have discovered element 93 via spectroscopy in minerals. They named their element sequanium, but the claim was opposed at the time because neptunium was thought to occur exclusively artificially. However, as neptunium does occur in nature, it is possible that Hulubei and Cauchois did in fact discover neptunium.

Enrico Fermi believed that bombarding uranium with neutrons and subsequent beta decay would lead to the formation of element 93. Chemical separation of the new formed elements from the uranium yielded material with low half-life, and, therefore, Fermi announced the discovery of a new element in 1934, though this was soon found to be mistaken. Soon it was speculated and later proven that most of the material is created by nuclear fission of uranium by neutrons. Small quantities of neptunium had to be produced in Otto Hahn's experiments in late 1930s as a result of decay of ²³⁹U. Hahn and his colleagues experimentally confirmed production and chemical properties of ²³⁹U, but were unsuccessful at isolating and detecting neptunium.

Discovery

In 1939, Edwin McMillan did some preliminary work leading to the eventual discovery of element 93. Uranium trioxide was placed on paper together with aluminium or paper foils and the result was irradiated with neutrons from a cyclotron. Examination revealed the presence of two components, both beta decaying: one turned out to be uranium-239 (half-life 23 minutes), while the other could not be characterized firmly. Emilio Segrè contradictorily labelled the second component as having atomic number 93 but not being a transuranic element, also noting that it behaved similarly to the rare earth elements. This lack of confidence in labelling the product as transuranic was from the absence of any observed activity from the beta decay product of element 93.

Neptunium (named for the planet Neptune, the next planet out from Uranus, after which uranium was named) was finally convincingly discovered by Edwin McMillan and Philip H. Abelson in 1940 at the Berkeley Radiation Laboratory of the University of California, Berkeley. The team produced the neptunium isotope ²³⁹Np (2.4 day half-life) by bombarding uranium with slow moving neutrons. It was the first transuranium element produced synthetically and the first actinide series transuranium element discovered.

$\mathrm {^{238}_{\ 92}U\ +\ _{0}^{1}n\ \longrightarrow \ _{\ 92}^{239}U\ {\xrightarrow[{23\ min}]{\beta ^{-}}}\ _{\ 93}^{239}Np\ {\xrightarrow[{2.355\ d}]{\beta ^{-}}}\ _{\ 94}^{239}Pu}$

Occurrence

The most stable isotope of neptunium is ²³⁷Np, with a half-life of two million years. Thus, all primordial neptunium should have decayed by now. However, trace amounts of the neptunium isotopes neptunium-237 through neptunium-240, are found naturally as decay products from transmutation reactions in uranium ores.

Artificial ²³⁷Np is produced through a reaction of ²³⁷NpF₃ with liquid barium or lithium at around 1200 °C and is most often extracted from spent nuclear fuel rods in kilogram amounts as a by-product in plutonium production.

2 Template:Chem + 3 Ba → 2 Np + 3 Template:Chem

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.

Characteristics

Silvery in appearance, neptunium metal is chemically fairly reactive and is found in at least three allotropes:

• α-neptunium, orthorhombic, density 20.45 g/cm³
• β-neptunium (above 280 °C), tetragonal, density (313 °C) 19.36 g/cm³
• γ-neptunium (above 577 °C), cubic, density (600 °C) 18 g/cm³

Neptunium has the largest liquid range of any element, 3363 K, between the melting point and boiling point. It is the densest of all the actinides and the fifth-densest of all naturally occurring elements. Neptunium has no biological role. It is not absorbed by the digestive tract. When injected into the body, it accumulates in bones, from which it is slowly released.

Isotopes

Mining Engineer (Excluding Oil ) Truman from Alma, loves to spend time knotting, largest property developers in singapore developers in singapore and stamp collecting. Recently had a family visit to Urnes Stave Church. 19 neptunium radioisotopes have been characterized, with the most stable being ²³⁷Np with a half-life 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 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 4 meta states, with the most stable being ^236mNp (t_½ 22.5 hours).

The isotopes of neptunium range in atomic weight from 225.0339 u (²²⁵Np) to 244.068 u (²⁴⁴Np). The primary decay mode before the most stable isotope, ²³⁷Np, is electron capture (with a good deal of alpha emission), and the primary mode after is beta emission. The primary decay products before ²³⁷Np are element 92 (uranium) isotopes (alpha emission produces element 91, protactinium, however) and the primary products after are element 94 (plutonium) isotopes.

²³⁷Np is fissionable. ²³⁷Np eventually decays to form bismuth-209 and thallium-205, unlike most other common heavy nuclei which decay to make isotopes of lead. This decay chain is known as the neptunium series.

Synthesis

Chemically, neptunium is prepared by the reduction of NpF₃ with barium or lithium vapor at about 1200 °C. Most Np is produced in nuclear reactions:

• 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. Further neutron capture creates ²³⁷U which has a half-life of 7 days and thus quickly decays to ²³⁷Np through beta decay. During beta decay, the excited ²³⁷U emits an electron, while the atomic weak interaction converts a neutron to a proton, thus creating ²³⁷Np.

$\mathrm {^{235}_{\ 92}U\ +\ _{0}^{1}n\ \longrightarrow \ _{\ 92}^{236}U_{m}\ {\xrightarrow[{120\ ns}]{}}\ _{\ 92}^{236}U\ +\ \gamma }$

$\mathrm {^{236}_{\ 92}U\ +\ _{0}^{1}n\ \longrightarrow \ _{\ 92}^{237}U\ {\xrightarrow[{6.75\ d}]{\beta ^{-}}}\ _{\ 93}^{237}Np}$

• 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 of ²⁴¹Am.

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.

Chemistry

Neptunium ions in solution.

This element has five ionic oxidation states while in solution:

• Np³⁺ (pale purple), analogous to the rare earth ion Pm³⁺
• Np⁴⁺ (yellow-green)
• Template:Chem (green-blue)
• Template:Chem (pale pink)
• Template:Chem (green). This may better be labelled as a hydroxo species Template:Chem.

Neptunium(III) hydroxide is not soluble in water and does not dissolve in excess alkali. Neptunium(III) is susceptible to oxidation in contact to air forming neptunium(IV).

Neptunium forms tri- and tetrahalides such as NpF₃, NpF₄, NpCl₄, NpBr₃, NpI₃, and oxides of the various compositions such as are found in the uranium-oxygen system, including Np₃O₈ and NpO₂.

Neptunium hexafluoride, NpF₆, is volatile like uranium hexafluoride.

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Neptunium, like protactinium, uranium, plutonium, and americium readily forms a linear dioxo neptunyl core (NpO₂ⁿ⁺), in its 5+ and 6+ oxidation states, which readily complexes with hard O-donor ligands such as OH^–, NO₂^–, NO₃^–, and SO₄^2– to form soluble anionic complexes which tend to be readily mobile with low affinities to soil. Neptunium is very reactive when in contact with oxygen, steam, or acid. However it is not attacked by alkalis.

• NpO₂(OH)₂^–
• NpO₂(CO₃)^–
• NpO₂(CO₃)₂^3–
• NpO₂(CO₃)₃^5–

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Applications

Precursor in plutonium-238 production

²³⁷Np is irradiated with neutrons to create ²³⁸Pu, an alpha emitter for radioisotope thermal generators for spacecraft and military applications. ²³⁷Np will capture a neutron to form ²³⁸Np and beta decay with a half-life of two days to ²³⁸Pu.

$\mathrm {^{237}_{\ 93}Np\ +\ _{0}^{1}n\ \longrightarrow \ _{\ 93}^{238}Np\ {\xrightarrow[{2.117\ d}]{\beta ^{-}}}\ _{\ 94}^{238}Pu}$

²³⁸Pu also exists in sizable quantities in spent nuclear fuel but would have to be separated from other isotopes of plutonium.

Weapons applications

Neptunium is fissionable, and could theoretically be used as fuel in a fast neutron reactor or a nuclear weapon, with a critical mass 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". 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 briefly created the first known nuclear critical mass using neptunium in combination with shells of enriched uranium (U-235), 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 U-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.

Physics applications

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

Role in nuclear waste

Neptunium-237 is the most mobile actinide in the deep geological repository environment. This makes it and its predecessors such as americium-241 candidates of interest for destruction by nuclear transmutation. Neptunium accumulates in commercial household ionization-chamber smoke detectors from decay of the (typically) 0.2 microgram of americium-241 initially present as a source of ionizing radiation. With a half-life of 432 years, the americium-241 in a smoke detector includes about 3% neptunium after 20 years, and about 15% after 100 years.

Due to its long half-life, neptunium becomes the major contributor of the total radiation 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 any biological role. It is absorbed via the digestive tract. When injected it concentrates in the bones, from which it is slowly released.

References

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Bibliography

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Literature

• Guide to the Elements – Revised Edition, Albert Stwertka, (Oxford University Press; 1998) ISBN 0-19-508083-1
• Lester R. Morss, Norman M. Edelstein, Jean Fuger (Hrsg.): The Chemistry of the Actinide and Transactinide Elements, Springer-Verlag, Dordrecht 2006, ISBN 1-4020-3555-1.
• One of the biggest reasons investing in a Singapore new launch is an effective things is as a result of it is doable to be lent massive quantities of money at very low interest rates that you should utilize to purchase it. Then, if property values continue to go up, then you'll get a really high return on funding (ROI). Simply make sure you purchase one of the higher properties, reminiscent of the ones at Fernvale the Riverbank or any Singapore landed property Get Earnings by means of Renting
  
  In its statement, the singapore property listing - website link, government claimed that the majority citizens buying their first residence won't be hurt by the new measures. Some concessions can even be prolonged to chose teams of consumers, similar to married couples with a minimum of one Singaporean partner who are purchasing their second property so long as they intend to promote their first residential property. Lower the LTV limit on housing loans granted by monetary establishments regulated by MAS from 70% to 60% for property purchasers who are individuals with a number of outstanding housing loans on the time of the brand new housing purchase. Singapore Property Measures - 30 August 2010 The most popular seek for the number of bedrooms in Singapore is 4, followed by 2 and three. Lush Acres EC @ Sengkang
  
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  Extending the tax exemption would help. The exemption, which may be as a lot as $2 million per family, covers individuals who negotiate a principal reduction on their existing mortgage, sell their house short (i.e., for lower than the excellent loans), or take part in a foreclosure course of. An extension of theexemption would seem like a common-sense means to assist stabilize the housing market, but the political turmoil around the fiscal-cliff negotiations means widespread sense could not win out. Home Minority Chief Nancy Pelosi (D-Calif.) believes that the mortgage relief provision will be on the table during the grand-cut price talks, in response to communications director Nadeam Elshami. Buying or promoting of blue mild bulbs is unlawful.
  
  A vendor's stamp duty has been launched on industrial property for the primary time, at rates ranging from 5 per cent to 15 per cent. The Authorities might be trying to reassure the market that they aren't in opposition to foreigners and PRs investing in Singapore's property market. They imposed these measures because of extenuating components available in the market." The sale of new dual-key EC models will even be restricted to multi-generational households only. The models have two separate entrances, permitting grandparents, for example, to dwell separately. The vendor's stamp obligation takes effect right this moment and applies to industrial property and plots which might be offered inside three years of the date of buy. JLL named Best Performing Property Brand for second year running
  
  The data offered is for normal info purposes only and isn't supposed to be personalised investment or monetary advice. Motley Fool Singapore contributor Stanley Lim would not personal shares in any corporations talked about. Singapore private home costs increased by 1.eight% within the fourth quarter of 2012, up from 0.6% within the earlier quarter. Resale prices of government-built HDB residences which are usually bought by Singaporeans, elevated by 2.5%, quarter on quarter, the quickest acquire in five quarters. And industrial property, prices are actually double the levels of three years ago. No withholding tax in the event you sell your property. All your local information regarding vital HDB policies, condominium launches, land growth, commercial property and more
  
  There are various methods to go about discovering the precise property. Some local newspapers (together with the Straits Instances ) have categorised property sections and many local property brokers have websites. Now there are some specifics to consider when buying a 'new launch' rental. Intended use of the unit Every sale begins with 10 p.c low cost for finish of season sale; changes to 20 % discount storewide; follows by additional reduction of fiftyand ends with last discount of 70 % or extra. Typically there is even a warehouse sale or transferring out sale with huge mark-down of costs for stock clearance. Deborah Regulation from Expat Realtor shares her property market update, plus prime rental residences and houses at the moment available to lease Esparina EC @ Sengkang
• Eric Scerri, A Very Short Introduction to the Periodic Table, Oxford University Press, Oxford, 2011, ISBN 978-0-19-958249-5.

External links

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• 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
• C&EN: It's Elemental: The Periodic Table – Neptunium

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