Neptunium(IV) oxalate

Neptunium(IV) oxalate
Neptunium(IV) oxalate hexahydrate under aqueous solution
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/2C2H2O4.Np/c2*3-1(4)2(5)6;/h2*(H,3,4)(H,5,6);/q;;+4/p-4
    Key: KBWUHCITSWHCDN-UHFFFAOYSA-J
  • C(=O)(C(=O)[O-])[O-].C(=O)(C(=O)[O-])[O-].[Np+4]
Properties
Np(C2O4)2·xH2O (0 ≤ x ≤ 6)
Appearance Green crystals
Highly insoluble
Structure[1][a]
monoclinic
C2/m
a = 9.0425 Å, b = 8.9475 Å, c = 7.8188 Å
α = 90.00°, β = 93.228°, γ = 90.00°
631.60 Å3
2
Related compounds
Other cations
Related neptunium oxalates
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Neptunium(IV) oxalate is a chemical compound made up of neptunium(IV) (Np4+) and oxalate (C2O2−4) ions with the formula Np(C2O4)2. It has been known at least since 1947. It is known to form several hydrates with formulas Np(C2O4)2·xH2O (x = 1, 2, 6). The hexahydrate (x = 6) is a highly insoluble solid prepared by adding oxalic acid to aqueous solutions containing neptunium(IV) and nitric acid, and forms green crystals. The structure of the compound was determined through X-ray diffraction.

At high temperatures, the hexahydrate decomposes, forming other hydrates and eventually neptunium(IV) oxide, NpO2. Due to this, the high-temperature calcination of neptunium(IV) oxalate is used to produce NpO2, which can be used for nuclear power applications or preparation of other neptunium compounds. Neptunium(IV) oxalate is also used to separate neptunium from other metals. The presence of neptunium in this compound causes it to be radioactive.

Synthesis

Neptunium(IV) oxalate production usually starts from neptunium-nitric acid (HNO3) solutions, though solutions with hydrochloric acid (HCl) can be used instead.[2] The presence of higher neptunium oxidation states like +5 reduces the amount of oxalate filtered out, so it must be ensured that neptunium is in the +4 oxidation state in the initial nitric acid solution. Hydrazine (N2H4) or hydrazinium nitrate (N2H5NO3) is added to the initial solution to stabilize the +4 oxidation state and prevent oxidation. Iron(II) sulfamate (Fe(NH2SO3)2) or ascorbic acid (C6H8O6) is then added to reduce any neptunium(V) to neptunium(IV).[3][4][5] With ascorbic acid, the reduction happens as follows:[6]

2 NpO2+2 + H2A → 2 NpO+2 + A + 2 H+
2 NpO+2 + 6 H+ + H2A → 2 Np4+ + A + 4 H2O[b]

Ascorbic acid is a slow reducing agent, but the process is sped up rapidly with increased nitric acid concentration and/or temperature. After neptunium(IV) solution is prepared, neptunium(IV) oxalate is produced via the addition of oxalic acid:[3][4]

Np4+ + 2 H2C2O4 + 6 H2O → Np(C2O4)2·6H2O + 4 H+

Oxalic acid is often added in a two-step precipitation process. After addition, the solid neptunium(IV) oxalate can easily be filtered out.[7]

Physical properties

Neptunium(IV) oxalate forms several hydrates, with formulas Np(C2O4)2·xH2O (x=1, 2, 6). When neptunium(IV) oxalate is precipitated from aqueous solutions, green crystals of the hexahydrate (Np(C2O4)2·6H2O) are formed.[4] Other hydrates, such as the monohydrate (Np(C2O4)2·H2O) and dihydrate (Np(C2O4)2·2H2O), are formed by heating this compound. The dihydrate can also be produced by the dehydration of the hexahydrate with sulfuric acid. An anhydrous (lacking water) form, Np(C2O4)2, is formed on further heating.[8][9]

Neptunium(IV) oxalate hexahydrate is highly insoluble in water. A study on its solubility in nitric acid–oxalic acid solutions found that its value ranges between 4.0 and 37.4 mg/L at 22 °C, but it increases with increasing temperature (19.0–373.5 mg/L at 45 °C, 32.4–420.1 mg/L at 60 °C). When the ratio of neptunium(IV) ions to oxalate ions is close to 1:2, solubility decreases as neptunium(IV) oxalate is precipitated out, but when it is less than or more than 1:2, solubility increases due to the formation of Np(C2O4)2+ and Np(C2O4)2−3 ions, respectively. Equilibrium equations:[10]

Np(C2O4)2·6H2O (s) ⇌ Np(C2O4)2 (aq) + 6 H2O
Np(C2O4)2 + 2 H+ ⇌ Np(C2O4)2+ + H2C2O4
Np(C2O4)2 + H2C2O4 ⇌ Np(C2O4)2−3 + 2 H+

Structure

The structure of the hexahydrate (Np(C2O4)2·6H2O) was determined via X-ray diffraction. While initial studies from Grigor'ev et al.[11] suggested that each neptunium atom was bonded to four oxalate groups with a coordination geometry of cubic, later studies from Sockwell et al.[1] suggest that each neptunium atom is bonded to two water molecules as well. Neptunium, oxalate, and water molecules join together to form layers of composition [Np(C2O4)2(H2O)2]n. Three of the oxalate groups per neptunium atom lie perpendicular to the layers, while the other lies parallel, providing room to fit the two water molecules. Between these [Np(C2O4)2(H2O)2]n layers lie the rest of the water molecules, four per formula unit. Each oxalate group donates two oxygen atoms to neptunium, and each water molecule donates one atom, so neptunium atoms are bonded to ten oxygen atoms total.[1]

A single layer.
The coordination sphere of neptunium within the layers.
Diagram of the [Np(C2O4)2(H2O)2]n layers in Np(C2O4)2·6H2O's structure. Hydrogen atoms are omitted. Blue is neptunium, grey is carbon, and red is oxygen.

Decomposition

Neptunium(IV) oxalate decomposes when heated. Starting with the hexahydrate, Np(C2O4)2·6H2O, four water molecules per formula unit are lost between 80 and 90 °C. The fifth one is split off at 100–120 °C, and the last is split off at 190–200 °C to form anhydrous neptunium(IV) oxalate. Between 270 °C and 300 °C, this compound begins to decompose. At 270–330 °C, 70% of the neptunium is converted to the +5 oxidation state, mainly due to the formation of neptunyl(V) oxalate, (NpO2)2C2O4. This compound further decomposes to neptunium(IV) oxide (NpO2), which is formed at satisfactory quality between 500–550 °C.[8][9][4]

Np(C2O4)2·6H2O → Np(C2O4)2·2H2O + 4 H2O (between 80 and 90 °C)
Np(C2O4)2·2H2O → Np(C2O4)2·H2O + H2O (between 100 and 120 °C)
Np(C2O4)2·H2O → Np(C2O4)2 + H2O (between 190 and 200 °C)
2 Np(C2O4)2 + 2 O2 → (NpO2)2C2O4 + 6 CO2
(NpO2)2C2O4 → 2 NpO2 + 2 CO2

Applications

Neptunium separation and purification

Neptunium(IV) oxalate is an intermediate in neptunium separation and purification. Adding oxalic acid to a solution of other metals, such as alkali, alkaline earth, or transition metals, will precipitate neptunium as neptunium(IV) oxalate, allowing it to be separated from most other metals. It is also used in the separation of neptunium from other actinides, where a modification of the PUREX process with adjusted acid and tributyl phosphate concentrations is used. Neptunium(IV) oxalate is the form of neptunium which is isolated in this process, and it can then be calcined to produce neptunium(IV) oxide, NpO2.[6][12]: 703 

Synthesis of other neptunium compounds

Neptunium(IV) oxalate can be easily filtered out and decomposed, allowing it to be used for the production of neptunium(IV) oxide, NpO2.[3] The calcination of neptunium(IV) oxalate is the main method of producing NpO2,[13][2] first appearing in 1961.[3] After being precipitated, neptunium(IV) oxalate is heated in a stream of air or nitrogen, where the temperature is raised to 100–150 °C over the course of an hour. After being held at that temperature for another hour, the temperature is further increased 500–550 °C for an hour, held there for two hours, and then cooled to room temperature under the gas stream. This method has been used by the Savannah River Plant facilities for production of plutonium-238 for radioisotope thermoelectric generators.[4][3][10] Neptunium(IV) oxide is also a major form of neptunium in radioactive waste, and is used to make other neptunium compounds, like neptunium(III) fluoride (via reaction with hydrogen gas and hydrogen fluoride), neptunium(IV) fluoride (via reaction with hydrogen fluoride) or neptunium(IV) chloride (via reaction with carbon tetrachloride).[14][2][12]: 730–731,736 

Neptunium(IV) oxalate has been known at least since 1947, when it was used in the synthesis of neptunium(IV) chloride by reacting it with carbon tetrachloride.[15][12]: 730–731,736  Neptunium(IV) oxalate, when reacted with ozone while suspended in water, is oxidized to a neptunium(V) oxalate compound, NpO2HC2O4, and subsequently to neptunyl(VI) hydroxide (NpO2(OH)2). This reaction is proposed as a method of producing NpO2(OH)2 for laboratory studies.[16]

Other oxalates where neptunium is in the +4 oxidation state include an acid oxalate with formula (H3O)2Np2(C2O4)5·7H2O. This compound can be formed in many of the same conditions as Np(C2O4)2·6H2O can, and can be obtained in pure form at nitric acid concentrations of >3 M and neptunium concentrations of 0.01–0.02 M. Other double salts with formulas M2Np2(C2O4)5 (M=Na, K, NH4) are known.[17] A neptunium(IV) oxalate complex with the formula Np(C2O4)6−5 is known, and can be crystallized with hexaaminecobalt(III) as the compound [Co(NH3)6]2[Np(C2O4)5]·4H2O. The neptunium atoms form ionic bonds with the oxygen atoms from the oxalate groups, and, unlike in neutral neptunium(IV) oxalate itself, the oxalate groups are non-bridging. As these related compounds contain neptunium, like with neutral neptunium(IV) oxalate, they are radioactive.[18]

Notes

  1. ↑ Structural data for the hexahydrate, Np(C2O4)2·6H2O.
  2. ↑ Here, H2A represents ascorbic acid (C6H8O6), and A represents dehydroascorbic acid (C6H6O6).

References

  1. 1 2 3 Sockwell, A. Kirstin; Sweet, Teagan F. M.; Barth, Brodie; Isbill, Sara B.; Diblasi, Nicole A.; Szymanowski, Jennifer E. S.; Sigmon, Ginger E.; Oliver, Allen G.; Miskowiec, Andrew J.; Burns, Peter C.; Hixon, Amy E. (2023). "Insight into the Structural Ambiguity of Actinide(IV) Oxalate Sheet Structures: A Case for Alternate Coordination Geometries". Chemistry – A European Journal. 29 (47) e202301164. Bibcode:2023ChEuJ..29E1164S. doi:10.1002/chem.202301164. PMID 37227412. Archived from the original on 2026-05-17. Retrieved 2026-04-07.
  2. 1 2 3 Peruski, Kathryn M.; Powell, Brian A. (2020). "Effect of calcination temperature on neptunium dioxide microstructure and dissolution". Environmental Science: Nano. 7 (12): 3869–3876. doi:10.1039/D0EN00689K. OSTI 1737655.
  3. 1 2 3 4 5 Porter, J. A. (July 1, 1961). Precipitation of neptunium oxalate and calcination to neptunium oxide (PDF) (Report). Du Pont de Nemours (E.I.) and Co., Aiken, S.C. (USA). Savannah River Lab. OSTI 4166658. Archived (PDF) from the original on May 18, 2026. Retrieved March 31, 2026.
  4. 1 2 3 4 5 Porter, J. A. (1964). "Production of Neptunium Dioxide". Industrial & Engineering Chemistry Process Design and Development. 3 (4): 289–292. doi:10.1021/i260012a001.
  5. ↑ Jordan, J.; Watkins, R.; Hensel, S. Neptunium Oxide Processing. OSTI 958296. Archived from the original on 2026-05-19. Retrieved 2026-05-10.
  6. 1 2 Kim, Eung-Ho; Chung, Dong-Yong; Kim, Won-Ho; Shin, Young-Joon; Lee, Eil-Hee; Yoo, Jae-Hyung; Choi, Cheong-Song (1997). "Neptunium Oxalate Precipitation from the Simulated Radioactive Liquid Waste". Journal of Nuclear Science and Technology. 34 (3): 283–287. Bibcode:1997JNST...34..283K. doi:10.1080/18811248.1997.9733662.
  7. ↑ Luerkens, D. W. (1983). "Two-stage precipitation of neptunium (IV) oxalate". Du Pont de Nemours (E.I.) and Co. Archived from the original on 2026-05-18. Retrieved 2026-03-31.
  8. 1 2 Kozlova, R. D.; Karelin, A. I.; Lobas, O. P.; Matyukha, V. A. (1984). "Thermal decomposition of neptunium (4) oxalate". Radiokhimiya (in Russian). 26 (3): 311–316. ISSN 0033-8311.
  9. 1 2 Karelin, A. I.; Krot, N. N.; Kozlova, R. D.; Lobas, O. P.; Matukha, V. A. (1990). "Thermal decomposition of Np(IV) and Pu(III, IV) oxalates". Journal of Radioanalytical and Nuclear Chemistry Articles. 143 (1): 241–252. Bibcode:1990JRNC..143..241K. doi:10.1007/BF02117565.
  10. 1 2 Luerkens, D. W. (1 July 1983). Neptunium (IV) oxalate solubility. [22, 45, 60/sup 0/C] (Report). doi:10.2172/5904308. OSTI 5904308. Archived from the original on 28 December 2025. Retrieved 31 March 2026.
  11. ↑ Grigor'ev, M. S.; Charushnikova, I. A.; Krot, N. N.; Yanovskii, A. I.; Struchkov, Y. T. (1997). "Crystal structure of neptunium(IV) oxalate hexahydrate Np(C2O4)2.6H2O". Radiochemistry. 39: 420–423.
  12. 1 2 3 Yoshida, Zenko; Johnson, Stephen; Kimura, Takaumi; Krsul, John (2011). "Neptunium". The Chemistry of the Actinide and Transactinide Elements (PDF). doi:10.1007/978-94-007-0211-0_6. ISBN 978-1-4020-3555-5.
  13. ↑ Peruski, Kathryn M.; Parker, Connor J.; Cary, Samantha K. (2023). "Analysis of neptunium oxides produced through modified direct denitration". Journal of Nuclear Materials. 587 154704. Bibcode:2023JNuM..58754704P. doi:10.1016/j.jnucmat.2023.154704. OSTI 2000387.
  14. ↑ Colle, J.-Y. (2011). "(Solid + gas) equilibrium studies for neptunium dioxide". Journal of Chemical Thermodynamics. 43 (3): 492–498. Bibcode:2011JChTh..43..492G. doi:10.1016/j.jct.2010.10.027.
  15. ↑ Fried, S.; Davidson, N. R. (1947). "The Basic Dry Chemistry of Neptunium" (PDF).
  16. ↑ Fedoseev, A. M.; Gogolev, A. V.; Shilov, V. P.; Charushnikova, I. A.; Makarenkov, V. I.; Perminov, V. P. (2017). "Reaction of ozone with Np(IV) and Pu(IV) oxalates in water". Radiochemistry. 59 (6): 570–578. Bibcode:2017Radch..59..570F. doi:10.1134/S1066362217060042.
  17. ↑ Bykhovskii, D. N.; Kuz'Mina, M. A.; Maksimov, V. F.; Novikov, G. S.; Smirnov, A. N.; Solntseva, L. V. (September 1988). "Synthesis conditions and some properties of neptunium (IV) oxalates in which C2O4Np = 2.5". Soviet Radiochemistry (Engl. Transl.). 30 (1). OSTI 5774959.
  18. ↑ Tamain, Christelle; Autillo, Matthieu; Guillaumont, Dominique; Guérin, Laetitia; Wilson, Richard E.; Berthon, Claude (2022). "Structural and Bonding Analysis in Monomeric Actinide(IV) Oxalate from Th(IV) to Pu(IV): Comparison with the An(IV) Nitrate Series". Inorganic Chemistry. 61 (31): 12337–12348. doi:10.1021/acs.inorgchem.2c01674. OSTI 1968736. PMID 35881850.
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