Plutonium tetrachloride
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| IUPAC name
Plutonium(IV) chloride
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| Identifiers | |
3D model (JSmol)
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CompTox Dashboard (EPA)
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| Properties | |
| PuCl4 | |
| Molar mass | 386 g·mol−1 |
| Related compounds | |
Other anions
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Plutonium tetrafluoride |
Other cations
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Plutonium tetrachloride or plutonium(IV) chloride is an inorganic compound of plutonium and chlorine with the chemical formula PuCl4. While it is not known as a solid, gaseous PuCl4 is known. In addition, it is known to form several stable adducts. The dimethoxyethane adduct, PuCl4(DME)2, has been used as a precursor to other plutonium compounds.
Synthesis
[edit]The compound is formed when plutonium trichloride is put in a stream of chlorine:[1]: 1094
- 2 PuCl3 + Cl2 → 2 PuCl4
Physical properties
[edit]The compound is not stable as a solid; however, it is known in the gas phase. When condensed, it forms plutonium(III) chloride and chlorine gas:[1]: 1094
- 2 PuCl4 → 2 PuCl3 + Cl2
However, several stable adducts, such as with dimethoxyethane (PuCl4(DME)2)[2] or diphenylsulfoxide,[3] and ammoniates (solids incorporating ammonia),[4] are known. The diphenylsulfoxide adduct appears as a red solid.[3]
Complexes
[edit]With dimethoxyethane
[edit]Plutonium tetrachloride forms a stable adduct with dimethoxyethane (CH3OCH2CH2OCH3) with formula PuCl4(DME)2 (DME=dimethoxyethane). This compound can be prepared via evaporation of a hydrochloric acid solution containing plutonium(IV), adding the product to dimethoxyethane, and then adding trimethylsilyl chloride.[2] This adduct can be used to prepare other compounds. For example, when it is dissolved in tetrahydrofuran, it is partially reduced to form the mixed-valence complex [PuIIICl2(THF)5]+[PuIVCl5(THF)]−. (THF=tetrahydrofuran).[5] It has also been used to prepare the compound plutonium(IV) N-(tert-butyl)isobutyramide (Pu(ita)4, ita=N-(tert-butyl)isobutyramide) through reaction with potassium N-(tert-butyl)isobutyramide. Pu(ita)4 has been investigated in the production of oxidation state-pure plutonium(IV) oxide.[6]
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Other complexes
[edit]Plutonium tetrachloride also forms an adduct with diphenylsulfoxide (Ph2SO). This adduct has been prepared by boiling a solution consisting of plutonium(IV) dissolved in hydrochloric acid, suspending the residue in acetonitrile, and adding to it an acetonitrile solution of diphenylsulfoxide. The resulting product has the formula PuCl4(Ph2SO)3, and is a rare example of plutonium in its +4 oxidation state with a coordination number of 7 (forming 7 bonds).[3]
When the related compound dicaesium hexachloroplutonate is reacted with liquid ammonia at low temperatures, the ammoniate (solid incorporating ammonia). The initial product has composition PuCl4·~7–8NH3, which decomposes over a period of weeks to form PuCl4·5NH3. PuCl4·5NH3 is stable at room temperature. Both compounds are ammine complexes, meaning that the ammonia in them is bonded to the plutonium atoms.[4]
Uses
[edit]A mixture of uranium tetrachloride and plutonium tetrachloride can be used as fuel for nuclear reactors.[7]
Related compounds
[edit]Anionic derivatives
[edit]Even though binary plutonium(IV) chloride is not known as a solid, solid compounds derived from it, such as dicaesium hexachloroplutonate (Cs2PuCl6), are known.[1]: 1094 In this compound, the +4 oxidation state of plutonium is stabilized by complexing with caesium chloride.[8]: 149 It is made up of discrete hexachloroplutonate (PuCl2−6) ions.[1]
References
[edit]- ^ a b c d Clark, David L.; Hecker, Siegfried S.; Jarvinen, Gordon D.; Neu, Mary P. (2011). "Plutonium". The Chemistry of the Actinide and Transactinide Elements (PDF). doi:10.1007/978-94-007-0211-0_7. ISBN 978-94-007-0211-0.
- ^ a b Reilly, Sean D.; Brown, Jessie L.; Scott, Brian L.; Gaunt, Andrew J. (2014). "Synthesis and characterization of NpCl4(DME)2 and PuCl4(DME)2 neutral transuranic An(iv) starting materials". Dalton Trans. 43 (4): 1498–1501. doi:10.1039/C3DT53058B. PMID 24285347.
- ^ a b c Cary, Samantha K.; Boland, Kevin S.; Cross, Justin N.; Kozimor, Stosh A.; Scott, Brian L. (2017). "Advances in containment methods and plutonium recovery strategies that led to the structural characterization of plutonium(IV) tetrachloride tris-diphenylsulfoxide, PuCl4(OSPh2)3". Polyhedron. 126: 220–226. doi:10.1016/j.poly.2017.01.013. OSTI 1371670.
- ^ a b Cleveland, J. M.; Bryan, G. H.; Sironen, R. J. (1 January 1972). "Ammoniates of plutonium(III) and (IV) halides". Inorganica Chimica Acta. 6: 54–58. doi:10.1016/S0020-1693(00)91758-4. ISSN 0020-1693. Retrieved 27 September 2025.
- ^ Pattenaude, Scott A.; Anderson, Nickolas H.; Bart, Suzanne C.; Gaunt, Andrew J.; Scott, Brian L. (2018). "Non-aqueous neptunium and plutonium redox behaviour in THF – access to a rare Np(III) synthetic precursor". Chemical Communications. 54 (48): 6113–6116. doi:10.1039/C8CC02611D. OSTI 1436357. PMID 29736543.
- ^ Peterson, Appie; Kelly, Sheridon N.; Arino, Trevor; Gunther, S. Olivia; Ouellette, Erik T.; Wacker, Jennifer N.; Woods, Joshua J.; Teat, Simon J.; Lukens, Wayne W.; Arnold, John; Abergel, Rebecca J.; Minasian, Stefan G. (2024). "Formation of Fully Stoichiometric, Oxidation-State Pure Neptunium and Plutonium Dioxides from Molecular Precursors". Inorganic Chemistry. 63 (39): 18417–18428. doi:10.1021/acs.inorgchem.4c02099. PMC 11445724. PMID 39284039.
- ^ Liu, Chunyu; Luo, Run; Macián-Juan, Rafael (15 October 2021). "A New Uncertainty-Based Control Scheme of the Small Modular Dual Fluid Reactor and Its Optimization". Energies. 14 (20): 6708. doi:10.3390/en14206708. ISSN 1996-1073.
- ^ Lemire, R. J. et al., Chemical Thermodynamics of Neptunium and Plutonium, Elsevier, Amsterdam, 2001.