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((More citations needed|date=January 2024))
((chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 477000218
| Name = Uranium tetrachloride
| ImageFile = ThCl4.png
| ImageName = Uranium Tetrachloride crystal structure
| ImageFile1 = File:UCl4_Powder.jpg
| IUPACName = Uranium(IV) chloride
| OtherNames = Tetrachlorouranium<br>Uranium tetrachloride<br>Uranous chloride
|Section1=((Chembox Identifiers
| CASNo_Ref = ((cascite|correct|CAS))
| CASNo = 10026-10-5
| UNII_Ref = ((fdacite|correct|FDA))
| UNII = 8E7IB152RL 
| ChemSpiderID_Ref = ((chemspidercite|correct|chemspider))
| ChemSpiderID =19969614 
| EINECS =  233-057-7  
| PubChem = 66210
| InChI = 1/4ClH.2U/h4*1H;;/q;;;;2*+2/p-4
| InChIKey = AYQSGSWJZFIBLR-XBHQNQODAS
| SMILES = [U+4].[Cl-].[Cl-].[Cl-].[Cl-]
| StdInChI_Ref = ((stdinchicite|correct|chemspider))
| StdInChI = 1S/4ClH.2U/h4*1H;;/q;;;;2*+2/p-4
| StdInChIKey_Ref = ((stdinchicite|correct|chemspider))
| StdInChIKey = AYQSGSWJZFIBLR-UHFFFAOYSA-J
  ))
|Section2=((Chembox Properties
| Formula = UCl<sub>4</sub>
| MolarMass = 379.84 g/mol
| Density = 4.87 g/cm<sup>3</sup>
| Appearance = olive green solid
| Solubility = Hydrolysis
| Solvent = 
| SolubleOther = Soluble in hydrochloric acid
| MeltingPtC = 590
| BoilingPtC = 791
  ))
|Section3=((Chembox Structure
| CrystalStruct = Octahedral
  ))
|Section4=((Chembox Related
| OtherCompounds = [[uranium trichloride]], [[uranium pentachloride]], [[uranium hexachloride]]
  ))
))

'''Uranium tetrachloride''' is an [[inorganic compound]], a salt of uranium and chlorine, with the formula UCl<sub>4</sub>. It is a hygroscopic olive-green solid. It was used in the electromagnetic [[isotope separation]] (EMIS) process of [[uranium enrichment]].  It is one of the main starting materials for [[organouranium chemistry]].

== Synthesis and structure ==
[[File:UCl4 single crystals.jpg|thumb|left| Single crystals of uranium tetrachloride (field of view about 7 mm)]]
Uranium tetrachloride is synthesised generally by the reaction of [[uranium trioxide]] (UO<sub>3</sub>) and [[hexachloropropene]].  Solvent UCl<sub>4</sub> adducts can be formed by a simpler reaction of UI<sub>4</sub> with [[hydrogen chloride]] in organic solvents.

Uranium tetrachloride also forms the nonahydrate, which can be produced by evaporating a mildly acidic solution of UCl<sub>4</sub>.<ref>((cite journal |author1=Thomas Kasperowicz |author2=Niko T. Flosbach |author3=Dennis Grödler |author4=Hannah Kasperowicz |author5=Jörg-M. Neudörfl |author6=Tobias Rennebaum |author7=Mathias S. Wickleder |author8=Markus Zegke |title=Solvated Actinoids: Methanol, Ethanol, and Water Adducts of Thorium and Uranium Tetrachloride |journal=European Journal of Inorganic Chemistry |date=2022 |volume=2022 |issue=31 |doi=10.1002/ejic.202200227 |language=en|doi-access=free ))</ref>

According to [[X-ray crystallography]] the uranium centers are eight-coordinate, being surrounded by eight chlorine atoms, four at 264 pm and the other four at 287pm.<ref>((cite journal|last=Taylor|first=J.C.|author2=Wilson, P.W. |year=1973|title=A neutron-diffraction study of anhydrous uranium tetrachloride|journal=Acta Crystallogr. B |volume=29|pages=1942–1944|doi=10.1107/S0567740873005790|issue=9|doi-access=free|bibcode=1973AcCrB..29.1942T ))</ref>

== Chemical properties ==
Dissolution in protic solvents is more complicated. When UCl<sub>4</sub> is added to water the uranium [[Metal ions in aqueous solution|aqua ion]] is formed.
:UCl<sub>4</sub> + ((mvar|x))H<sub>2</sub>O → [U(H<sub>2</sub>O)<sub>((mvar|x))</sub>]<sup>4+</sup> + 4Cl<sup>−</sup>
The aqua ion [U(H<sub>2</sub>O)<sub>((mvar|x))</sub>]<sup>4+</sup>, (x is 8 or 9<ref>((cite journal|last=David|first=F.|year=1986|title=Thermodynamic properties of lanthanide and actinide ions in aqueous solution|journal=Journal of the Less Common Metals|volume=121|pages=27–42|doi=10.1016/0022-5088(86)90511-4))</ref>) is strongly hydrolyzed. 
:[U(H<sub>2</sub>O)<sub>((mvar|x))</sub>]<sup>4+</sup> ((eqm)) [U(H<sub>2</sub>O)<sub>((math|''x''−1))</sub>(OH)]<sup>3+</sup> + H<sup>+</sup>
The [[acid dissociation constant|pK<sub>a</sub>]] for this reaction is ca. 1.6,<ref name=scdb>[http://swww.acadsoft.co.uk/scdbase/scdbase.htm IUPAC SC-Database]((Dead link|date=July 2018 |bot=InternetArchiveBot |fix-attempted=yes )) A comprehensive database of published data on equilibrium constants of metal complexes and ligands</ref> so hydrolysis is absent only in solutions of acid strength 1&nbsp;mol dm<sup>−3</sup> or stronger (pH < 0). Further hydrolysis occurs at pH > 3. Weak chloro complexes of the aqua ion may be formed. Published estimates of the log K value for the formation of [UCl]<sup>3+</sup>(aq) vary from −0.5 to +3 because of difficulty in dealing with simultaneous hydrolysis.<ref name=scdb/>

With alcohols, partial [[solvolysis]] may occur.
:UCl<sub>4</sub> + ((mvar|x))ROH ((eqm)) UCl<sub>((math|4−''x''))</sub>(OR)<sub>((mvar|x))</sub> + ((mvar|x))HCl

Uranium tetrachloride dissolves in non-protic solvents such as [[tetrahydrofuran]], [[acetonitrile]], [[dimethyl formamide]] etc. that can act as [[Lewis base]]s. Solvates of formula UCl<sub>4</sub>L<sub>((mvar|x))</sub> are formed which may be isolated. The solvent must be completely free of dissolved water, or hydrolysis will occur, with the solvent, S, picking up the released proton.
:UCl<sub>4</sub> + H<sub>2</sub>O + S ((eqm)) UCl<sub>3</sub>(OH) + SH<sup>+</sup> +Cl<sup>−</sup>
The solvent molecules may be replaced by other ligand in a reaction such as 
:UCl<sub>4</sub> + 2Cl<sup>−</sup> → [UCl<sub>6</sub>]<sup>2−</sup>.
The solvent is not shown, just as when complexes of other metal ions are formed in aqueous solution.

Solutions of UCl<sub>4</sub> are susceptible to oxidation by air, resulting in the production of complexes of the [[uranyl]] ion.

== Applications ==
Uranium tetrachloride is produced commercially by the reaction of [[carbon tetrachloride]] with pure [[uranium dioxide]] UO<sub>2</sub> at 370&nbsp;°C. It has been used as feed in the electromagnetic [[isotope separation]] (EMIS) process of [[uranium enrichment]]. Beginning in 1944, the [[Y-12 National Security Complex|Oak Ridge Y-12 Plant]] converted UO<sub>3</sub> to UCl<sub>4</sub> feed for the [[Ernest O. Lawrence]]'s [[calutron|Alpha Calutrons]]. Its major benefit being the uranium tetrachloride used in the calutrons is not as corrosive as the [[uranium hexafluoride]] used in most other enrichment technologies This process was abandoned in the 1950s. In the 1980s, however, [[Iraq]] unexpectedly revived this option as part of its nuclear weapons program. In the enrichment process, uranium tetrachloride is ionized into a uranium [[plasma (physics)|plasma]].

The uranium ions are then accelerated and passed through a strong [[magnetic field]]. After traveling along half of a circle, the beam is split into a region nearer the outside wall, which is [[depleted uranium|depleted]], and a region nearer the inside wall, which is [[enriched uranium|enriched]] in [[uranium-235|<sup>235</sup>U]]. The large amounts of energy required in maintaining the strong magnetic fields as well as the low recovery rates of the uranium feed material and slower more inconvenient facility operation make this an unlikely choice for large scale enrichment plants.

Work is being done in the use of molten uranium chloride–alkali chloride mixtures as reactor fuels in [[molten salt reactor]]s. Uranium tetrachloride melts dissolved in a [[lithium chloride]]–[[potassium chloride]] eutectic have also been explored as a means to recover [[actinides]] from irradiated [[nuclear fuel]]s through pyrochemical [[nuclear reprocessing]].<ref>Olander, D. R. and Camahort, J. L. (1966), Reaction of chlorine and uranium tetrachloride in the fused lithium chloride-potassium chloride eutectic. AIChE Journal, 12: 693–699. ((doi|10.1002/aic.690120414))</ref>

== Safety ==
Like all water soluble uranium salts, uranium tetrachloride is [[nephrotoxic]] (poisonous to the kidney) and can cause severe renal damage and acute renal failure if ingested.

== References ==
((reflist))

((Uranium compounds))
((Chlorides))
((Actinide halides))

((DEFAULTSORT:Uranium Tetrachloride))
[[Category:Uranium(IV) compounds]]
[[Category:Chlorides]]
[[Category:Actinide halides]]
[[Category:Nuclear materials]]

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