Thorium(IV) chloride

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Thorium(IV) chloride
ThCl4.png
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.030.039 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 233-056-1
PubChem CID
RTECS number
  • XO6475000
UNII
  • InChI=1S/4ClH.Th/h4*1H;/q;;;;+4/p-4
    Key: WEQHQGJDZLDFID-UHFFFAOYSA-J
  • Cl[Th](Cl)(Cl)Cl
Properties
ThCl4
Molar mass 373.849 g/mol
Appearancewhite needles
hygroscopic
Density 4.59 g/cm3, solid
Melting point 770 °C (1,420 °F; 1,040 K)
Boiling point 921 °C (1,690 °F; 1,194 K)
Structure
tetragonal
Hazards
not listed
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Thorium(IV) chloride describes a family of inorganic compounds with the formula ThCl4(H2O)n. Both the anhydrous and tetrahydrate (n = 4) forms are known. They are hygroscopic, water-soluble white solids.

Contents

Structures

Alternative view of the structure of solid ThCl4. Kristallstruktur Uran(IV)-fluorid.png
Alternative view of the structure of solid ThCl4.

The structure of thorium(IV) chloride features 8-coordinate Th centers with doubly bridging chloride ligands. [1]

Synthesis

ThCl4 was an intermediate in the original isolation of thorium metal by Jons Jacob Berzelius. [2]

Thorium(IV) chloride can be produced in a variety of ways. One method, a carbothermic reaction, 700 °C to 2600 °C, involving thorium oxides and carbon in a stream of chlorine gas:

ThO2 + 2 C + 4 Cl2 → ThCl4 + 2 CO

The chlorination reaction can be effected with carbon tetrachloride: [3] [4]

Th(C2O4)2 + CCl4 → ThCl4 + 3 CO + 3 CO2

In another two-step method, thorium metal reacts with ammonium chloride:

Th + 6 NH4Cl → (NH4)2ThCl6 + 4 NH3 + 2 H2

The hexachloride salt is then heated at 350 °C under a high vacuum to produce ThCl4. [5]

Reactions

Lewis base adducts

ThCl4 reacts with Lewis bases to give molecular adducts, such as ThCl4(DME)2 and ThCl4(TMEDA)2. [5]

Reduction to Th metal

Thorium(IV) chloride is an intermediate in the purification of thorium, which can be effected by

  1. Reduction of ThCl4 with alkali metals.
  2. Electrolysis of anhydrous thorium(IV) chloride in fused mixture of NaCl and KCl.
  3. Ca reduction of a mixture of ThCl4 with anhydrous zinc chloride. [6]

Related Research Articles

Protactinium Chemical element with atomic number 91

Protactinium is a chemical element with the symbol Pa and atomic number 91. It is a dense, silvery-gray actinide metal which readily reacts with oxygen, water vapor and inorganic acids. It forms various chemical compounds in which protactinium is usually present in the oxidation state +5, but it can also assume +4 and even +3 or +2 states. Concentrations of protactinium in the Earth's crust are typically a few parts per trillion, but may reach up to a few parts per million in some uraninite ore deposits. Because of its scarcity, high radioactivity and high toxicity, there are currently no uses for protactinium outside scientific research, and for this purpose, protactinium is mostly extracted from spent nuclear fuel.

Silicon tetrachloride or tetrachlorosilane is the inorganic compound with the formula SiCl4. It is a colourless volatile liquid that fumes in air. It is used to produce high purity silicon and silica for commercial applications.

Zinc chloride Chemical compound

Zinc chloride is the name of chemical compounds with the formula ZnCl2 and its hydrates. Zinc chlorides, of which nine crystalline forms are known, are colorless or white, and are highly soluble in water. This white salt is hygroscopic and even deliquescent. Samples should therefore be protected from sources of moisture, including the water vapor present in ambient air. Zinc chloride finds wide application in textile processing, metallurgical fluxes, and chemical synthesis. No mineral with this chemical composition is known aside from the very rare mineral simonkolleite, Zn5(OH)8Cl2·H2O.

Titanium tetrachloride Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms spectacular opaque clouds of titanium dioxide (TiO2) and hydrated hydrogen chloride. It is sometimes referred to as "tickle" or "tickle 4" due to the phonetic resemblance of its molecular formula (TiCl4) to the word.

Samarium(III) chloride Chemical compound

Samarium(III) chloride, also known as samarium trichloride, is an inorganic compound of samarium and chloride. It is a pale yellow salt that rapidly absorbs water to form a hexahydrate, SmCl3.6H2O. The compound has few practical applications but is used in laboratories for research on new compounds of samarium.

Tin(IV) chloride, also known as tin tetrachloride or stannic chloride, is an inorganic compound with the formula SnCl4. It is a colorless hygroscopic liquid, which fumes on contact with air. It is used as a precursor to other tin compounds. It was first discovered by Andreas Libavius (1550–1616) and was known as spiritus fumans libavii.

Chromium(III) chloride Chemical compound

Chromium(III) chloride (also called chromic chloride) describes any of several compounds of with the formula CrCl3 • xH2O, where x can be 0, 5, and 6. The anhydrous compound with the formula CrCl3 is a violet solid. The most common form of the trichloride is the dark green hexahydrate, CrCl3 • 6H2O. Chromium chlorides find use as catalysts and as precursors to dyes for wool.

Nickel(II) chloride Chemical compound

Nickel(II) chloride (or just nickel chloride), is the chemical compound NiCl2. The anhydrous salt is yellow, but the more familiar hydrate NiCl2·6H2O is green. Nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. The nickel chlorides are deliquescent, absorbing moisture from the air to form a solution. Nickel salts have been shown to be carcinogenic to the lungs and nasal passages in cases of long-term inhalation exposure.

Rhodium(III) chloride Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic solids featuring octahedral Rh(III) centres. Depending on the value of n, the material is either a dense brown solid or a soluble reddish salt. The soluble trihydrated (n = 3) salt is widely used to prepare compounds used in homogeneous catalysis, notably for the industrial production of acetic acid and hydroformylation.

Tantalum(V) chloride Chemical compound

Tantalum(V) chloride, also known as tantalum pentachloride, is an inorganic compound with the formula TaCl5. It takes the form of a white powder and is commonly used as a starting material in tantalum chemistry. It readily hydrolyzes to form tantalum(V) oxychloride (TaOCl3) and eventually tantalum pentoxide (Ta2O5); this requires that it be synthesised and manipulated under anhydrous conditions, using air-free techniques.

Scandium oxide Chemical compound

Scandium(III) oxide or scandia is a inorganic compound with formula Sc2O3. It is one of several oxides of rare earth elements with a high melting point. It is used in the preparation of other scandium compounds as well as in high-temperature systems (for its resistance to heat and thermal shock), electronic ceramics, and glass composition (as a helper material).

Hafnium tetrachloride Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

Boron trichloride is the inorganic compound with the formula BCl3. This colorless gas is a reagent in organic synthesis. It is highly reactive toward water.

Zirconium(IV) chloride Chemical compound

Zirconium(IV) chloride, also known as zirconium tetrachloride, (ZrCl4) is an inorganic compound frequently used as a precursor to other compounds of zirconium. This white high-melting solid hydrolyzes rapidly in humid air.

Titanium tetrabromide Chemical compound

Titanium tetrabromide is the chemical compound with the formula TiBr4. It is the most volatile transition metal bromide. The properties of TiBr4 are an average of TiCl4 and TiI4. Some key properties of these four-coordinated Ti(IV) species are their high Lewis acidity and their high solubility in nonpolar organic solvents. TiBr4 is diamagnetic, reflecting the d0 configuration of the metal centre.

Organoactinide chemistry

Organoactinide chemistry is the science exploring the properties, structure and reactivity of organoactinide compounds, which are organometallic compounds containing a carbon to actinide chemical bond.

Niobium(IV) chloride Chemical compound

Niobium(IV) chloride, also known as niobium tetrachloride, is the chemical compound of formula NbCl4. This compound exists as dark violet crystals, is highly sensitive to air and moisture, and disproportiates into niobium(III) chloride and niobium(V) chloride when heated.

Metal halides

Metal halides are compounds between metals and halogens. Some, such as sodium chloride are ionic, while others are covalently bonded. Covalently bonded metal halides may be discrete molecules, such as uranium hexafluoride, or they may form polymeric structures, such as palladium chloride.

Lead(IV) chloride Chemical compound

Lead tetrachloride, also known as lead(IV) chloride, has the molecular formula PbCl4. It is a yellow, oily liquid which is stable below 0 °C, and decomposes at 50 °C. It has a tetrahedral configuration, with lead as the central atom. The Pb–Cl covalent bonds have been measured to be 247 pm and the bond energy is 243 kJ⋅mol−1.

Compounds of thorium

Many compounds of thorium are known: this is because thorium and uranium are the most stable and accessible actinides and are the only actinides that can be studied safely and legally in bulk in a normal laboratory. As such, they have the best-known chemistry of the actinides, along with that of plutonium, as the self-heating and radiation from them is not enough to cause radiolysis of chemical bonds as it is for the other actinides. While the later actinides from americium onwards are predominantly trivalent and behave more similarly to the corresponding lanthanides, as one would expect from periodic trends, the early actinides up to plutonium have relativistically destabilised and hence delocalised 5f and 6d electrons that participate in chemistry in a similar way to the early transition metals of group 3 through 8: thus, all their valence electrons can participate in chemical reactions, although this is not common for neptunium and plutonium.

References

  1. Mason, J. T.; Jha, M. C.; Chiotti, P. (1974). "Crystal Structures of ThCl4 Polymorphs". Journal of the Less Common Metals. 34: 143–151. doi:10.1016/0022-5088(74)90224-0.
  2. Weeks, Mary Elvira (1932-07-01). "The Discovery of the Elements. XI. Some Elements Isolated with the Aid of Potassium and Sodium: Zirconium, Titanium, Cerium, and Thorium". Journal of Chemical Education. 9 (7): 1231. Bibcode:1932JChEd...9.1231W. doi:10.1021/ed009p1231. ISSN   0021-9584.
  3. Brauer, Georg (1963). Handbook Of Preparative Inorganic Chemistry. New York: Academic Press.
  4. Gutierrez, R. L.; Herbst, R. J. (October 1979). "Preliminary Fabrication Studies of Alternative LMFBR Carbide Fuels". Los Alamos Scientific Laboratory.
  5. 1 2 Cantat, Thibault; Scott, Brian L.; Kiplinger, Jaqueline L. (2010-01-25). "Convenient Access to the Anhydrous Thorium Tetrachloride Complexes ThCl4(DME)2, ThCl4(1,4-dioxane)2 and ThCl4(THF)3.5 using Commercially Available and Inexpensive Starting Materials". Chemical Communications. 46 (6): 919–21. doi:10.1039/b923558b. ISSN   1364-548X. PMID   20107650.
  6. "Periodic Table of Elements: Los Alamos National Laboratory". periodic.lanl.gov. Retrieved 2016-04-29.