Lanthanide trichlorides are a family of inorganic compound with the formula LnCl3, where Ln stands for a lanthanide metal. The trichlorides are standard reagents in applied and academic chemistry of the lanthanides. They exist as anhydrous solids and as hydrates.
The anhydrous solids have melting points range from ca. 582 (Tb) - 925 °C (Lu). They are generally pale colored, often white. As coordination polymers, they only dissolve in donor solvents, including water.
| MCl3 | color | structure type | f-configuration | comment |
|---|---|---|---|---|
| ScCl3 | colorless | AlCl3-type | f0 | not classified as a lanthanide usually |
| YCl3 | colorless | AlCl3-type | f0 | not classified as a lanthanide usually |
| LaCl3 | colorless | UCl3-type | f0 | diamagnetic |
| CeCl3 | colorless | UCl3-type | f1, doublet | - |
| PrCl3 | green | UCl3-type | f2, triplet | - |
| NdCl3 | pink | UCl3-type | f3, quartet | - |
| PmCl3 | green | UCl3-type | f4, quintet | radioactive |
| SmCl3 | yellow | UCl3-type | f5, sextet | - |
| EuCl3 | yellow | UCl3-type | f6, septet | - |
| GdCl3 | colorless | UCl3-type | f7, octet | symmetrical electronic shell |
| TbCl3 | white | PuBr3-type | f8, septet | - |
| DyCl3 | white | AlCl3-type | f9, sextet | - |
| HoCl3 | yellow | AlCl3-type | f10, quintet | - |
| ErCl3 | violet | AlCl3-type | f11, quartet | - |
| TmCl3 | yellow | AlCl3-type | f12, triplet | - |
| YbCl3 | colorless | YCl3-type | f13, doublet | - |
| LuCl3 | colorless | AlCl3-type | f14 | diamagnetic |
The lanthanide oxides and carbonates dissolve in hydrochloric acid to give chloride salt of the hydrated cations:
Anhydrous trichlorides are produced commercially by carbothermic reaction of the oxide: [2]
The ammonium chloride route refers to a general procedure to produce anhydrous lanthanide chlorides. The method has the advantages of being general for the 14 lanthanides and it produces air-stable intermediates that resist hydrolysis. The use of ammonium chloride as a reagent is convenient because the salt is anhydrous, even when handled in air. Ammonium chloride is also attractive because it thermally decomposes to volatile products at temperatures compatible with the stability of the trichloride targets. [3] [4] [5]
The reaction of an intimate mixture of lanthanide oxides with excess ammonium chloride produces anhydrous ammonium salts of the penta- and hexachlorides. Typical reaction conditions are hours at 230-250 °C. [4] Some lanthanides (as well as scandium and yttrium) form pentachlorides:
(M = Dy, Ho, Er, Tm, Lu, Yb, Y, Sc)
Other lanthanides for hexachlorides:
(M = La, Ce, Nd, Pm, Sm, Eu, Gd)
These reactions can also start with the metals, e.g.: [4]
The ammonium lanthanum chlorides are converted to the trichlorides by heating in a vacuum. Typical reaction temperatures are 350–400 °C: [4]
Hydrated lanthanide trichlorides dehydrate under a hot stream of hydrogen chloride. [3]
![Structure of GdCl3 6H2O, which consists of [GdCl2(H2O)6] centers. The coordination spheres are interconnected by hydrogen bonds between the protons and both the coordinated and the ionic chlorides. ICCD22343.png](http://upload.wikimedia.org/wikipedia/commons/thumb/9/9f/ICCD22343.png/320px-ICCD22343.png)
As indicated in the table, the anhydrous trichlorides follow two main motifs, UCl3 and YCl3. The UCl3 structure features 9-coordinate metal centers. The PuBr3 structure, adopted uniquely by TbCl3, features 8-coordinated metals. The remaining later metals are 6-coordinate as is aluminium trichloride. [7]
Lanthanide trichlorides are commercial precursors to the metals by reduction, e.g. with aluminium: [2]
In some cases, the trifluoride is preferred.
They react with humid air to give oxychlorides:
For synthetic chemists, this reaction is a problematic since the oxychlorides are less reactive.
Zinc chloride is the name of inorganic chemical compounds with the formula ZnCl2. It forms hydrates. Zinc chloride, anhydrous and its hydrates are colorless or white crystalline solids, and are highly soluble in water. Five hydrates of zinc chloride are known, as well as four forms of anhydrous zinc chloride. This salt is hygroscopic and even deliquescent. 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.
Cerium(III) chloride (CeCl3), also known as cerous chloride or cerium trichloride, is a compound of cerium and chlorine. It is a white hygroscopic salt; it rapidly absorbs water on exposure to moist air to form a hydrate, which appears to be of variable composition, though the heptahydrate CeCl3·7H2O is known. It is highly soluble in water, and (when anhydrous) it is soluble in ethanol and acetone.
Praseodymium(III) chloride is the inorganic compound with the formula PrCl3. Like other lanthanide trichlorides, it exists both in the anhydrous and hydrated forms. It is a blue-green solid that rapidly absorbs water on exposure to moist air to form a light green heptahydrate.
Neodymium(III) chloride or neodymium trichloride is a chemical compound of neodymium and chlorine with the formula NdCl3. This anhydrous compound is a mauve-colored solid that rapidly absorbs water on exposure to air to form a purple-colored hexahydrate, NdCl3·6H2O. Neodymium(III) chloride is produced from minerals monazite and bastnäsite using a complex multistage extraction process. The chloride has several important applications as an intermediate chemical for production of neodymium metal and neodymium-based lasers and optical fibers. Other applications include a catalyst in organic synthesis and in decomposition of waste water contamination, corrosion protection of aluminium and its alloys, and fluorescent labeling of organic molecules (DNA).
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.
Europium(III) chloride is an inorganic compound with the formula EuCl3. The anhydrous compound is a yellow solid. Being hygroscopic it rapidly absorbs water to form a white crystalline hexahydrate, EuCl3·6H2O, which is colourless. The compound is used in research.
Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula AlCl3. It forms a hexahydrate with the formula [Al(H2O)6]Cl3, containing six water molecules of hydration. Both the anhydrous form and the hexahydrate are colourless crystals, but samples are often contaminated with iron(III) chloride, giving them a yellow colour.
Dysprosium(III) chloride (DyCl3), also known as dysprosium trichloride, is a compound of dysprosium and chlorine. It is a white to yellow solid which rapidly absorbs water on exposure to moist air to form a hexahydrate, DyCl3·6H2O. Simple rapid heating of the hydrate causes partial hydrolysis to an oxychloride, DyOCl.
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.
Iridium(III) chloride is the inorganic compound with the formula IrCl3. The anhydrous compound is relatively rare, but the related hydrate is much more commonly encountered. The anhydrous salt has two polymorphs, α and β, which are brown and red colored respectively. More commonly encountered is the hygroscopic dark green trihydrate IrCl3(H2O)3 which is a common starting point for iridium chemistry.
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).
Terbium(III,IV) oxide, occasionally called tetraterbium heptaoxide, has the formula Tb4O7, though some texts refer to it as TbO1.75. There is some debate as to whether it is a discrete compound, or simply one phase in an interstitial oxide system. Tb4O7 is one of the main commercial terbium compounds, and the only such product containing at least some Tb(IV) (terbium in the +4 oxidation state), along with the more stable Tb(III). It is produced by heating the metal oxalate, and it is used in the preparation of other terbium compounds. Terbium forms three other major oxides: Tb2O3, TbO2, and Tb6O11.
Erbium(III) chloride is a violet solid with the formula ErCl3. It is used in the preparation of erbium metal.
Gadolinium(III) chloride, also known as gadolinium trichloride, is GdCl3. It is a colorless, hygroscopic, water-soluble solid. The hexahydrate GdCl3∙6H2O is commonly encountered and is sometimes also called gadolinium trichloride. Gd3+ species are of special interest because the ion has the maximum number of unpaired spins possible, at least for known elements. With seven valence electrons and seven available f-orbitals, all seven electrons are unpaired and symmetrically arranged around the metal. The high magnetism and high symmetry combine to make Gd3+ a useful component in NMR spectroscopy and MRI.
Yttrium(III) chloride is an inorganic compound of yttrium and chloride. It exists in two forms, the hydrate (YCl3(H2O)6) and an anhydrous form (YCl3). Both are colourless salts that are highly soluble in water and deliquescent.
Ytterbium(III) chloride (YbCl3) is an inorganic chemical compound. It reacts with NiCl2 to form a very effective catalyst for the reductive dehalogenation of aryl halides. It is poisonous if injected, and mildly toxic by ingestion. It is an experimental teratogen, known to irritate the skin and eyes.
Lanthanum chloride is the inorganic compound with the formula LaCl3. It is a common salt of lanthanum which is mainly used in research. It is a white solid that is highly soluble in water and alcohols.
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 salts.
Thulium(III) chloride or thulium trichloride is as an inorganic salt composed of thulium and chlorine with the formula TmCl3. It forms yellow crystals. Thulium(III) chloride has the YCl3 (AlCl3) layer structure with octahedral thulium ions. It has been used as a starting material for some exotic nanostructures prepared for NIR photocatalysis.
Erbium compounds are compounds containing the element erbium (Er). These compounds are usually dominated by erbium in the +3 oxidation state, although the +2, +1 and 0 oxidation states have also been reported.
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