Terbium(III,IV) oxide

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Terbium(III,IV) oxide
Tetraterbium heptaoxide.jpg
Names
IUPAC name
Tetraterbium heptaoxide
Other names
Terbium(III,IV) oxide,
Terbium peroxide
Identifiers
3D model (JSmol)
ECHA InfoCard 100.031.675 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
  • InChI=1S/7O.4Tb
  • O=[Tb]O[Tb](=O)O[Tb](=O)O[Tb]=O
Properties
Tb4O7
Molar mass 747.6972 g/mol
AppearanceDark brown-black
hygroscopic solid.
Density 7.3 g/cm3
Melting point Decomposes to Tb2O3
Insoluble
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Oxidising agent.
Related compounds
Other cations
Terbium(III) oxide
Terbium(IV) oxide
Related compounds
 Cerium(IV) oxide
Praseodymium(III,IV) oxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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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.

Contents

Synthesis

Tb4O7 is most often produced by ignition of the oxalate or the sulfate in air. [1] The oxalate (at 1000 °C) is generally preferred, since the sulfate requires a higher temperature, and it produces an almost black product contaminated with Tb6O11 or other oxygen-rich oxides.

Chemical properties

Terbium(III,IV) oxide loses O2 when heated at high temperatures; at more moderate temperatures (ca. 350 °C) it reversibly loses oxygen, as shown by exchange with18O2. This property, also seen in Pr6O11 and V2O5, allows it to work like V2O5 as a redox catalyst in reactions involving oxygen. It was found as early as 1916 that hot Tb4O7 catalyses the reaction of coal gas (CO + H2) with air, leading to incandescence and often ignition. [2]

Tb4O7 reacts with atomic oxygen to produce TbO2, but more convenient preparations are available. [3]

Tb
4O
7 (s) + 6 HCl (aq) → 2 TbO
2 (s) + 2 TbCl
3 (aq) + 3 H
2O (l)

. Tb4O7 reacts with other hot concentrated acids to produce terbium(III) salts. For example, reaction with sulfuric acid gives terbium(III) sulfate. Terbium oxide reacts slowly with hydrochloric acid to form terbium(III) chloride solution, and elemental chlorine. At ambient temperature, complete dissolution might require a month; in a hot water bath, about a week.

Anhydrous terbium(III) chloride can be produced by the ammonium chloride route [4] [5] [6] In the first step, terbium oxide is heated with ammonium chloride to produce the ammonium salt of the pentachloride:

Tb4O7 + 22 NH4Cl → 4 (NH4)2TbCl5 + 7 H2O + 14 NH3

In the second step, the ammonium chloride salt is converted to the trichlorides by heating in a vacuum at 350-400 °C:

(NH4)2TbCl5 → TbCl3 + 2 HCl + 2 NH3

Related Research Articles

<span class="mw-page-title-main">Terbium</span> Chemical element, symbol Tb and atomic number 65

Terbium is a chemical element with the symbol Tb and atomic number 65. It is a silvery-white, rare earth metal that is malleable, and ductile. The ninth member of the lanthanide series, terbium is a fairly electropositive metal that reacts with water, evolving hydrogen gas. Terbium is never found in nature as a free element, but it is contained in many minerals, including cerite, gadolinite, monazite, xenotime and euxenite.

<span class="mw-page-title-main">Praseodymium(III) chloride</span> Chemical compound

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).

<span class="mw-page-title-main">Samarium(III) chloride</span> 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.

<span class="mw-page-title-main">Europium(III) chloride</span> Chemical compound

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.

<span class="mw-page-title-main">Dysprosium(III) chloride</span> Chemical compound

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.

<span class="mw-page-title-main">Iridium(III) chloride</span> Chemical compound

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.

<span class="mw-page-title-main">Tantalum(V) chloride</span> 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.

<span class="mw-page-title-main">Erbium(III) chloride</span> Chemical compound

Erbium(III) chloride is a violet solid with the formula ErCl3. It is used in the preparation of erbium metal.

<span class="mw-page-title-main">Gadolinium(III) chloride</span> Chemical compound

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.

<span class="mw-page-title-main">Yttrium(III) chloride</span> Chemical compound

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 solids that are highly soluble in water and deliquescent.

<span class="mw-page-title-main">Ytterbium(III) chloride</span> Chemical compound

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.

Indium(III) sulfate (In2(SO4)3) is a sulfate salt of the metal indium. It is a sesquisulfate, meaning that the sulfate group occurs 11/2 times as much as the metal. It may be formed by the reaction of indium, its oxide, or its carbonate with sulfuric acid. An excess of strong acid is required, otherwise insoluble basic salts are formed. As a solid indium sulfate can be anhydrous, or take the form of a pentahydrate with five water molecules or a nonahydrate with nine molecules of water. Indium sulfate is used in the production of indium or indium containing substances. Indium sulfate also can be found in basic salts, acidic salts or double salts including indium alum.

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.

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.

Praseodymium compounds are compounds formed by the lanthanide metal praseodymium (Pr). In these compounds, praseodymium generally exhibits the +3 oxidation state, such as PrCl3, Pr(NO3)3 and Pr(CH3COO)3. However, compounds with praseodymium in the +2 and +4 oxidation states, and unlike other lanthanides, the +5 oxidation state, are also known.

<span class="mw-page-title-main">Terbium compounds</span> Chemical compounds with at least one terbium atom

Terbium compounds are compounds formed by the lanthanide metal terbium (Tb). Terbium generally exhibits the +3 oxidation state in these compounds, such as in TbCl3, Tb(NO3)3 and Tb(CH3COO)3. Compounds with terbium in the +4 oxidation state are also known, such as TbO2 and BaTbF6. Terbium can also form compounds in the 0, +1 and +2 oxidation states.

Cerium compounds are compounds containing the element cerium (Ce), a lanthanide. Cerium exists in two main oxidation states, Ce(III) and Ce(IV). This pair of adjacent oxidation states dominates several aspects of the chemistry of this element. Cerium(IV) aqueous solutions may be prepared by reacting cerium(III) solutions with the strong oxidizing agents peroxodisulfate or bismuthate. The value of E⦵(Ce4+/Ce3+) varies widely depending on conditions due to the relative ease of complexation and hydrolysis with various anions, although +1.72 V is representative. Cerium is the only lanthanide which has important aqueous and coordination chemistry in the +4 oxidation state.

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.

References

  1. ↑ Hartmut Bergmann, Leopold Gmelin (1986). Gmelin Handbook of Inorganic Chemistry, System Number 39. Springer-Verlag. p. 397. ISBN   9783540935254.
  2. ↑ Bissell, D. W.; James, C. (1916). "Gadolinium Sodium Sulfate". Journal of the American Chemical Society. 38 (4): 873–875. doi:10.1021/ja02261a012.
  3. ↑ Edelmann, F.T.; Poremba, P. (1967). Herrmann, W.A. (ed.). Synthetic Methods of Organometallic and Inorganic Chemistry. Vol. 6. Stuttgart: Georg Thieme Verlag. ISBN   3-13-103071-2.
  4. ↑ Brauer, G., ed. (1963). Handbook of Preparative Inorganic Chemistry (2nd ed.). New York: Academic Press.
  5. ↑ Meyer, G. (1989). The Ammonium Chloride Route to Anhydrous Rare Earth Chlorides-The Example of YCl3. Inorganic Syntheses. Vol. 25. pp. 146–150. doi:10.1002/9780470132562.ch35. ISBN   978-0-470-13256-2.
  6. ↑ Edelmann, F. T.; Poremba, P. (1997). Herrmann, W. A. (ed.). Synthetic Methods of Organometallic and Inorganic Chemistry. Vol. VI. Stuttgart: Georg Thieme Verlag. ISBN   978-3-13-103021-4.

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