Ammonium perrhenate

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Ammonium perrhenate
Ammonium perrhenate.png
Ammonium perrhenate.jpg
Names
Other names
Ammonium perrhenate,
Ammonium perrhenate(VII)
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.690 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 237-075-6
PubChem CID
  • InChI=1S/H3N.4O.Re/h1H3;;;;;/q;;;;-1;/p+1 Yes check.svgY
    Key: HOJYZCWLNWENHS-UHFFFAOYSA-O Yes check.svgY
  • InChI=1/H3N.4O.Re/h1H3;;;;;/q;;;;-1;/p+1/rH3N.O4Re/c;1-5(2,3)4/h1H3;/q;-1/p+1
    Key: HOJYZCWLNWENHS-WUACXKGRAA
  • [O-] [Re](=O)(=O)=O.[NH4+]
Properties
NH4ReO4
Molar mass 268.2359 g/mol
Density 3.97 g/cm3, solid
Melting point 200°C (decomposes) [1]
2.8 g/100 mL (0 °C), 6.2 g/100 mL (20 °C), 12.0 g/100 mL (40 °C), 20.7 g/100 mL (60 °C), 32.3 g/100 mL (80 °C), 39.1 g/100 mL (90 °C)
Structure
scheelite
N/A
Hazards
Flash point Non-flammable
Related compounds
Other anions
Ammonium permanganate; ammonium pertechnetate
Other cations
Sodium perrhenate; perrhenic acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Ammonium perrhenate (APR) is the ammonium salt of perrhenic acid, NH4ReO4. It is the most common form in which rhenium is traded. It is a white salt; soluble in ethanol and water, and mildly soluble in NH4Cl. [2] It was first described soon after the discovery of rhenium. [3]

Contents

Structure

The crystal structure of ammonium perrhenate with orientationally ordered ammonium ions (blue) and ReO4 (grey) tetrahedra. Ammonium perrhenate Image.png
The crystal structure of ammonium perrhenate with orientationally ordered ammonium ions (blue) and ReO4 (grey) tetrahedra.

The crystal structure of APR resembles that of scheelite, with atomic cation is replaced by ammonium. The pertechnetate (NH4TcO4), periodate (NH4IO4), tetrachlorothallate (NH4TlCl4), and tetrachloroindate (NH4InCl4) follow this motif. [4] It undergoes a molecular orientational ordering transition on cooling without change of space group, but with a highly anisotropic change in the shape of the unit cell, resulting in the unusual property of having a positive temperature and pressure Re NQR coefficient. [5] APR does not give hydrates. [2]

Preparation

Ammonium perrhenate may be prepared from virtually all common sources of rhenium. The metal, oxides, and sulfides can be oxidized with nitric acid and the resulting solution treated with aqueous ammonia. Alternatively an aqueous solution of Re2O7 can be treated with ammonia followed by crystallisation. [6] [7]

Reactions

Ammonium perrhenate is weak oxidizer. It slowly reacts with hydrochloric acid: [2]

NH4ReO4 + 6 HCl → NH4[ReCl4O] + Cl2 ↑ + 3H2O.

It is reduced to metallic Re upon heating under hydrogen: [1]

2 NH4ReO4 + 7 H2 → 2 Re + 8 H2O + 2 NH3

Ammonium perrhenate decomposes to volatile Re2O7 starting at 250 °C. When heated in a sealed tube at 500 °C, It decomposes to rhenium dioxide: [1]

2NH4ReO4 → 2ReO2 + N2 + 4 H2O

The ammonium ion can be displaced with some concentrated nitrates e.g. potassium nitrate,, silver nitrate, etc.: [2]

NH4ReO4 + KNO3 → KReO4 ↓ + NH4NO3

It can be reduced to nonahydridorhenate with sodium in ethanol: [2]

NH4ReO4 + 18Na + 13C2H5OH → Na2[ReH9] + 13NaC2H5O + 3NaOH + NH3•H2O.

Related Research Articles

<span class="mw-page-title-main">Rhenium</span> Chemical element, symbol Re and atomic number 75

Rhenium is a chemical element; it has symbol Re and atomic number 75. It is a silvery-gray, heavy, third-row transition metal in group 7 of the periodic table. With an estimated average concentration of 1 part per billion (ppb), rhenium is one of the rarest elements in the Earth's crust. It has the third-highest melting point and second-highest boiling point of any element at 5869 K. It resembles manganese and technetium chemically and is mainly obtained as a by-product of the extraction and refinement of molybdenum and copper ores. It shows in its compounds a wide variety of oxidation states ranging from −1 to +7.

Urea, also called carbamide, is an organic compound with chemical formula CO(NH2)2. This amide has two amino groups joined by a carbonyl functional group. It is thus the simplest amide of carbamic acid.

<span class="mw-page-title-main">Group 7 element</span> Group of chemical elements

Group 7, numbered by IUPAC nomenclature, is a group of elements in the periodic table. It contains manganese (Mn), technetium (Tc), rhenium (Re) and bohrium (Bh). This group lies in the d-block of the periodic table, and are hence transition metals. This group is sometimes called the manganese group or manganese family after its lightest member; however, the group itself has not acquired a trivial name because it belongs to the broader grouping of the transition metals.

<span class="mw-page-title-main">Tollens' reagent</span> Chemical reagent used to distinguish between aldehydes and ketones

Tollens' reagent is a chemical reagent used to distinguish between aldehydes and ketones along with some alpha-hydroxy ketones which can tautomerize into aldehydes. The reagent consists of a solution of silver nitrate, ammonium hydroxide and some sodium hydroxide. It was named after its discoverer, the German chemist Bernhard Tollens. A positive test with Tollens' reagent is indicated by the precipitation of elemental silver, often producing a characteristic "silver mirror" on the inner surface of the reaction vessel.

<span class="mw-page-title-main">Ammonium bromide</span> Chemical compound

Ammonium bromide, NH4Br, is the ammonium salt of hydrobromic acid. The chemical crystallizes in colorless prisms, possessing a saline taste; it sublimes on heating and is easily soluble in water. On exposure to air it gradually assumes a yellow color because of the oxidation of traces of bromide (Br−) to bromine (Br2).

<span class="mw-page-title-main">Ammonium chlorate</span> Chemical compound

Ammonium chlorate is an inorganic compound with the formula NH4ClO3.

<span class="mw-page-title-main">Perrhenic acid</span> Chemical compound

Perrhenic acid is the chemical compound with the formula Re2O7(H2O)2. It is obtained by evaporating aqueous solutions of Re2O7. Conventionally, perrhenic acid is considered to have the formula HReO4, and a species of this formula forms when rhenium(VII) oxide sublimes in the presence of water or steam. When a solution of Re2O7 is kept for a period of months, it breaks down and crystals of HReO4·H2O are formed, which contain tetrahedral ReO−4. For most purposes, perrhenic acid and rhenium(VII) oxide are used interchangeably. Rhenium can be dissolved in nitric or concentrated sulfuric acid to produce perrhenic acid.

<span class="mw-page-title-main">Tetraamminecopper(II) sulfate</span> Chemical compound

Tetra ammine copper(II) sulphate is the salt with the formula [Cu(NH3)4]SO4·H2O. This dark blue to purple solid is a salt of the metal complex [Cu(NH3)4(H2O)]2+. It is closely related to Schweizer's reagent, which is used for the production of cellulose fibers in the production of rayon.

<span class="mw-page-title-main">Rhenium(VII) oxide</span> Chemical compound

Rhenium(VII) oxide is the inorganic compound with the formula Re2O7. This yellowish solid is the anhydride of HOReO3. Perrhenic acid, Re2O7·2H2O, is closely related to Re2O7. Re2O7 is the raw material for all rhenium compounds, being the volatile fraction obtained upon roasting the host ore.

<span class="mw-page-title-main">Sodium perrhenate</span> Chemical compound

Sodium perrhenate (also known as sodium rhenate(VII)) is the inorganic compound with the formula NaReO4. It is a white salt that is soluble in water. It is a common precursor to other rhenium compounds. Its structure resembles that of sodium perchlorate and sodium permanganate.

<span class="mw-page-title-main">Potassium nonahydridorhenate</span> Chemical compound

Potassium nonahydridorhenate(VII) is an inorganic compound having the formula K2[ReH9]. This colourless salt is soluble in water but only poorly soluble in most alcohols. This salt contains the nonahydridorhenate(VII) anion, [ReH9]2−, which is a rare example of a coordination complex bearing only hydride ligands.

<span class="mw-page-title-main">Chloroauric acid</span> Chemical compound

Chloroauric acid is an inorganic compound with the chemical formula H[AuCl4]. It forms hydrates H[AuCl4]·nH2O. Both the trihydrate and tetrahydrate are known. Both are orange-yellow solids consisting of the planar [AuCl4]− anion. Often chloroauric acid is handled as a solution, such as those obtained by dissolution of gold in aqua regia. These solutions can be converted to other gold complexes or reduced to metallic gold or gold nanoparticles.

<span class="mw-page-title-main">Oxotrichlorobis(triphenylphosphine)rhenium(V)</span> Chemical compound

Oxotrichlorobis(triphenylphosphine)rhenium(V) is the chemical compound with the formula ReOCl3(PPh3)2. This yellow, air-stable solid is a precursor to a variety of other rhenium complexes. In this diamagnetic compound, Re has an octahedral coordination environment with one oxo, three chloro and two mutually trans triphenylphosphine ligands. The oxidation state of rhenium is +5 and its configuration is d2.

The perrhenate ion is the anion with the formula ReO−
4, or a compound containing this ion. The perrhenate anion is tetrahedral, being similar in size and shape to perchlorate and the valence isoelectronic permanganate. The perrhenate anion is stable over a broad pH range and can be precipitated from solutions with the use of organic cations. At normal pH, perrhenate exists as metaperrhenate, but at high pH mesoperrhenate forms. Perrhenate, like its conjugate acid perrhenic acid, features rhenium in the oxidation state of +7 with a d0 configuration. Solid perrhenate salts takes on the color of the cation.

<span class="mw-page-title-main">Ammonium cyanide</span> Chemical compound

Ammonium cyanide is an unstable inorganic compound with the formula NH4CN.

<span class="mw-page-title-main">Potassium perrhenate</span> Chemical compound

Potassium perrhenate is an inorganic compound with the chemical formula KReO4.

Rhenium compounds are compounds formed by the transition metal rhenium (Re). Rhenium can form in many oxidation states, and compounds are known for every oxidation state from -3 to +7 except -2, although the oxidation states +7, +4, and +3 are the most common. Rhenium is most available commercially as salts of perrhenate, including sodium and ammonium perrhenates. These are white, water-soluble compounds. The tetrathioperrhenate anion [ReS4]− is possible.

<span class="mw-page-title-main">Scandium perrhenate</span> Chemical compound

Scandium perrhenate is an inorganic compound, with the chemical formula Sc(ReO4)3. Its thermal stability is lower than that of the corresponding compounds of the yttrium and lanthanum perrhenates.

<span class="mw-page-title-main">Gallium perrhenate</span> Chemical compound

Gallium perrhenate is an inorganic compound with the chemical formula of Ga(ReO4)3. It exists in the anhydrous and hydrate forms.

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

Rhenium(III) iodide is a binary chemical compound of rhenium and iodide with the chemical formula ReI
3.

References

  1. 1 2 3 Georg Brauer (1954), Ammoniumperrhenat, Ferdinand Enke Verlag, p. 1108
  2. 1 2 3 4 5 Lidin, R. (2007). Неорганическая химия в реакциях[Inorganic chemistry in reactions] (in Russian) (2nd ed.). Moscow: Drofa. p. 332. ISBN   978-5-358-01303-2.
  3. ↑ Noddack, J.; Noddack, W. (1929). "Die Sauerstoffverbindungen des Rheniums" [The oxygen compounds of rhenium]. Zeitschrift für anorganische und allgemeine Chemie (in German). 181 (6): 1–37. Bibcode:1929NW.....17...93N. doi:10.1002/zaac.19291810102.
  4. ↑ I. P. Swainson and R. J. C. Brown (1997). "Refinement of ammonium perrhenate structure using a pseudo-spin model for the ammonium ion orientation". Acta Crystallographica . B53 (1): 76–81. Bibcode:1997AcCrB..53...76S. doi:10.1107/S0108768196011160.
  5. ↑ R. J. C. Brown and S. L. Segel (1977). "187Re, 14N, and 2H nuclear quadrupole couplings in NH4ReO4: Evidence for a possible phase transition". Journal of Chemical Physics . 67 (7): 3163–7. Bibcode:1977JChPh..67.3163B. doi:10.1063/1.435229.
  6. ↑ O. Glemser "Ammonium Perrhenate" in Handbook of Preparative Inorganic Chemistry , 2nd Ed. Edited by G. Brauer, Academic Press, 1963, New York. vol. 1. p. 1476–85.
  7. ↑ Richard J. Thompson (1966). "Ammonium Perrhenate". Inorganic Syntheses. Inorganic Syntheses. Vol. 8. pp. 171–173. doi:10.1002/9780470132395.ch44. ISBN   9780470132395.
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