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Perrhenic acid

May 09, 2024

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.[2] 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.[3] 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.

Perrhenic acid
Names
IUPAC name
Tetraoxorhenic(VII) acid
Other names
Hydrated rhenium(VII) oxide
Identifiers
  • 13768-11-1 N
3D model (JSmol)
  • Interactive image
ChemSpider
  • 21106462 Y
ECHA InfoCard 100.033.968
EC Number
  • 237-380-4
  • 83718
RTECS number
  • TT4550000
  • DTXSID80894065
  • InChI=1S/2H2O.7O.2Re/h2*1H2;;;;;;;;; Y
    Key: JOTGKJVGIIKFIQ-UHFFFAOYSA-N Y
  • InChI=1/2H2O.7O.2Re/h2*1H2;;;;;;;;;/rH4O9Re2/c1-10(2,3)9-11(4,5,6,7)8/h4-5H2
    Key: JOTGKJVGIIKFIQ-SEUCOXMMAB
  • [OH2][Re](=O)(=O)(=O)([OH2])O[Re](=O)(=O)=O
Properties
H4Re2O9 (solid)
HReO4 (gas)
Molar mass 251.2055 g/mol
Appearance Pale yellow solid
Boiling point sublimes
Soluble
Acidity (pKa) -1.25[1]
Conjugate base Perrhenate
Structure
octahedral-tetrahedral (solid)
tetrahedral (gas)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Corrosive
GHS labelling:
Danger
H302, H314, H332
P260, P261, P264, P270, P271, P280, P301+P312, P301+P330+P331, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P310, P312, P321, P330, P363, P405, P501
NFPA 704 (fire diamond)
Health 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability (red): no hazard codeInstability (yellow): no hazard codeSpecial hazards (white): no code
3
Flash point Non-flammable
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)

Properties edit

The structure of solid perrhenic acid is [O3Re−O−ReO3(H2O)2].[4] This species is a rare example of a metal oxide coordinated to water; most often metal–oxo–aquo species are unstable with respect to their corresponding hydroxides:

M(O)(H2O) → M(OH)2

The two rhenium atoms have different bonding geometries, with one being tetrahedral and the other octahedral, and with the water ligands coordinated to the latter.

Gaseous perrhenic acid is tetrahedral, as suggested by its formula HReO4.

Reactions edit

Perrhenic acid or the related anhydrous oxide Re2O7 converts to dirhenium heptasulfide upon treatment with hydrogen sulfide:

Re2O7 + 7 H2S → Re2S7 + 7 H2O

The heptasulfide catalyzes various reductions.[5]

Perrhenic acid in the presence of hydrochloric acid undergoes reduction in the presence of thioethers and tertiary phosphines to give rhenium(V) complexes with the formula ReOCl3L2.[6]

Perrhenic acid combined with platinum on a support gives rise to a useful hydrogenation and hydrocracking catalyst for the petroleum industry.[7] For example, silica impregnated with a solution of perrhenic acid is reduced with hydrogen at 500 °C.[citation needed] This catalyst is used in the dehydrogenation of alcohols and also promotes the decomposition of ammonia.

Catalysis edit

Perrhenic acid is a precursor to a variety of homogeneous catalysts, some of which are promising in niche applications that can justify the high cost of rhenium. In combination with tertiary arsines, perrhenic acid gives a catalyst for the epoxidation of alkenes with hydrogen peroxide.[8] Perrhenic acid catalyses the dehydration of oximes to nitriles.[9]

 

Other uses edit

Perrhenic acid is also used in the manufacture of x-ray targets.[10][11]

See also edit

References edit

  1. ^ http://www.iupac.org/publications/pac/1998/pdf/7002x0355.pdf [bare URL PDF]
  2. ^ Glemser, O.; Müller, A.; Schwarzkopf, H. (1964). "Gasförmige Hydroxide. IX. Über ein Gasförmiges Hydroxid des Rheniums". Zeitschrift für anorganische und allgemeine Chemie (in German). 334 (1–2): 21–26. doi:10.1002/zaac.19643340105..
  3. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  4. ^ Beyer, H.; Glemser, O.; Krebs, B. "Dirhenium Dihydratoheptoxide Re
    2    O
    7    (OH
    2    )
    2     – New Type of Water Bonding in an Aquoxide" Angewandte Chemie, International Edition English 1968, Volume 7, Pages 295 - 296. doi:10.1002/anie.196802951.
  5. ^ Schwarz, D. E.; Frenkel, A. I.; Nuzzo, R. G.; Rauchfuss, T. B.; Vairavamurthy, A. (2004). "Electrosynthesis of ReS
    4    . XAS Analysis of ReS
    2    , Re
    2    S
    7    , and ReS
    4    ". Chemistry of Materials. 16: 151–158. doi:10.1021/cm034467v.
  6. ^ Parshall, G. W.; Shive, L. W.; Cotton, F. A. (1997). Phosphine Complexes of Rhenium. Inorganic Syntheses. Vol. 17. pp. 110–112. doi:10.1002/9780470132487.ch31. ISBN 9780470132487.
  7. ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  8. ^ van Vliet, M. C. A.; Arends, I. W. C. E.; Sheldon, R. A. (1999). "Rhenium Catalysed Epoxidations with Hydrogen Peroxide: Tertiary Arsines as Effective Cocatalysts". J. Chem. Soc., Perkin Trans. 1 (3): 377–80. doi:10.1039/a907975k.
  9. ^ Ishihara, K.; Furuya, Y.; Yamamoto, H. (2002). "Rhenium(VII) Oxo Complexes as Extremely Active Catalysts in the Dehydration of Primary Amides and Aldoximes to Nitriles". Angewandte Chemie International Edition. 41 (16): 2983–2986. doi:10.1002/1521-3773(20020816)41:16<2983::AID-ANIE2983>3.0.CO;2-X. PMID 12203432.
  10. ^ http://www.gehealthcare.com/usen/service/time_material_support/docs/Radplus2100.pdf[permanent dead link]
  11. ^ X-ray#Sources

May 09, 2024
perrhenic, acid, chemical, compound, with, formula, re2o7, obtained, evaporating, aqueous, solutions, re2o7, conventionally, perrhenic, acid, considered, have, formula, hreo4, species, this, formula, forms, when, rhenium, oxide, sublimes, presence, water, stea. 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 2 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 3 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 Perrhenic acid Names IUPAC name Tetraoxorhenic VII acid Other names Hydrated rhenium VII oxide Identifiers CAS Number 13768 11 1 N 3D model JSmol Interactive image ChemSpider 21106462 Y ECHA InfoCard 100 033 968 EC Number 237 380 4 PubChem CID 83718 RTECS number TT4550000 CompTox Dashboard EPA DTXSID80894065 InChI InChI 1S 2H2O 7O 2Re h2 1H2 YKey JOTGKJVGIIKFIQ UHFFFAOYSA N YInChI 1 2H2O 7O 2Re h2 1H2 rH4O9Re2 c1 10 2 3 9 11 4 5 6 7 8 h4 5H2Key JOTGKJVGIIKFIQ SEUCOXMMAB SMILES OH2 Re O O O OH2 O Re O O O Properties Chemical formula H4Re2O9 solid HReO4 gas Molar mass 251 2055 g mol Appearance Pale yellow solid Boiling point sublimes Solubility in water Soluble Acidity pKa 1 25 1 Conjugate base Perrhenate Structure Coordination geometry octahedral tetrahedral solid tetrahedral gas Hazards Occupational safety and health OHS OSH Main hazards Corrosive GHS labelling Pictograms Signal word Danger Hazard statements H302 H314 H332 Precautionary statements P260 P261 P264 P270 P271 P280 P301 P312 P301 P330 P331 P303 P361 P353 P304 P312 P304 P340 P305 P351 P338 P310 P312 P321 P330 P363 P405 P501 NFPA 704 fire diamond 3 Flash point Non flammable Related compounds Related compounds PerrhenateManganese VII oxideTechnetium VII oxideRhenium VII oxidePermanganic acidPertechnetic acidPerchloric acid Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references Contents 1 Properties 2 Reactions 2 1 Catalysis 3 Other uses 4 See also 5 ReferencesProperties editThe structure of solid perrhenic acid is O3Re O ReO3 H2O 2 4 This species is a rare example of a metal oxide coordinated to water most often metal oxo aquo species are unstable with respect to their corresponding hydroxides M O H2O M OH 2 The two rhenium atoms have different bonding geometries with one being tetrahedral and the other octahedral and with the water ligands coordinated to the latter Gaseous perrhenic acid is tetrahedral as suggested by its formula HReO4 Reactions editPerrhenic acid or the related anhydrous oxide Re2O7 converts to dirhenium heptasulfide upon treatment with hydrogen sulfide Re2O7 7 H2S Re2S7 7 H2O The heptasulfide catalyzes various reductions 5 Perrhenic acid in the presence of hydrochloric acid undergoes reduction in the presence of thioethers and tertiary phosphines to give rhenium V complexes with the formula ReOCl3L2 6 Perrhenic acid combined with platinum on a support gives rise to a useful hydrogenation and hydrocracking catalyst for the petroleum industry 7 For example silica impregnated with a solution of perrhenic acid is reduced with hydrogen at 500 C citation needed This catalyst is used in the dehydrogenation of alcohols and also promotes the decomposition of ammonia Catalysis edit Perrhenic acid is a precursor to a variety of homogeneous catalysts some of which are promising in niche applications that can justify the high cost of rhenium In combination with tertiary arsines perrhenic acid gives a catalyst for the epoxidation of alkenes with hydrogen peroxide 8 Perrhenic acid catalyses the dehydration of oximes to nitriles 9 nbsp Other uses editPerrhenic acid is also used in the manufacture of x ray targets 10 11 See also editPerrhenate Rhenium VII oxideReferences edit http www iupac org publications pac 1998 pdf 7002x0355 pdf bare URL PDF Glemser O Muller A Schwarzkopf H 1964 Gasformige Hydroxide IX Uber ein Gasformiges Hydroxid des Rheniums Zeitschrift fur anorganische und allgemeine Chemie in German 334 1 2 21 26 doi 10 1002 zaac 19643340105 Greenwood Norman N Earnshaw Alan 1997 Chemistry of the Elements 2nd ed Butterworth Heinemann ISBN 978 0 08 037941 8 Beyer H Glemser O Krebs B Dirhenium Dihydratoheptoxide Re2 O7 OH2 2 New Type of Water Bonding in an Aquoxide Angewandte Chemie International Edition English 1968 Volume 7 Pages 295 296 doi 10 1002 anie 196802951 Schwarz D E Frenkel A I Nuzzo R G Rauchfuss T B Vairavamurthy A 2004 Electrosynthesis of ReS4 XAS Analysis of ReS2 Re2 S7 and ReS4 Chemistry of Materials 16 151 158 doi 10 1021 cm034467v Parshall G W Shive L W Cotton F A 1997 Phosphine Complexes of Rhenium Inorganic Syntheses Vol 17 pp 110 112 doi 10 1002 9780470132487 ch31 ISBN 9780470132487 Holleman A F Wiberg E Inorganic Chemistry Academic Press San Diego 2001 ISBN 0 12 352651 5 van Vliet M C A Arends I W C E Sheldon R A 1999 Rhenium Catalysed Epoxidations with Hydrogen Peroxide Tertiary Arsines as Effective Cocatalysts J Chem Soc Perkin Trans 1 3 377 80 doi 10 1039 a907975k Ishihara K Furuya Y Yamamoto H 2002 Rhenium VII Oxo Complexes as Extremely Active Catalysts in the Dehydration of Primary Amides and Aldoximes to Nitriles Angewandte Chemie International Edition 41 16 2983 2986 doi 10 1002 1521 3773 20020816 41 16 lt 2983 AID ANIE2983 gt 3 0 CO 2 X PMID 12203432 http www gehealthcare com usen service time material support docs Radplus2100 pdf permanent dead link X ray Sources Retrieved from https en wikipedia org w index php title Perrhenic acid amp oldid 1181392771, wikipedia, wiki, book, books, library,

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