Aluminium perchlorate
Aluminium perchlorate
Names
Other names
  • Aluminium triperchlorate
Identifiers
  • 14452-39-2 checkY
  • nonahydrate: 81029-06-3
3D model (JSmol)
  • Interactive image
  • nonahydrate: Interactive image
ChemSpider
  • 140453
  • nonahydrate: 17339508
ECHA InfoCard 100.034.927
EC Number
  • 238-437-6
  • 159740
  • nonahydrate: 16211522
UNII
  • MTO74513XK
  • DTXSID60890742
  • Key: ZRGUXTGDSGGHLR-UHFFFAOYSA-K
  • InChI=1S/Al.3ClHO4/c;3*2-1(3,4)5/h;3*(H,2,3,4,5)/q+3;;;/p-3
  • nonahydrate: InChI=1S/Al.3ClHO4.9H2O/c;3*2-1(3,4)5;;;;;;;;;/h;3*(H,2,3,4,5);9*1H2/q+3;;;;;;;;;;;;/p-3
    Key: CYRDFMGMNQJULY-UHFFFAOYSA-K
  • [O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[Al+3]
  • nonahydrate: [O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[Al+3].O.O.O.O.O.O.O.O.O
Properties
Al(ClO4)3
Molar mass 325.33 g/mol (anhydrous)
487.46 g/mol (nonahydrate)
Appearance White solid
Density 2.30 g/cm3 (anhydrous)[1]
1.86 g/cm3 (nonahydrate)[2]
Melting point 82 °C (180 °F; 355 K)[3] (nonahydrate, decomposition)
nonahydrate
180.4 g/100 mL (0 °C)
209.6 g/100 mL (25 °C)[3][4]
Solubility Soluble in ethanol, insoluble in chloroform and dichloromethane[3][5]
Structure[2]
Trigonal
R3c
a = 10.12 Å
α = 106.7°, β = 106.7°, γ = 106.7°
869.5 Å3
Thermochemistry
–571.1 kJ/mol[6]
Hazards
GHS labelling:
GHS03: OxidizingGHS05: Corrosive
Danger
H272, H314
P210, P220, P260, P264, P280, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P321, P363, P370+P378, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazard OX: Oxidizer. E.g. potassium perchlorate
3
0
0
OX
Related compounds
Other anions
 Aluminium nitrate
Other cations
 Gallium perchlorate
Indium perchlorate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Chemical compound

Aluminium perchlorate is an inorganic chemical compound of aluminium with the formula Al(ClO4)3·nH2O, where n can range from 0 to 9. It is most commonly found as the nonahydrate Al(ClO4)3·9H2O, but other hydrates, such as the trihydrate, have also been reported. All forms of aluminium perchlorate are hygroscopic white solids that are soluble in water.

Preparation

The nonahydrate is produced by the dissolution of aluminium hydroxide in aqueous perchloric acid, followed by the evaporation of the solution:[2]

Al(OH)3 + 3 HClO4 → Al(ClO4)3 + 3 H2O

The dehydration of the nonahydrate by heating at 82 °C produces a basic perchlorate. However, heating at 80 °C under vacuum produces the trihydrate. Further heating of the trihydrate does not form the anhydrous form; instead, it decomposes to aluminium oxide.[1][7][3][8][9]

Anhydrous aluminium perchlorate is produced by the reaction of aluminium chloride and dichlorine hexoxide at –20 °C:[10][11]

8 Cl2O6 + 2 AlCl3 → 2 ClO2Al(ClO4)4 + 6 ClO2 + 3 Cl2

The resulting ClO2Al(ClO4)4 is then heated to 90 °C under vacuum to yield anhydrous aluminium perchlorate.[11]

Structure

The nonahydrate, structurally [Al(H2O)6](ClO4)3(H2O)3, has a trigonal crystal structure and consists of octahederal [Al(H2O)6]3+ centers as well as perchlorate and three molecules of water of crystallization.[2]

The anhydrous form, on the other hand, consists of bidentate perchlorate ligands with a hexagonal crystal lattice.[1]

Reactions and complexes

Aluminium perchlorate dissolves in water to form discrete [Al(H2O)6]3+ and ClO4– ions. The [Al(H2O)6]3+ partially hydrolyses, similar to the hexaaquoiron(III) ion:[12]

[Al(H2O)6]3+ ⇌ [Al(H2O)5OH]2+ + H+

This can be suppressed by the addition of perchloric acid. Like other aqueous Al3+ solutions, the addition of base, such as ammonium hydroxide or sodium hydroxide results in the precipitation of aluminium hydroxide; when base is further added, the precipitate redissolves to form [Al(OH)4]–.[12][13][14]

The hydrates, the tri- and nonahydrate, are soluble in various organic solvents and are used to prepare multiple complexes with organic ligands, such as pyridine, dimethylacetamide, dimethyl sulfoxide, and acetonitrile. Specifically, the dimethyl sulfoxide complex, [Al(DMSO)6](ClO4)3 is explosive. Other aluminium perchlorate complexes tetraperchloratoaluminate and hexaperchloratoaluminate are also known.[5][15][16][17][18]

Anhydrous aluminium perchlorate decomposes when heated to 160 °C to Al2O(ClO4)4:[1]

4 Al(ClO4)3 → 2 Al2O(ClO4)4 + 2 Cl2 + 7 O2

The oxyperchlorate decomposes to aluminium oxide if further heated to 450 °C.[1]

See also

References

  1. ^ a b c d e Nikitina, Z. K.; Karelin, A. I.; Rosolovskii, V. Ya. (1973). "Vibrational spectra and certain properties of anhydrous aluminum perchlorate". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 22 (5): 937–939. doi:10.1007/BF00854226. ISSN 0568-5230.
  2. ^ a b c d Davidian, A. G.; Pestova, O. N.; Starova, G. L.; Gurzhii, V. V.; Myund, L. A.; Khripun, M. K. (2012). "X-ray diffraction study of isomorphous crystal nonahydrates of aluminum, gallium, and scandium perchlorates". Russian Journal of General Chemistry. 82 (4): 621–625. doi:10.1134/S1070363212040019. ISSN 1070-3632.
  3. ^ a b c d Haynes, W. M., ed. (2016). CRC Handbook of Chemistry and Physics (96th ed.). Boca Raton, Florida: CRC Press/Taylor & Francis. ISBN 978-1482260960.
  4. ^ Pestova, O. N.; David’yan, A. G.; Myund, L. A.; Khripun, M. K. (2011). "Solubility of aluminum, gallium, and indium perchlorates in water". Russian Journal of General Chemistry. 81 (8): 1583–1587. doi:10.1134/S1070363211080020. ISSN 1070-3632.
  5. ^ a b Nikitina, Z. K.; Rosolovskii, V. Ya. (1980). "Solvation, solvolysis, and complexing of anhydrous aluminum perchlorate in anhydrous media". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 29 (6): 849–852. doi:10.1007/BF00958792. ISSN 0568-5230.
  6. ^ Krivtsov, N. V.; Nikitina, Z. K.; Rosolovskii, V. Ya. (1973). "Enthalpy of formation of anhydrous aluminum perchlorate". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 22 (11): 2560–2561. doi:10.1007/BF00926423. ISSN 0568-5230.
  7. ^ Gmelin's "Handbuch der anorganischen Chimie," 8th ed., no. 35, Part B, 1934, p. 217
  8. ^ Hackenberg, E. G.; Ulich, H. (1939). "Über wasserfreies Aluminiumperchlorat". Zeitschrift für anorganische und allgemeine Chemie. 243 (1): 99–109. Bibcode:1939ZAACh.243...99H. doi:10.1002/zaac.19392430109. ISSN 0863-1786.
  9. ^ Marvin, George G.; Woolaver, Lawrence B. (1945). "Thermal Decomposition of Perchlorates". Industrial & Engineering Chemistry Analytical Edition. 17 (8): 474–476. doi:10.1021/i560144a004. ISSN 0096-4484.
  10. ^ Pascal, Jean-Louis; Favier, Frédéric (1998). "Inorganic perchlorato complexes". Coordination Chemistry Reviews. 178–180 (1): 865–902. doi:10.1016/S0010-8545(98)00102-7.
  11. ^ a b Nikitina, Z. K.; Karelin, A. I.; Rosolovskii, V. Ya. (1973). "The reaction of chlorine hexaoxide with aluminum chloride". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 22 (4): 705–709. doi:10.1007/BF00857033. ISSN 0568-5230.
  12. ^ a b David’yan, A. G.; Kudrev, A. G.; Myund, L. A.; Khripun, M. K. (2013). "Structure of aqueous solutions of group IIIA metals perchlorates by near infrared spectroscopy". Russian Journal of General Chemistry. 83 (3): 415–422. doi:10.1134/S107036321303002X. ISSN 1070-3632.
  13. ^ Pacewska, Barbara; Kluk-Płoskońska, Olga; Szychowski, D. (2006). "Influence of aluminium precursor on physico-chemical properties of aluminium hydroxides and oxides Part II. Al(ClO4)3·9H2O". Journal of Thermal Analysis and Calorimetry. 86 (3): 751–760. doi:10.1007/s10973-005-7377-1. ISSN 1388-6150.
  14. ^ Housecroft, Catherine E.; Sharpe, Alan G. (2018). Inorganic Chemistry (5th ed.). Harlow, England ; New York: Pearson Higher Education. p. 415. ISBN 978-1-292-13414-7.
  15. ^ Górska, Natalia; Mikuli, Edward (2016). "Fourier transform infrared spectroscopy and differential scanning calorimetry studies of the phase transitions and molecular motions in polycrystalline [Al(DMSO)6](ClO4)3 and [Al(DMSO)6](BF4)3". Vibrational Spectroscopy. 86: 253–261. doi:10.1016/j.vibspec.2016.07.014.
  16. ^ Nikitina, Z. K.; Rosolovskii, V. Ya. (1978). "Ammonium perchloratoaluminates". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 27 (3): 449–452. doi:10.1007/BF00923912. ISSN 0568-5230.
  17. ^ Franz, G. (1963). "Synthesis of anhydrous aluminium perchlorates". Journal of Inorganic and Nuclear Chemistry. 25 (6): 737–739. doi:10.1016/0022-1902(63)80171-2.
  18. ^ Suzuki, Honoh; Ishiguro, Shin-ichi (2006). "N,N-Dimethylacetamide complex of aluminium(III) perchlorate". Acta Crystallographica Section E. 62 (3): 576–578. Bibcode:2006AcCrE..62M.576S. doi:10.1107/S1600536806005575. ISSN 1600-5368.
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