Silicotungstic acid or tungstosilicic acid is a heteropoly acid with the chemical formula H4[SiW12O40]. It forms hydrates H4[SiW12O40nH2O. In freshly prepared samples, n is approximately 29, but after prolonged desiccation, n = 6.[1] It is a white solid although impure samples appear yellow. It is used as a catalyst in the chemical industry.[2]

Silicotungstic acid
Names
Other names
Tungstosilicic acid
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.206.333 Edit this at Wikidata
UNII
  • InChI=1S/H4O4Si.36O.12W/c1-5(2,3)4;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;/h1-4H;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;
    Key: CGFYHILWFSGVJS-UHFFFAOYSA-N
  • (hydrate): InChI=1S/H4O4Si.H2O.36O.12W/c1-5(2,3)4;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;/h1-4H;1H2;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;
    Key: ACTPFSYIGLFGLY-UHFFFAOYSA-N
  • (anhydrous): [W]18!$(O[W]#(O[W]56(O1)(O[W]247(O[W]9"(O[W](O2)(O[W]3(O[W](O[W](O3)(O4)(O5)([O ]67[Si] [O ]89[W](O[W](O[W](O)(O)(O)([O ])[O-])(O)(O)([O ] )[O-])(O!)(O")[O-])O)(O#)[O-])[O-])[O-])(O$)O)[O-])O)[O-])O
Properties
H4[SiW12O40]
Molar mass 2878.2 g/mol
Appearance White solid
Melting point 53 °C (127 °F; 326 K)
Structure
0 D
Hazards
GHS labelling:
GHS05: CorrosiveGHS07: Exclamation mark
Danger
H314, H315, H319, H335, H412
P260, P261, P264, P271, P273, P280, P301 P330 P331, P302 P352, P303 P361 P353, P304 P340, P305 P351 P338, P310, P312, P321, P332 P313, P337 P313, P362, P363, P403 P233, P405, P501
Flash point Non-flammable
Related compounds
Phosphotungstic acid
Related compounds
Tungsten trioxide
Tungstic 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 checkY☒N ?)

Applications

edit

Silicotungstic acid is used to manufacture ethyl acetate by the alkylation of acetic acid by ethylene:

C2H4 CH3CO2H → CH3CO2C2H5

It has also been commercialized for the oxidation of ethylene to acetic acid:[2]

C2H4 O2 → CH3CO2H

This route is claimed as a "greener" than methanol carbonylation. The heteropoly acid is dispersed on silica gel at 20-30 wt% to maximize catalytic ability.

It has also recently been proposed as a mediator in production of hydrogen through electrolysis of water by a process that would reduce the danger of explosion while allowing efficient hydrogen production at low current densities, conducive to hydrogen production using renewable energy.[3]

Synthesis and structure

edit

The free acid is produced by combining sodium silicate and tungsten trioxide followed treatment of the mixture with hydrochloric acid.[1][4] The polyoxo cluster adopts a Keggin structure, with Td point group symmetry.

Hazards

edit

Silicotungstic acid is an irritating and odorless substance.

References

edit
  1. ^ a b Dias, J. A.; Dias, S. C. L.; Caliman, E. (2014). "Keggin Structure Polyoxometalates". Keggin Structure Polyoxoometalates. Inorganic Syntheses. Vol. 36. p. 210-217. doi:10.1002/9781118744994.ch39. ISBN 9781118744994.
  2. ^ a b Misono, Makoto (2009). "Recent progress in the practical applications of heteropolyacid and perovskite catalysts: Catalytic technology for the sustainable society". Catalysis Today. 144 (3–4): 285–291. doi:10.1016/j.cattod.2008.10.054.
  3. ^ Rausch, Benjamin; Symes, Mark D.; Chisholm, Greig; Cronin, Leroy (September 12, 2014). "Decoupled catalytic hydrogen evolution from a molecular metal oxide redox mediator in water splitting". Science. 345 (6202). American Association for the Advancement of Science: 1326–1330. Bibcode:2014Sci...345.1326R. doi:10.1126/science.1257443. PMID 25214625. S2CID 20572410.
  4. ^ Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY.