Chromium(III) sulfate

Chromium(III) sulfate usually refers to the inorganic compounds with the formula Cr2(SO4)3.x(H2O), where x can range from 0 to 18. Additionally, ill-defined but commercially important "basic chromium sulfates" are known. These salts are usually either violet or green solids that are soluble in water. It is commonly used in tanning leather.

Chromium(III) sulfate
Names
IUPAC name
Chromium(III) sulfate
Other names
Basic chromium sulfate, chromic sulfate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.030.217
EC Number
  • 233-253-2
UNII
UN number 2240 3077
  • InChI=1S/2Cr.3H2O4S.12H2O/c;;3*1-5(2,3)4;;;;;;;;;;;;/h;;3*(H2,1,2,3,4);12*1H2/q2*+3;;;;;;;;;;;;;;;/p-6 ☒N
    Key: ANNXSSGQVXBUEI-UHFFFAOYSA-H ☒N
  • InChI=1/2Cr.3H2O4S.12H2O/c;;3*1-5(2,3)4;;;;;;;;;;;;/h;;3*(H2,1,2,3,4);12*1H2/q2*+3;;;;;;;;;;;;;;;/p-6
    Key: ANNXSSGQVXBUEI-CYFPFDDLAL
  • [Cr+3].[Cr+3].[O-]S(=O)(=O)[O-].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.O.O.O.O.O.O.O.O.O.O.O.O
Properties
Cr2(SO4)3 • 12H2O
Molar mass 392.16 g/mol
608.363 g/mol (dodecahydrate)

716.45 g/mol (octadecahydrate)

Appearance reddish-brown crystals (anhydrous), purple crystals (hydrated)
Density 3.10 g/cm3 (anhydrous)
1.86 g/cm3 (pentadecahydrate)
1.709 g/cm3 (octadecahydrate)
Melting point 90 °C
Boiling point >700 °C (decomposes to chromic acid)
insoluble (anhydrous)
soluble (hydrated)
Solubility soluble in alcohol
practically insoluble in acid
+11,800·10−6 cm3/mol
Hazards
GHS labelling:
GHS05: CorrosiveGHS07: Exclamation markGHS08: Health hazardGHS09: Environmental hazard
Warning
H314, H317, H332, H334, H335, H340, H350, H373, H412
P201, P202, P260, P261, P264, P271, P272, P273, P280, P281, P285, P301+P330+P331, P302+P352, P303+P361+P353, P304+P312, P304+P340, P304+P341, P305+P351+P338, P308+P313, P310, P312, P314, P321, P333+P313, P342+P311, P363, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
1
0
0
Flash point Non-flammable
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 1 mg/m3[1]
REL (Recommended)
 TWA 0.5 mg/m3[1]
IDLH (Immediate danger)
 250 mg/m3[1]
Safety data sheet (SDS) MSDS
Related compounds
Other cations
 Aluminium sulfate
Related double salts
 Chrome alum
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Chromium(III) sulfates

Three chromium(III) sulfates are well characterized:

  • Anhydrous chromium(III) sulfate, Cr2(SO4)3, (CAS #10101-53-8) is a violet solid that dissolves in water upon addition of a reducing agent, which generates chromium(II) sulfates.
  • Hydrated chromium(III) sulfate, Cr2(SO4)3·18H2O, (CAS #13520-66-6) is a violet solid that readily dissolves in water to give the metal aquo complex, [Cr(H2O)6]3+. The formula of this compound can be written more descriptively as [Cr(H2O)6]2(SO4)3·6H2O. Six of the eighteen water molecules in this formula unit are water of crystallization.
  • Hydrated chromium(III) sulfate, Cr2(SO4)3·15(H2O), (CAS #10031-37-5) is a green solid that also readily dissolves in water. It is obtained by heating the 18-hydrate material above 70 °C. Further heating yields the anhydrous sulfate.

A variety of other chromium(III) sulfates are known, but also contain hydroxide or oxide ligands. Most important commercially is basic chromium sulfate, which is thought to be [Cr2(H2O)6(OH)4]SO4 (CAS#39380-78-4).[2] It results from the partial neutralization of the hexahydrates. Other chromium(III) hydroxides have been reported.[3]

Structure of Cr(SO4)(H2O)(OH), showing the CrO6 coordination sphere typical of many chromium(III) compounds.

Production

The most useful source of chromium(III) sulfate are the Cr(III) wastes from the chromate oxidation of various organic compounds. Anthroquinone and quinone are produced on large scale by treatment of anthracene and phenol with chromic acid. A chromium(III) oxide coproduct is generated which is readily extracted into sulfuric acid. Evaporation of these acidic solutions affords the hydrate salt described above. The hydrated salts of chromium sulfate can also be produced, albeit impure, by extraction of various other chromium compounds, but these routes are not economically viable.. Extraction of chromite ore with sulfuric acid in the presence of some chromate gives solutions of chromium(III) sulfate contaminated with other metal ions. Similarly, dissolution of chrome alloys gives chromium sulfate together with ferrous sulfate.

Basic chromium(III) sulfate

Basic chromium sulfate is produced from chromate salts by reduction with sulfur dioxide, although other methods exist.[4][5] The reduction could formally be written:

Na2Cr2O7 + 3 SO2 + H2O → Cr2(SO4)3 + 2 NaOH

Since 33% of the anion charges are due to hydroxy ions the basicity is 33% (but in tanning jargon it is known as 33% reduced). Products with higher basicities, e.g. 42% or 50% may be obtained by the addition of sodium carbonate, these are often used in combination with sodium formate. The sodium sulfate is often left in the technical product since it is inert with respect to the tanning process. It is important to fully reduce the hexavalent chromium to trivalent since the hexavalent is more likely to cause health problems for tanners and leather consumers.

Natural occurrence

Pure chromium(III) sulfate, both in anhydrous and hydrous form, is as yet (2020) unknown among mineral species. There are 3 complex minerals being, in part, Cr(III) sulfates: bentorite, reddingtonite, and putnisite.[6][7][8][9]

References
  1. NIOSH Pocket Guide to Chemical Hazards. "#0141". National Institute for Occupational Safety and Health (NIOSH).
  2. Covington, A. D.; Lampard, G. S.; Menderes, O.; Chadwick, A. V.; Rafeletos, G.; O'Brien, P. "Extended X-ray absorption fine structure studies of the role of chromium in leather tanning" Polyhedron 2001, volume 20, 461–466. doi:10.1016/S0277-5387(00)00611-2
  3. Riou, A.; Bonnin, A. (1982). "Structure de l'Hydroxysulfate de Chrome monohydrate". Acta Crystallographica B. 24 (5): 1968–38. doi:10.1107/S0567740881005001.
  4. Gerd Anger, Jost Halstenberg, Klaus Hochgeschwender, Christoph Scherhag, Ulrich Korallus, Herbert Knopf, Peter Schmidt, Manfred Ohlinger. "Chromium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a07_067.{{cite encyclopedia}}: CS1 maint: multiple names: authors list (link)
  5. CW Harland; J Simpson. "Chromium sulfate tanning powder" (PDF). Farmers Fertiliser Ltd - a subsidiary of Fernz Corporation Ltd.
  6. "Bentorite".
  7. "Redingtonite".
  8. "Putnisite".
  9. "List of Minerals". 21 March 2011.
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