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Dichromate

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Dichromate

This article is about chromium(VI) cation. For chromium(III) cation, see chromite (compound).

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Chromate salts contain the chromate anion, CrO42−. Dichromate salts contain the dichromate anion, Cr2O72−. They are oxoanions of chromium in the oxidation state +6. They are moderately strong oxidizing agents.

Chemical properties

Chromates react with hydrogen peroxide giving products in which peroxide, O22−, replaces one or more oxygen atoms. In acid solution the unstable blue peroxo complex Chromium(VI) oxide peroxide, CrO(O2)2, is formed; it is an uncharged covalent molecule which may be extracted into ether. Addition of pyridine results in the formation of the more stable complex CrO(O2)2py.[1]

Acid-base properties



In aqueous solution, chromate and dichromate anions exist in a chemical equilibrium.

2 CrO42− + 2 H+ is in equilibrium with Cr2O72− + H2O

The illustrated

Further condensation reactions can occur in strongly acidic solution with the formation of trichromates, Cr3O102−, and tetrachromates, Cr4O132−. All polyoxyanions of chromium(VI) have structures made up of tetrahedral CrO4 units sharing corners.[2]

The chromate ion is a weak acid.

HCrO4 is in equilibrium with CrO42− + H+; pKa = ca. 5.9

The hydrogen chromate ion, HCrO4-, is also in equilibrium with the dichromate ion.

2HCrO4 is in equilibrium with Cr2O72− + H2O

This equilibrium does not involve a change in hydrogen ion concentration, so should be independent of pH. The red line on the predominance diagram is not quite horizontal due to the simultaneous equilibrium with the chromate ion. The hydrogenchromate ion may be protonated, with the formation of molecular chromic acid, H2CrO4,but the pKa for the equilibrium

H2CrO4 is in equilibrium with [HCrO4] + H+

is not well characterized. Reported values vary between about -0.8 to 1.6.[3]

The dichromate ion is a somewhat weaker base than the chromate ion.

[HCr2O7] is in equilibrium with [Cr2O7]2− + H+, pK = 1.8[4]

The pK value for this reaction shows that is can be ignored at pH > 4.

Oxidation-reduction properties

The chromate and dichromate ions are fairly strong oxidizing agents. Commonly three electrons are added to a chromium atom, reducing it to oxidation state +3. In acid solution the aquated Cr3+ ion is produced.

Cr2O72− + 14 H3O+ + 6 e → 2 Cr3+ + 21 H2O (ε0 = 1.33 V)

In alkaline solution chromium(III) hydroxide is produced. The redox potential shows that chromates are weaker oxidizing agent in alkaline solution than in acid solution.[5]

CrO42- + 4 Template:Chem/link + 3 e-Template:Chem/link + 5 Template:Chem/link0 = −0.13 V)

Applications

Approximately 136,000,000 kilograms (300,000,000 lb) of hexavalent chromium, mainly sodium dichromate, were produced in 1985.[7] Chromates and dichromates are used in chrome plating to protect metals from corrosion and to improve paint adhesion. Chromate and dichromate salts of heavy metals, lanthanides and alkaline earth metals are only very slightly soluble in water and are thus used as pigments. The lead containing pigment Chrome Yellow was used for a very long time before environmental regulations discouraged its use.[6] When used as oxidizing agents or titrants in a redox chemical reaction, chromates and dichromates convert into trivalent chromium, Cr3+, salts of which typically have a distinctively different blue-green color.[7]

Natural occurrence and production

The primary chromium ore is the mixed metal oxide chromite, FeCr2O4, found as brittle metallic black crystals or granules. The rare mineral crocoite, PbCrO4, occurs as spectacular long red crystals. Rare potassium chromate minerals and related compounds are found in the Atacama desert.

Chromite ore is heated with a mixture of calcium carbonate and sodium carbonate in the presence of air. The chromium is oxidized to the hexavalent form, while the iron forms iron(III) oxide, Fe2O3.

4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2Fe2O3 + 8 CO2

The subsequent leaching at higher temperatures dissolves the chromates and leaves the insoluble iron oxide. Normally the chromate solution is further processed to make chromium metal, but a chromate salt may be obtained directly from the liquor.[8]

Safety

All hexavalent chromium compounds are toxic due to their oxidizing power. They may be carcinogenic, especially when air-borne. The use of chromate compounds in manufactured goods is restricted in the EU (and by market commonality the rest of the world) by EU Parliament directive 2002/95/EC

See also

Notes

References

External links

  • National Pollutant Inventory - Chromium VI and compounds fact sheet
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