Sodium dithionate Na₂S₂O₆ is an important compound for inorganic chemistry. It is also known under names disodium dithionate, sodium hyposulfate, and sodium metabisulfate. The sulfur can be considered to be in its +5

oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...

. It should not be confused with

sodium dithionite Sodium dithionite (also known as sodium hydrosulfite) is a white crystalline powder with a sulfurous odor. Although it is stable in dry air, it decomposes in hot water and in acid solutions. Structure The structure has been examined by Raman s ...

, Na₂S₂O₄, which is a very different compound, and is a powerful reducing agent with many uses in chemistry and biochemistry. Confusion between dithionate and dithionite is commonly encountered, even in manufacturers' catalogues.

Preparation

Sodium dithionate is produced by the oxidation of

sodium bisulfite Sodium bisulfite (or sodium bisulphite, sodium hydrogen sulfite) is a chemical mixture with the approximate chemical formula NaHSO3. Sodium bisulfite in fact is not a real compound, but a mixture of salts that dissolve in water to give solutions ...

by manganese dioxide: :2 NaHSO₃ + MnO₂ → Na₂S₂O₆ + MnO + H₂O Alternatively, it can be prepared by the oxidation of

sodium sulfite Sodium sulfite (sodium sulphite) is the inorganic compound with the chemical formula Na2 SO3. A white, water-soluble solid, it is used commercially as an antioxidant and preservative. A heptahydrate is also known but it is less useful because of ...

by the

silver Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical ...

(I) cation: : + 2 Ag + SO → + 2 Ag Another method is via oxidation of

sodium thiosulfate Sodium thiosulfate (sodium thiosulphate) is an inorganic compound with the formula . Typically it is available as the white or colorless pentahydrate, . The solid is an efflorescent (loses water readily) crystalline substance that dissolves well in ...

with

chlorine Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine i ...

: :3 Cl₂ + Na₂S₂O₃·5H₂O + 6 NaOH → Na₂S₂O₆ + 6 NaCl + 8 H₂O And another method to produce sodium dithionate is treating sodium thiosulfate with sodium hypochlorite solution.

Structure

The dithionate ion represents sulfur that is oxidized relative to elemental sulfur, but not totally oxidized. Sulfur can be reduced to sulfide or totally oxidized to sulfate, with numerous intermediate oxidation states in inorganic moieties, as well as organosulfur compounds. Example inorganic ions include sulfite and

thiosulfate Thiosulfate ( IUPAC-recommended spelling; sometimes thiosulphate in British English) is an oxyanion of sulfur with the chemical formula . Thiosulfate also refers to the compounds containing this anion, which are the salts of thiosulfuric acid, ...

. Sodium dithionate crystallize as orthorhombic crystals of the dihydrate (). The

water of crystallization In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization i ...

is lost when heated to 90 °C, and the structure becomes

hexagonal In geometry, a hexagon (from Greek , , meaning "six", and , , meaning "corner, angle") is a six-sided polygon. The total of the internal angles of any simple (non-self-intersecting) hexagon is 720°. Regular hexagon A '' regular hexagon'' has ...

. Large single crystals of () have been grown and studied for pulsed lasing purposes (pico second spectroscopy) with great success by E. Haussühl and cols.

Properties

Sodium dithionate is a very stable compound which is not oxidized by permanganate, dichromate or bromine. It can be oxidized to sulfate under strongly oxidizing conditions: these include boiling for one hour with 5 M sulfuric acid with an excess of potassium dichromate, or treating with an excess of hydrogen peroxide then boiling with concentrated hydrochloric acid. The

Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature and ...

change for (for example) the dithionate anion's oxidation to sulfate is a negative −300 kJ/mol, making it thermodynamically unstable against oxidation, but the kinetics for this reaction are rather poor. For similar reasons, the dithionate anion has been used to form single crystals of large cation complexes in high oxidation states, as the resulting salts are very likely highly kinetically stable(unless in extraordinary conditions that obviously do not belong to crystal analysis- see above), enough to survive all the way throughout the analysis of the crystal.

References

{{Sodium compounds Dithionates Sodium compounds