Purple acid

Purple acid

Names
Other names Blue acid Nitrogen oxide nitrosyl hydrogen sulfate Sulphonitronic acid Sulfonitronic acid Violet acid
Properties
Chemical formula	N2O2HSO4
Molar mass	157.08 g/mol
Appearance	Purple, dark blue or indigo solution
Melting point	Decomposes
Boiling point	Decomposes
Solubility in water	Reacts
Solubility	Reacts with organic solvents
Hazards
Safety data sheet	None
Flash point	Non-flammable
Related compounds
Related compounds	Nitrosylsulfuric acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Sulfonitronic acid, blue acid or more commonly purple acid, is an unstable inorganic compound, which yields a purple solution in sulfuric acid, hence its name. It has not been isolated in the pure state and is only known in solution.

The compound has been poorly characterized in literature. Most old sources regard it as a derivative of quadrivalent nitrogen, like nitrosylsulfuric acid (NOHSO₄) or peroxylaminic acid (NO(SO₂.OH)₂). However, its exact formula and even the composition have been debated for a long time. According to more recent investigations it appears that the " acid" is either an oxide of nitrogen intermediate between NO and N₂O₃, or a compound of sulfuric acid with such an oxide. On account of this uncertainty the compound is frequently referred to merely as "purple acid" (also "blue acid " and "violet acid"). It should be kept in mind, that because the compound is very unstable and has only been made in solution (which thwarts attempts at simple analytical determination), many of the older theories about its structure were only reasoned from sometimes contradictory evidence and othertimes purely from analogy with known compounds based on their color.

The current (since the 1950s) consensus in the literature is that the purple acid is the salt of the cation N₂O₂⁺. The argument is based on the following:

• The idea of a molecular compound like some sulfonic acid in the spirit of Frémys salt is incompatible with the observations that reduction of NOClO₄ in 80% HClO₄ with Hg produces the same color.
• The idea of a simple adduct of NO and H₂SO₄ has been attractive, because pressing NO into H₂SO₄ can form the purple compound, however, on closer inspection it turns out that NO can be oxidized fairly easily in such a solution, producing NOHSO₄. It seems that NOHSO₄ is essential for the formation.
• Similarly adducts of NO with strong Lewis acids are known, such as with HCl, BF₃ and SO₃.
• Raman studies of N₂O₃⁺ are in agreement with the proposed bonding.
• Similar compounds have been obtained by pressing NO into NOAlCl₄ and NOSbCl₆ in liquid SO₂ (N₂O₂AlCl₄ can also be made in NOCl as solvent at high pressures), and both show the characteristic thermochromism of purple acid.

Properties

Chemical

Purple solution is unstable and decomposes slowly, with formation of sulfuric acid, sulfur dioxide and nitrogen dioxide. When shaken with air or submitted to oxidation by chlorine, nitric acid or hydrogen peroxide, conversion into nitrosylsulfuric acid is effected, brown fumes being liberated.

Dilution with water also destroys the colored compound. If strongly cooled, the solution changes to an intense red, so that if a solution is too weak to possess a marked color at the ordinary temperature, the presence of the "purple acid" can easily be detected by cooling in a mixture of acetone and dry ice.

Some metal ions cause the solution to have a stronger color than it would have in their absence, and in some cases increase the stability. In the older texts this was interpreted as formation of salts of purple acid. A deep blue solution of the "copper salt" for example may be obtained by the reduction of nitrosylsulfuric acid in sulphuric acid by mercury in the presence of copper. It has been suggested that the color in the "brown ring" test for a nitrate is due to the formation of the ferrous salt of "purple acid," but this is improbable.

The idea of salt formation is incompatible with the modern notion of purple acid as the cationic species N₂O₂⁺. The deep blue color of the "copper salt" has instead be interpreted as a complex like CuSO₄ · NO or [CuNO]²⁺. The optical spectra of these copper(II)-nitrogen monoxide complexes is very different from the spectrum of free purple acid, and the similarity in color seems to be coincidental. Therefore, when copper(II) is added to purple acid, the solution seems to serve purely as a donor of NO.

Physical

Purple acid is a blue or purple liquid, only stable in sulfuric acid, hence all of its properties are derived from said solution.

Availability

Purple acid is not sold and has to be made in situ.

Preparation

Purple acid can be prepared by passing nitrogen dioxide with air into a saturated solution of sulfur dioxide in diluted sulfuric acid (1:1 by volume) at 0° C. Sulfur dioxide can be easily prepared from sodium or potassium metabisulfite, as well as sodium sulfite.

It can also be formed by the addition of sodium bisulfite to a solution of nitrosylsulfuric acid, which can be produced by dissolving sodium nitrite in slightly diluted sulfuric acid. These methods depend on the reduction of the nitrosylsulfuric acid by sulfurous acid or sulfur dioxide. The reduction can also be effected by metals, e.g. mercury.

Projects

• Chemical demonstrations

Handling

Safety

Purple acid is corrosive and unstable.

Storage

Cannot be stored for long. It is only stable in sulfuric acid for a few days under the best conditions.

Disposal

Purple acid can be safely neutralized by diluting it with water and neutralize the resulting acidic solution with a base.

References

Relevant Sciencemadness threads

• Purple acid, N2O2HSO4