Perchloric acid

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{acid, form, water}

-17 C (azeotrope)[1]
-112 °C (anhydrous)

203 C (azeotrope)[2]

Perchloric acid is the inorganic compound with the formula HClO4. Usually encountered as an aqueous solution, this colourless compound is a strong acid comparable in strength to sulfuric and nitric acids, as well as a powerful oxidizing agent. It is useful for preparing perchlorate salts, especially ammonium perchlorate, an important rocket fuel. Perchloric acid is also dangerously corrosive and readily forms explosive mixtures.

Contents

Production

Perchloric acid is produced industrially by two routes. The traditional method exploits the very high aqueous solubility of sodium perchlorate (209 g/100 mL of water at room temperature). Treatment of such solutions with hydrochloric acid gives perchloric acid, precipitating solid sodium chloride:

The concentrated acid can be purified by distillation. The alternative route, which is more direct and involves no salts, entails anodic oxidation of aqueous chlorine at a platinum electrode.[4]

Laboratory preparations

Treatment of barium perchlorate with sulfuric acid precipitates barium sulfate, leaving perchloric acid. It also can be made by mixing nitric acid with ammonium perchlorate. The reaction gives nitrous oxide and perchloric acid due to a concurrent reaction involving the ammonium ion.

Properties

Anhydrous perchloric acid is an oily liquid at room temperature. It forms at least five hydrates, several of which have been characterized crystallographically. These solids consist of the perchlorate anion linked via hydrogen bonds to H2O and H3O+ centers[5] Perchloric acid forms an azeotrope with water, consisting of about 72.5% perchloric acid. This form of the acid is stable indefinitely and is commercially available. Such solutions are hygroscopic. Thus, if left open to the air, concentrated perchloric acid dilutes itself by absorbing water from the air.

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