Perchloric acid is a

mineral acid A mineral acid (or inorganic acid) is an acid derived from one or more inorganic compounds, as opposed to organic acids which are acidic, organic compounds. All mineral acids form hydrogen ions and the conjugate base when dissolved in water. Cha ...

with the formula H Cl O₄. Usually found as an aqueous solution, this colorless compound is a stronger acid than

sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...

nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitri ...

and

hydrochloric acid Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid Acid strength is the tendency of an acid, symbol ...

. It is a powerful

oxidizer An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or " accepts"/"receives" an electron from a (called the , , or ). In other words, an oxid ...

when hot, but

aqueous solution An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, or sodium chloride (NaCl), in water would be re ...

s up to approximately 70% by weight at room temperature are generally safe, only showing strong acid features and no oxidizing properties. Perchloric acid is useful for preparing

perchlorate A perchlorate is a chemical compound containing the perchlorate ion, . The majority of perchlorates are commercially produced salts. They are mainly used as oxidizers for pyrotechnic devices and to control static electricity in food packaging. Per ...

salts, especially

ammonium perchlorate Ammonium perchlorate ("AP") is an inorganic compound with the formula NH4 ClO4. It is a colorless or white solid that is soluble in water. It is a powerful oxidizer. Combined with a fuel, it can be used as a rocket propellant called ammonium pe ...

, an important

rocket fuel Rocket propellant is the reaction mass of a rocket. This reaction mass is ejected at the highest achievable velocity from a rocket engine to produce thrust. The energy required can either come from the propellants themselves, as with a chemical ...

component. Perchloric acid is dangerously corrosive and readily forms potentially explosive mixtures.

History

Perchloric acid was first synthesized (together with potassium perchlorate) by Austrian chemist and called "oxygenated chloric acid" in mid-1810s; French pharmacist

Georges-Simon Serullas Georges-Simon Serullas (2 November 1774 in Poncin – 25 May 1832 in Paris) was a professor of pharmacy notable for being the first to publish a work on Iodoform, an early antiseptic and disinfectant. Biography He was a professor and head pharm ...

introduced the modern designation along with discovering its solid monohydrate (which he, however, mistook for an anhydride).

Production

Perchloric acid is produced industrially by two routes. The traditional method exploits the high aqueous solubility of

sodium perchlorate Sodium perchlorate is the inorganic compound with the chemical formula Na ClO4. It is a white crystalline, hygroscopic solid that is highly soluble in water and in alcohol. It is usually encountered as the monohydrate. The compound is noteworthy ...

(209 g/100 mL of water at room temperature). Treatment of such solutions with

gives perchloric acid, precipitating solid sodium chloride: :NaClO₄ + HCl → NaCl + HClO₄ The concentrated acid can be purified by

distillation Distillation, or classical distillation, is the process of separation process, separating the components or substances from a liquid mixture by using selective boiling and condensation, usually inside an apparatus known as a still. Dry distilla ...

. The alternative route, which is more direct and avoids salts, entails anodic oxidation of aqueous chlorine at a platinum electrode.Helmut Vogt, Jan Balej, John E. Bennett, Peter Wintzer, Saeed Akbar Sheikh, Patrizio Gallone "Chlorine Oxides and Chlorine Oxygen Acids" in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. .

Laboratory preparations

Treatment of

barium perchlorate Barium perchlorate is a powerful oxidizing agent, with the formula Ba(ClO4)2. It is used in the pyrotechnic industry. Barium perchlorate decomposes at 505 °C. Structure of barium perchlorate trihydrate Gallucci and Gerkin (1988) analyze ...

with

precipitates

barium sulfate Barium sulfate (or sulphate) is the inorganic compound with the chemical formula Ba SO4. It is a white crystalline solid that is odorless and insoluble in water. It occurs as the mineral barite, which is the main commercial source of barium an ...

, leaving perchloric acid. It can also be made by mixing

with

and boiling while adding hydrochloric acid. The reaction gives

nitrous oxide Nitrous oxide (dinitrogen oxide or dinitrogen monoxide), commonly known as laughing gas, nitrous, or nos, is a chemical compound, an oxide of nitrogen with the formula . At room temperature, it is a colourless non-flammable gas, and has a ...

and perchloric acid due to a concurrent reaction involving the

ammonium The ammonium cation is a positively-charged polyatomic ion with the chemical formula or . It is formed by the protonation of ammonia (). Ammonium is also a general name for positively charged or protonated substituted amines and quaternary a ...

ion and can be concentrated and purified significantly by boiling off the remaining nitric and hydrochloric acids.

Properties

Anhydrous perchloric acid is an unstable oily liquid at room temperature. It forms at least five

hydrates In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...

, several of which have been characterized crystallographically. These solids consist of the

anion linked via

hydrogen bond In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing a ...

s to H₂O and H₃O⁺ centers. An example is

hydronium perchlorate Hydronium perchlorate is the chemical compound with the formula . It is an unusual salt due to it being a solid and stable hydronium salt. Production Hydronium perchlorate is produced by the reaction of anhydrous perchloric acid and water in a 1: ...

. Perchloric acid forms an

azeotrope An azeotrope () or a constant heating point mixture is a mixture of two or more liquids whose proportions cannot be altered or changed by simple distillation.Moore, Walter J. ''Physical Chemistry'', 3rd e Prentice-Hall 1962, pp. 140–142 This ...

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 Hygroscopy is the phenomenon of attracting and holding water molecules via either absorption or adsorption from the surrounding environment, which is usually at normal or room temperature. If water molecules become suspended among the substance ...

. Thus, if left open to the air, concentrated perchloric acid dilutes itself by absorbing water from the air. Dehydration of perchloric acid gives the anhydride

dichlorine heptoxide Dichlorine heptoxide is the chemical compound with the formula Cl2O7. This chlorine oxide is the anhydride of perchloric acid. It is produced by the careful distillation of perchloric acid in the presence of the dehydrating agent phosphorus pentox ...

: :2 HClO₄ + P₄O₁₀ → Cl₂O₇ + H₂P₄O₁₁

Uses

Perchloric acid is mainly produced as a precursor to

, which is used in rocket fuel. The growth in rocketry has led to increased production of perchloric acid. Several million kilograms are produced annually. Perchloric acid is one of the most proven materials for

etching Etching is traditionally the process of using strong acid or mordant to cut into the unprotected parts of a metal surface to create a design in intaglio (incised) in the metal. In modern manufacturing, other chemicals may be used on other types ...

liquid crystal displays A liquid-crystal display (LCD) is a flat-panel display or other electronically modulated optical device that uses the light-modulating properties of liquid crystals combined with polarizers. Liquid crystals do not emit light directly but i ...

and critical electronics applications as well as ore extraction and has unique properties in analytical chemistry. Additionally it is a useful component in etching of chrome.

As an acid

Perchloric acid, a

superacid In chemistry, a superacid (according to the classical definition) is an acid with an acidity greater than that of 100% pure sulfuric acid (), which has a Hammett acidity function (''H''0) of −12. According to the modern definition, a superacid ...

, is one of the strongest Brønsted–Lowry acids. That its p''K''_a is lower than −9 is evidenced by the fact that its monohydrate contains discrete

hydronium ions In chemistry, hydronium (hydroxonium in traditional British English) is the common name for the aqueous cation , the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is ...

and can be isolated as a stable, crystalline solid, formulated as ₃O⁺]. The most recent estimate of its aqueous p''K''_a is . It provides strong acidity with minimal interference because perchlorate is weakly nucleophile, nucleophilic (explaining the high acidity of HClO₄). Other acids of

noncoordinating anion Anions that interact weakly with cations are termed non-coordinating anions, although a more accurate term is weakly coordinating anion. Non-coordinating anions are useful in studying the reactivity of electrophilic cations. They are commonly found ...

s, such as

fluoroboric acid Fluoroboric acid or tetrafluoroboric acid (archaically, fluoboric acid) is an inorganic compound with the chemical formula +BF4−], where H+ represents the solvated proton. The solvent can be any suitably Lewis-basic entity. For instance, in w ...

and

hexafluorophosphoric acid Hexafluorophosphoric acid is the inorganic compound with the chemical formula (also written ). This strong Brønsted acid features a non-coordinating anion, hexafluorophosphate (). It is formed from the reaction of hydrogen fluoride with phosp ...

are susceptible to hydrolysis, whereas perchloric acid is not. Despite hazards associated with the explosiveness of its salts, the acid is often preferred in certain syntheses. For similar reasons, it is a useful

eluent In analytical and organic chemistry, elution is the process of extracting one material from another by washing with a solvent; as in washing of loaded ion-exchange resins to remove captured ions. In a liquid chromatography experiment, for exa ...

in ion-exchange chromatography. It is also used for

electropolishing Electropolishing, also known as electrochemical polishing, anodic polishing, or electrolytic polishing (especially in the metallography field), is an electrochemical process that removes material from a metallic workpiece, reducing the surface roug ...

or etching of aluminium, molybdenum, and other metals.

Safety

Given its strong

oxidizing Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...

properties, perchloric acid is subject to extensive regulations as it can react violently with metals and flammable substances such as wood, plastics, and oils. Work conducted with perchloric acid must be conducted in fume hoods with a wash-down capability to prevent accumulation of oxidisers in the ductwork. On February 20, 1947 in Los Angeles, California, 17 people were killed and 150 injured in the

O'Connor Plating Works disaster On 20 February 1947, a large accidental explosion at the O'Connor Plating Works at 926 East Pico Boulevard in Los Angeles killed seventeen people and injured more than one hundred. Eleven nearby buildings were damaged beyond repair. Press report ...

. A bath, consisting of over 1000 litres of 75% perchloric acid and 25%

acetic anhydride Acetic anhydride, or ethanoic anhydride, is the chemical compound with the formula (CH3CO)2O. Commonly abbreviated Ac2O, it is the simplest isolable anhydride of a carboxylic acid and is widely used as a reagent in organic synthesis. It is a col ...

by volume which was being used to electro-polish aluminium furniture, exploded. Organic compounds were added to the overheating bath when an iron rack was replaced with one coated with cellulose acetobutyrate ( Tenit-2 plastic). A few minutes later the bath exploded. The O'Connor Electro-Plating plant, 25 other buildings, and 40 automobiles were destroyed, and 250 nearby homes were damaged.

References

External links

International Chemical Safety Card 1006
{{Authority control * Halogen oxoacids Hydrogen compounds Mineral acids Oxidizing acids Oxidizing agents Superacids