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. Ch ...

with the formula H Cl O₄. It is an

oxoacid An oxyacid, oxoacid, or ternary acid is an acid that contains oxygen. Specifically, it is a compound that contains hydrogen, oxygen, and at least one other element, with at least one hydrogen atom bonded to oxygen that can dissociate to produce ...

chlorine Chlorine is a chemical element; it has Symbol (chemistry), 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 ...

. Usually found as an

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, also known as sodium chloride (NaCl), in water ...

, this colorless compound is a stronger acid than

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

nitric acid Nitric acid is an inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into nitrogen oxide, oxides of nitrogen. Most com ...

and

hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...

. 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 ''electron donor''). In ot ...

when hot, but

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 conjugate base of perchloric acid (ionic perchlorate). As counterions, there can be metal cations, quaternary ammonium cations or other ions, for example, nitronium cat ...

salts, especially

ammonium perchlorate Ammonium perchlorate ("AP") is an inorganic compound with the formula . 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 perchlorat ...

, an important

rocket fuel Rocket propellant is used as reaction mass ejected from a rocket engine to produce thrust. The energy required can either come from the propellants themselves, as with a chemical rocket, or from an external source, as with ion engines. Overvi ...

component. Perchloric acid is dangerously

corrosive Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engine ...

and readily forms potentially

explosive An explosive (or explosive material) is a reactive substance that contains a great amount of potential energy that can produce an explosion if released suddenly, usually accompanied by the production of light, heat, sound, and pressure. An ex ...

mixtures.

History

Perchloric acid was first synthesized (together with

potassium perchlorate Potassium perchlorate is the inorganic salt with the chemical formula K Cl O4. Like other perchlorates, this salt is a strong oxidizer when the solid is heated at high temperature, although it usually reacts very slowly in solution with reducin ...

) by Austrian chemist and called "oxygenated

chloric acid Chloric acid, H Cl O3, is an oxoacid of chlorine, and the formal precursor of chlorate salts. It is a strong acid ( p''K''a ≈ −2.7) and an oxidizing agent. Properties Chloric acid is thermodynamically unstable with respect to disproportio ...

" in mid-1810s. French pharmacist Georges-Simon Serullas introduced the modern designation along with discovering its solid monohydrate, which he mistook for an

anhydride An acid anhydride is a type of chemical compound derived by the removal of water molecules from an acid (chemistry), acid. In organic chemistry, organic acid anhydrides contain the functional group . Organic acid anhydrides often form when one ...

. Berzelius produced dilute perchloric acid by electrolysis of chloric acid. In the late 1800's German and Swedish workers commercialized the electrolysis.

Production

Perchloric acid is produced industrially by two routes. The traditional method exploits the high aqueous solubility of sodium perchlorate (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, also classical distillation, is the process of separating the component substances of a liquid mixture of two or more chemically discrete substances; the separation process is realized by way of the selective boiling of the mixt ...

. The alternative route, which is more direct and avoids salts, entails anodic oxidation of aqueous chlorine at a platinum electrode.

Laboratory preparations

It can be distilled from a solution of potassium perchlorate in sulfuric acid. Treatment of barium perchlorate 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 in nature as the mineral barite, which is the main commercial source of ...

, 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 factitious air, among others, is a chemical compound, an Nitrogen oxide, oxide of nitrogen with the Chemical formula, formula . At room te ...

and perchloric acid due to a concurrent reaction involving the

ammonium Ammonium is a modified form of ammonia that has an extra hydrogen atom. It is a positively charged (cationic) polyatomic ion, molecular ion with the chemical formula or . It is formed by the protonation, addition of a proton (a hydrogen nucleu ...

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 (H-bond) is a specific type of molecular interaction that exhibits partial covalent character and cannot be described as a purely electrostatic force. It occurs when a hydrogen (H) atom, Covalent bond, covalently b ...

s to H₂O and H₃O⁺ centers. An example is hydronium perchlorate. 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 changed by simple distillation.Moore, Walter J. ''Physical Chemistry'', 3rd e Prentice-Hall 1962, pp. 140–142 This happens beca ...

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 (chemistry), absorption or adsorption from the surrounding Natural environment, environment, which is usually at normal or room temperature. If water mol ...

. 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: :2 HClO₄ + P₄O₁₀ → Cl₂O₇ + H₂P₄O₁₁

Uses

Perchloric acid is mainly produced as a precursor to

, which is used in rocket propellant. 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 type ...

liquid crystal displays A liquid-crystal display (LCD) is a flat-panel display or other Electro-optic modulator, electronically modulated optical device that uses the light-modulating properties of liquid crystals combined with polarizers to display information. Liq ...

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 original 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 i ...

, 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 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 anions, such as fluoroboric acid and hexafluorophosphoric acid 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

ion-exchange chromatography Ion chromatography (or ion-exchange chromatography) is a form of chromatography that separates ions and ionizable polar molecules based on their affinity to the ion exchanger. It works on almost any kind of Charge (chemistry), charged molecule ...

. It is also used in

electropolishing Electropolishing principle: 1. Electrolyte 2. Cathode 3. Workpiece to polish (Anode) 4. Particle moving from the work-piece to the cathode 5. Surface before polishing 6. Surface after polishing Electropolishing, also known as electrochemical poli ...

or the etching of aluminium, molybdenum, and other metals. In geochemistry, perchloric acid aids in the digestion of silicate mineral samples for analysis, and also for complete digestion of organic matter.

Safety

Given its strong

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

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. 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 chemical formula, formula . Commonly abbreviated , it is one the simplest organic acid anhydride, anhydrides of a carboxylic acid and is widely used in the production of c ...

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 Perchlorates Halogen oxoacids Mineral acids Oxidizing acids Superacids