Perchloric acid

Perchloric acid

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Perchloric acid is the inorganic compound
Inorganic compound
Inorganic compounds have traditionally been considered to be of inanimate, non-biological origin. In contrast, organic compounds have an explicit biological origin. However, over the past century, the classification of inorganic vs organic compounds has become less important to scientists,...

 with the formula HClO4. Usually encountered as an aqueous solution, this colourless compound is a strong acid
Strong acid
A strong acid is an acid that ionizes completely in an aqueous solution by losing one proton, according to the equationFor sulfuric acid which is diprotic, the "strong acid" designation refers only to dissociation of the first protonMore precisely, the acid must be stronger in aqueous solution than...

 comparable in strength to sulfuric
Sulfuric acid
Sulfuric acid is a strong mineral acid with the molecular formula . Its historical name is oil of vitriol. Pure sulfuric acid is a highly corrosive, colorless, viscous liquid. The salts of sulfuric acid are called sulfates...

 and nitric acid
Nitric acid
Nitric acid , also known as aqua fortis and spirit of nitre, is a highly corrosive and toxic strong acid.Colorless when pure, older samples tend to acquire a yellow cast due to the accumulation of oxides of nitrogen. If the solution contains more than 86% nitric acid, it is referred to as fuming...

s. It is a powerful oxidizer, but its aqueous solutions up to appr. 70% are remarkably inert, only showing strong acid properties and no other oxidizing properties. Above concentrations of appr. 70% the speed of oxidizing reactions rapidly increases with increasing acid concentration. It is useful for preparing perchlorate
Perchlorate
Perchlorates are the salts derived from perchloric acid . They occur both naturally and through manufacturing. They have been used as a medicine for more than 50 years to treat thyroid gland disorders. They are used extensively within the pyrotechnics industry, and ammonium perchlorate is also a...

 salts, especially ammonium perchlorate
Ammonium perchlorate
Ammonium perchlorate is an inorganic compound with the formula NH4ClO4. It is the salt of perchloric acid and ammonia. It is a powerful oxidizer, which is why its main use is in solid propellants...

, an important rocket oxidizer. Perchloric acid is also dangerously corrosive and readily forms explosive mixtures.

Production


Perchloric acid is produced industrially by two routes. The traditional method exploits the high aqueous solubility of sodium perchlorate
Sodium perchlorate
Sodium perchlorate is the inorganic compound with the chemical formula NaClO4. It is the most soluble of the common perchlorate salts. It is a white crystalline, hygroscopic solid that is highly soluble in water and in alcohol...

 (209 g/100 mL of water at room temperature). Treatment of such solutions with hydrochloric acid
Hydrochloric acid
Hydrochloric acid is a solution of hydrogen chloride in water, that is a highly corrosive, strong mineral acid with many industrial uses. It is found naturally in gastric acid....

 gives perchloric acid, precipitating solid sodium chloride:
NaClO4 + HCl → NaCl + HClO4

The concentrated acid can be purified by distillation
Distillation
Distillation is a method of separating mixtures based on differences in volatilities of components in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction....

. The alternative route, which is more direct and involves no salts, entails anodic oxidation of aqueous chlorine at a platinum electrode.

Laboratory preparations


Treatment of barium perchlorate with sulfuric acid precipitates barium sulfate
Barium sulfate
Barium sulfate is the inorganic compound with the chemical formula BaSO4. 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 and materials prepared from it...

, leaving perchloric acid. It also can be made by mixing nitric acid
Nitric acid
Nitric acid , also known as aqua fortis and spirit of nitre, is a highly corrosive and toxic strong acid.Colorless when pure, older samples tend to acquire a yellow cast due to the accumulation of oxides of nitrogen. If the solution contains more than 86% nitric acid, it is referred to as fuming...

 with ammonium perchlorate
Ammonium perchlorate
Ammonium perchlorate is an inorganic compound with the formula NH4ClO4. It is the salt of perchloric acid and ammonia. It is a powerful oxidizer, which is why its main use is in solid propellants...

. The reaction gives nitrous oxide
Nitrous oxide
Nitrous oxide, commonly known as laughing gas or sweet air, is a chemical compound with the formula . It is an oxide of nitrogen. At room temperature, it is a colorless non-flammable gas, with a slightly sweet odor and taste. It is used in surgery and dentistry for its anesthetic and analgesic...

 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
Water of crystallization
In crystallography, water of crystallization or water of hydration or crystallization water is water that occurs in crystals. Water of crystallization is necessary for the maintenance of crystalline properties, but capable of being removed by sufficient heat...

, several of which have been characterized crystallographically
X-ray crystallography
X-ray crystallography is a method of determining the arrangement of atoms within a crystal, in which a beam of X-rays strikes a crystal and causes the beam of light to spread into many specific directions. From the angles and intensities of these diffracted beams, a crystallographer can produce a...

. These solids consist of the perchlorate
Perchlorate
Perchlorates are the salts derived from perchloric acid . They occur both naturally and through manufacturing. They have been used as a medicine for more than 50 years to treat thyroid gland disorders. They are used extensively within the pyrotechnics industry, and ammonium perchlorate is also a...

 anion linked via hydrogen bond
Hydrogen bond
A hydrogen bond is the attractive interaction of a hydrogen atom with an electronegative atom, such as nitrogen, oxygen or fluorine, that comes from another molecule or chemical group. The hydrogen must be covalently bonded to another electronegative atom to create the bond...

s to H2O and H3O+
Hydronium
In chemistry, a hydronium ion is the cation , a type of oxonium ion produced by protonation of water. This cation is often used to represent the nature of the proton in aqueous solution, where the proton is highly solvated...

 centers Perchloric acid forms an azeotrope
Azeotrope
An azeotrope is a mixture of two or more liquids in such a ratio that its composition cannot be changed by simple distillation. This occurs because, when an azeotrope is boiled, the resulting vapor has the same ratio of constituents as the original mixture....

 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
Hygroscopy is the ability of a substance to attract and hold water molecules from the surrounding environment. This is achieved through either absorption or adsorption with the absorbing or adsorbing material becoming physically 'changed,' somewhat, by an increase in volume, stickiness, or other...

. 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
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 pentoxide:...

, which is even more dangerous:
2 HClO4 + P4O10 → Cl2O7 + "H2P4O11"

Uses


Perchloric acid is mainly produced as a precursor to ammonium perchlorate
Ammonium perchlorate
Ammonium perchlorate is an inorganic compound with the formula NH4ClO4. It is the salt of perchloric acid and ammonia. It is a powerful oxidizer, which is why its main use is in solid propellants...

, which is used as rocket fuel. The growth in rocketry has led to increased production of perchloric acid. Several million kilograms are produced annually.

As an acid


Perchloric acid, a superacid
Superacid
According to the classical definition superacid is an acid with an acidity greater than that of 100% pure sulfuric acid, which has a Hammett acidity function of −12. According to the modern definition, superacid is a medium, in which the chemical potential of the proton is higher than in pure...

, is one of the strongest Brønsted-Lowry acids. Its pKa
PKA
PKA, pKa, or other similar variations may stand for:* pKa, the symbol for the acid dissociation constant at logarithmic scale* Protein kinase A, a class of cAMP-dependent enzymes* Pi Kappa Alpha, the North-American social fraternity...

 is −10. It provides strong acidity with minimal interference because perchlorate is weakly nucleophilic (explaining the high acidity of HClO4). Other acids of noncoordinating anions, such as fluoroboric acid
Fluoroboric acid
Fluoroboric acid is the chemical compound with the formula HBF4. It is the conjugate acid of tetrafluoroborate. It is available commercially as a solution in water and other solvents such as diethyl ether...

 and hexafluorophosphoric acid
Hexafluorophosphoric acid
Hexafluorophosphoric acid is the chemical compound with the chemical formula HPF6. This strong Brønsted acid features a non-coordinating anion, hexafluorophosphate . It is formed from the reaction of hydrogen fluoride with phosphorus pentafluoride....

 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.

It is also used for electropolishing
Electropolishing
Electropolishing, also known as electrochemical polishing or electrolytic polishing , is an electrochemical process that removes material from a metallic workpiece. It is used to polish, passivate, and deburr metal parts. It is often described as the reverse of electroplating...

/etching of aluminum, molybdenum, and other metals.

Safety


Given its strong oxidizing
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....

 properties, perchloric acid is subject to extensive regulations. It is highly reactive with metals (e.g., aluminium
Aluminium
Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances....

) and organic matter (wood, plastics). On February 20, 1947, in Los Angeles California, 17 people were killed and 150 injured when a bath, consisting of over 1000 litres of 75% perchloric acid and 25% acetic anhydride
Acetic anhydride
Acetic anhydride, or ethanoic anhydride, is the chemical compound with the formula 2O. Commonly abbreviated Ac2O, it is the simplest isolatable acid anhydride and is a widely used reagent in organic synthesis...

 by volume, exploded. The plant, 25 other buildings and 40 automobiles were obliterated and 250 nearby homes were damaged. The bath was being used to electro-polish
Electropolishing
Electropolishing, also known as electrochemical polishing or electrolytic polishing , is an electrochemical process that removes material from a metallic workpiece. It is used to polish, passivate, and deburr metal parts. It is often described as the reverse of electroplating...

aluminum furniture. In addition, 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.

Work conducted with perchloric acid must be conducted in fume hoods with a wash-down capability to prevent accumulation of oxidisers in ductwork.

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