Perchloric acid

Names

Systematic IUPAC name

Perchloric acid

Other names

Hyperchloric acid^[1]

Identifiers

CAS Number

7601-90-3^Y

3D model (JSmol)

Interactive image

ChEBI

CHEBI:29221^Y

ChEMBL

ChEMBL1161634^Y

ChemSpider

22669^Y

ECHA InfoCard

100.028.648

EC Number

231-512-4

PubChem CID

24247

RTECS number

SC7500000

UNII

V561V90BG2^Y

UN number

1873

CompTox Dashboard (EPA)

DTXSID8047004

InChI

InChI=1S/ClHO4/c2-1(3,4)5/h(H,2,3,4,5)^Y
Key: VLTRZXGMWDSKGL-UHFFFAOYSA-N^Y
InChI=1/ClHO4/c2-1(3,4)5/h(H,2,3,4,5)
Key: VLTRZXGMWDSKGL-UHFFFAOYAD

SMILES

O[Cl+3]([O-])([O-])[O-]

Properties

Chemical formula

HClO₄

Molar mass

100.46 g/mol

Appearance

colorless liquid

Odor

odorless

Density

1.768 g/cm³

Melting point

−17 °C (1 °F; 256 K) (72% aqueous solution)^[2]
−112 °C (anhydrous)

Boiling point

203 °C (397 °F; 476 K) (azeotrope)^[2]

Solubility in water

Miscible

Acidity (pK_a)

−15.2 (±2.0);^[3] ≈ −10

Conjugate base

Perchlorate

Hazards

Occupational safety and health (OHS/OSH):

Main hazards

Powerful oxidizer, highly corrosive

GHS labelling:

Pictograms

Signal word

Danger

Hazard statements

H271, H290, H302, H314, H373

Precautionary statements

P210, P280, P303+P361+P353, P304+P340, P305+P351+P338, P310, P371, P375, P380

NFPA 704 (fire diamond)

Flash point

Non-flammable

Safety data sheet (SDS)

ICSC 1006

Related compounds

Hydrochloric acid
Hypochlorous acid
Chlorous acid
Chloric acid

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Y verify (what is ^YN ?)

Infobox references

Chemical compound

Perchloric acid is a mineral acid with the formula H Cl O₄. Usually found as an aqueous solution, this colorless compound is a stronger acid than sulfuric acid, nitric acid and hydrochloric acid. It is a powerful oxidizer when hot, but aqueous solutions 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 salts, especially ammonium perchlorate, an important rocket fuel component. Perchloric acid is dangerously corrosive and readily forms potentially explosive mixtures.^[4]

History

Perchloric acid was first synthesized (together with potassium perchlorate) by Austrian chemist Friedrich von Stadion [de] and called "oxygenated chloric acid" in mid-1810s. French pharmacist Georges-Simon Serullas introduced the modern designation along with discovering its solid monohydrate (which he, however, mistook for an anhydride).^[5]

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 hydrochloric acid gives perchloric acid, precipitating solid sodium chloride:

NaClO₄ + HCl → NaCl + HClO₄

The concentrated acid can be purified by distillation. The alternative route, which is more direct and avoids salts, entails anodic oxidation of aqueous chlorine at a platinum electrode.^[6]^[7]

Laboratory preparations

Treatment of barium perchlorate with sulfuric acid precipitates barium sulfate, leaving perchloric acid. It can also be made by mixing nitric acid with ammonium perchlorate and boiling while adding hydrochloric acid. The reaction gives nitrous oxide and perchloric acid due to a concurrent reaction involving the ammonium 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, several of which have been characterized crystallographically. These solids consist of the perchlorate anion linked via hydrogen bonds to H₂O and H₃O⁺ centers.^[8] An example is hydronium perchlorate. 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.

Dehydration of perchloric acid gives the anhydride dichlorine heptoxide:^[9]

2 HClO₄ + P₄O₁₀ → Cl₂O₇ + H₂P₄O₁₁

Uses

Perchloric acid is mainly produced as a precursor to ammonium perchlorate, which is used in rocket fuel. The growth in rocketry has led to increased production of perchloric acid. Several million kilograms are produced annually.^[6] Perchloric acid is one of the most proven materials for etching of liquid crystal displays and critical electronics applications as well as ore extraction and has unique properties in analytical chemistry.^[10] Additionally it is a useful component in etching of chrome.^[11]

As an acid

Perchloric acid, a superacid, is one of the strongest Brønsted–Lowry acids. That its pK_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 [H₃O⁺][ClO^–
₄].^[12] The most recent estimate of its aqueous pK_a is −15.2±2.0.^[3] 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 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.^[13] For similar reasons, it is a useful eluent in ion-exchange chromatography.

It is also used for electropolishing or etching of aluminium, molybdenum, and other metals.

Safety

Given its strong oxidizing properties, perchloric acid is subject to extensive regulations as it can react violently with metals and flammable substances such as wood, plastics, and oils.^[14] 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 35% acetic anhydride 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.^[15]^[16] The O'Connor Electro-Plating plant, 25 other buildings, and 40 automobiles were destroyed, and 250 nearby homes were damaged.

References

^ Fomon, S. (1920). Medicine and the Allied Sciences. D. Appleton. p. 148.
^ ^a ^b "Safety (MSDS) data for perchloric acid, 70%". msds.chem.ox.ac.uk. 2 July 2008. Archived from the original on 2 July 2008. Retrieved 24 February 2022.
^ ^a ^b Trummal, Aleksander; Lipping, Lauri; Kaljurand, Ivari; Koppel, Ilmar A.; Leito, Ivo (6 May 2016). "Acidity of Strong Acids in Water and Dimethyl Sulfoxide". The Journal of Physical Chemistry A. 120 (20). American Chemical Society (ACS): 3663–3669. Bibcode:2016JPCA..120.3663T. doi:10.1021/acs.jpca.6b02253. ISSN 1089-5639. PMID 27115918. S2CID 29697201.
^ "Perchloric Acid | Environmental Health & Safety | Michigan State University". ehs.msu.edu. Retrieved 2023-11-02.
^ Perchloric acid and perchlorates
^ ^a ^b 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. doi:10.1002/14356007.a06_483.
^ Müler, W.; Jönck, P. (1963). "Herstellung von Perchlorsäure durch anodische Oxydation von Chlor". Chemie Ingenieur Technik. 35 (2): 78. doi:10.1002/cite.330350203.; German patent DE1031288B; US patent US2846383A.
^ Almlöf, J.; Lundgren, J. O.; Olovsson, I. (15 May 1971). "Hydrogen bond studies. XLV. The crystal structure of HClO4.2.5H2O". Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry. 27 (5). International Union of Crystallography (IUCr): 898–904. doi:10.1107/s0567740871003236. ISSN 0567-7408.
^ Holleman, Arnold F.; Wiberg, Egon (2001). Inorganic chemistry. Translated by Mary Eagleson, William Brewer. San Diego: Academic Press. p. 464. ISBN 0-12-352651-5.
^ "Perchloric Acid". GFS chemicals. Archived from the original on 2015-01-31. Retrieved 2014-01-14.
^ "Metal Etching". Thayer School of Engineering.
^ Kathleen Sellers; Katherine Weeks; William R. Alsop; Stephen R. Clough; Marilyn Hoyt; Barbara Pugh (2006). Perchlorate: environmental problems and solutions. CRC Press. p. 16. ISBN 0-8493-8081-2.
^ A. T. Balaban, C. D. Nenitzescu, K. Hafner and H. Kaiser (1973). "2,4,6-Trimethylpyrilium Perchlorate". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 1106.
^ "Materials Safety Data Sheet - Perchloric Acid, 60%, GR" (PDF). emd chemicals. 2003. Archived from the original (PDF) on 24 March 2012. Retrieved 24 February 2022.
^ R. C. Nester; G. F. Vander Voort (1992). Safety in the Metallographic Laboratory. ASTM Standardization News. p. 34.
^ "CALIFORNIA: The Amazing Brew". Time.com. March 3, 1947.