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Perchloric acid

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Perchloric acid

Perchloric acid
Perchloric acidHydroxidotrioxidochlorine Perchloric acidHydroxidotrioxidochlorine
Identifiers
CAS number  YesY
PubChem
ChemSpider  YesY
EC number
UN number 1873
ChEBI  YesY
ChEMBL  YesY
RTECS number SC7500000
Jmol-3D images Image 1
Properties
Molecular formula HClO4
Molar mass 100.46 g/mol
Appearance colorless liquid
Density 1.67 g/cm3
Melting point −17 °C (1 °F; 256 K) (azeotrope)[2]
-112 °C (anhydrous)
Boiling point 203 °C (397 °F; 476 K) (azeotrope)[3]
Solubility in water miscible
Acidity (pKa) ≈ −8[4]
Hazards
MSDS ICSC 1006
EU Index 017-006-00-4
EU classification Oxidant (O)
Corrosive (C)
R-phrases R5, R8, R35
S-phrases (S1/2), S23, S26, S36, S45
NFPA 704
0
3
3
OX
Related compounds
Related compounds Hydrochloric acid
Hypochlorous acid
Chlorous acid
Chloric acid
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 YesY   YesY/N?)

Perchloric acid is an sulfuric and nitric acid. It is a powerful oxidizer when hot, but its aqueous solutions up to approximately 70% and 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. Overall, perchloric acid is dangerously corrosive and readily forms potentially explosive mixtures.

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.[5][6]

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[7] 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, which is even more dangerous:[8]

2 HClO4 + P4O10 → Cl2O7 + "H2P4O11"

Uses

Perchloric acid is mainly produced as a precursor to ammonium perchlorate, which is used as rocket fuel. The growth in rocketry has led to increased production of perchloric acid. Several million kilograms are produced annually.[5] 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.[9] Additionally it is a useful component in etching of chrome[10]

Its use in analytical chemistry was championed in the U.S. by George Frederick Smith under the tutelage of H.H. Willard, for its unique properties. He used perchloric acid to produce magnesium perchlorate in his garage for the steel industry and later established a company, G. Frederick Smith Chemical Co, to produce additional perchlorate salts.

As an acid

Perchloric acid, a superacid, is one of the strongest Brønsted-Lowry acids. Its pKa is −10.[11] 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.[12] For similar reasons, it is a useful eluent in ion-exchange chromatography.

It is also used for electropolishing/etching of aluminum, molybdenum, and other metals.

Safety

Given its strong [14][15]

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

See also

References

  1. ^ Samuel Fomon. Medicine and the Allied Sciences 1. p. 148. 
  2. ^ Safety data for concentrated perchloric acid, ca. 70% msds.chem.ox.ac.uk
  3. ^ Handling of Perchloric acid ameslab.gov
  4. ^ Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. p. 171.  
  5. ^ 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.
  6. ^ Müler, W.; Jönck, P. (1963). "Herstellung von Perchlorsäure durch anodische Oxydation von Chlor". Chemie Ingenieur Technik - CIT 35 (2): 78.   ; German patent DE1031288B; US patent US2846383A
  7. ^ Almlöf, Jan; Lundgren, Jan O.; Olovsson, Ivar "Hydrogen Bond Studies. XLV. Crystal structure of perchloric acid 2.5 hydrate" Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry 1971, volume 27, pp. 898-904.doi:10.1107/S0567740871003236
  8. ^ Holleman, Arnold F.; Wiberg, Egon (2001). Inorganic chemistry. Translated by Mary Eagleson, William Brewer. San Diego: Academic Press. p. 464.  
  9. ^ http://www.gfschemicals.com/statics/coreproducts/Perchloric_acid.html
  10. ^ http://engineering.dartmouth.edu/microeng/processing/etching/metal.etch.html
  11. ^ Kathleen Sellers; Katherine Weeks; William R. Alsop; Stephen R. Clough; Marilyn Hoyt; Barbara Pugh (2006). Perchlorate: environmental problems and solutions. CRC Press. p. 16.  
  12. ^ A. T. Balaban, C. D. Nenitzescu, K. Hafner and H. Kaiser (1973), "2,4,6-Trimethylpyrilium Perchlorate",  
  13. ^ Perchloric Acid, 60%, GR Material Safety Data Sheet Seton Resource Center
  14. ^ R. C. Nester; G. F. Vander Voort (1992). Safety in the Metallographic Laboratory. ASTM Standardization News. p. 34. 
  15. ^ "CALIFORNIA: The Amazing Brew". Time.com. March 3, 1947. 

External links

  • International Chemical Safety Card 1006
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