Perchloric acid

Perchloric acid is a mineral acid with the formula HClO4 .

Perchloric acid
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.

Contents
History
Production
Laboratory preparations
Properties
Uses
As an acid
Safety
See also
References Names
External links Systematic IUPAC name
chloric(VII) acid
Other names
History Hyperchloric acid[1]

Perchloric acid was first synthesized (together with potassium Identifiers

perchlorate) by Austrian chemist Friedrich von Stadion and called CAS Number 7601-90-3 (https://c
"oxygenated chloric acid" in mid-1810s; French pharmacist ommonchemistry.c
Georges-Simon Serullas introduced the modern designation along as.org/detail?cas_r
with discovering its solid monohydrate (which he, however,
n=7601-90-3) 
mistook for an anhydride).[4]
3D model Interactive image
(JSmol) (https://chemapps.s
Production tolaf.edu/jmol/jmol.
php?model=O%5B
Perchloric acid is produced industrially by two routes. The
traditional method exploits the high aqueous solubility of sodium Cl%2B3%5D%28%
perchlorate (209 g/100 mL of water at room temperature). 5BO-%5D%29%2
Treatment of such solutions with hydrochloric acid gives 8%5BO-%5D%29%
perchloric acid, precipitating solid sodium chloride: 5BO-%5D)
 NaClO4 + HCl → NaCl + HClO4 ChEBI CHEBI:29221 (http
s://www.ebi.ac.uk/c
The concentrated acid can be purified by distillation. The
hebi/searchId.do?c
alternative route, which is more direct and avoids salts, entails
hebiId=29221) 
anodic oxidation of aqueous chlorine at a platinum electrode.[5][6]
ChEMBL ChEMBL1161634
(https://www.ebi.ac.
Laboratory preparations
uk/chembldb/index.
php/compound/insp
Treatment of barium perchlorate with sulfuric acid precipitates
barium sulfate, leaving perchloric acid. It can also be made by ect/ChEMBL11616
mixing nitric acid with ammonium perchlorate and boiling while 34) 
adding hydrochloric acid. The reaction gives nitrous oxide and ChemSpider 22669 (https://www.
perchloric acid due to a concurrent reaction involving the
chemspider.com/C
ammonium ion and can be concentrated and purified significantly
hemical-Structure.2
by boiling off the remaining nitric and hydrochloric acids.
2669.html) 

Properties ECHA InfoCard 100.028.648 (http

s://echa.europa.eu/
Anhydrous perchloric acid is an unstable oily liquid at room substance-informati
temperature. It forms at least five hydrates, several of which have on/-/substanceinfo/
been characterized crystallographically. These solids consist of the 100.028.648)
perchlorate anion linked via hydrogen bonds to H2 O and H3 O+ EC Number 231-512-4
centers.[7] An example is hydronium perchlorate. Perchloric acid
PubChem CID 24247 (https://pubc
forms an azeotrope with water, consisting of about 72.5%
perchloric acid. This form of the acid is stable indefinitely and is hem.ncbi.nlm.nih.g
commercially available. Such solutions are hygroscopic. Thus, if ov/compound/2424
left open to the air, concentrated perchloric acid dilutes itself by 7)
absorbing water from the air. RTECS SC7500000
Dehydration of perchloric acid gives the anhydride dichlorine number
heptoxide:[8] UNII V561V90BG2 (http
s://fdasis.nlm.nih.g
2 HClO4 + P4O10 → Cl2O7 + H2P4O11
ov/srs/srsdirect.js
p?regno=V561V90
Uses BG2) 
UN number 1873
Perchloric acid is mainly produced as a precursor to ammonium
perchlorate, which is used in rocket fuel. The growth in rocketry CompTox DTXSID8047004 (h
Dashboard
has led to increased production of perchloric acid. Several million ttps://comptox.epa.
(EPA)
kilograms are produced annually.[5] Perchloric acid is one of the gov/dashboard/che
most proven materials for etching of liquid crystal displays and mical/details/DTXSI
critical electronics applications as well as ore extraction and has D8047004)
unique properties in analytical chemistry.[9] Additionally it is a
InChI
useful component in etching of chrome.[10]
InChI=1S/ClHO4/c2-1(3,4)5/h(H,2,3,
4,5)  
As an acid Key: VLTRZXGMWDSKGL-UHFFFA
OYSA-N 
Perchloric acid, a superacid, is one of the strongest Brønsted– InChI=1/ClHO4/c2-1(3,4)5/h(H,2,3,4,
Lowry acids. That its pKa is lower than −9 is evidenced by the 5)
fact that its monohydrate contains discrete hydronium ions and Key: VLTRZXGMWDSKGL-UHFFFA
OYAD
can be isolated as a stable, crystalline solid, formulated as [H3 O+]
[ClO–4 ].[11] The most recent estimate of its aqueous pKa is SMILES
−15.2 ± 2.0.[3] It provides strong acidity with minimal O[Cl+3]([O-])([O-])[O-]
interference because perchlorate is weakly nucleophilic Properties
(explaining the high acidity of HClO4 ). Other acids of
Chemical HClO4
noncoordinating anions, such as fluoroboric acid and
formula
hexafluorophosphoric acid are susceptible to hydrolysis, whereas
perchloric acid is not. Despite hazards associated with the Molar mass 100.46 g/mol
explosiveness of its salts, the acid is often preferred in certain Appearance colorless liquid
syntheses.[12] For similar reasons, it is a useful eluent in ion- Odor odorless
exchange chromatography.
Density 1.768 g/cm3
It is also used for electropolishing or etching of aluminium, Melting point −17 °C (1 °F;
molybdenum, and other metals.
256 K) (72%
aqueous solution)[2]
Safety −112 °C
(anhydrous)
Given its strong oxidizing properties, perchloric acid is subject to
Boiling point 203 °C (397 °F;
extensive regulations as it can react violently with metals and
476 K)
flammable substances such as wood, plastics, and oils.[13] Work
(azeotrope)[2]
conducted with perchloric acid must be conducted in fume hoods
with a wash-down capability to prevent accumulation of oxidisers Solubility in Miscible
in the ductwork. water
Acidity (pKa) −15.2 (±2.0);[3] ≈
On February 20, 1947 in Los Angeles, California, 17 people were −10
killed and 150 injured in the O'Connor Plating Works disaster. A
bath, consisting of over 1000 litres of 75% perchloric acid and Conjugate Perchlorate
25% acetic anhydride by volume which was being used to base
electro-polish aluminium furniture, exploded. Organic compounds Hazards
were added to the overheating bath when an iron rack was
Occupational safety and health
replaced with one coated with cellulose acetobutyrate (Tenit-2
(OHS/OSH):
plastic). A few minutes later the bath exploded.[14][15] The
O'Connor Electro-Plating plant, 25 other buildings, and 40 Main hazards Powerful oxidizer,
automobiles were destroyed, and 250 nearby homes were highly corrosive
damaged.
GHS labelling:
Pictograms
See also
Chloric acid
Oxidizing acid

Signal word Danger

References Hazard H271, H290, H302,
1. Fomon, S. (1920). Medicine and the Allied Sciences (ht statements H314, H373
tps://books.google.com/books?id=v8E0AQAAMAAJ). Precautionary P210, P280,
Medicine and the Allied Sciences. D. Appleton. p. 148. statements P303+P361+P353,
2. "Safety (MSDS) data for perchloric acid, 70%" (https://w P304+P340,
eb.archive.org/web/20080702194644/http://msds.che P305+P351+P338,
m.ox.ac.uk/PE/perchloric_acid.html). P310, P371, P375,
msds.chem.ox.ac.uk. 2 July 2008. Archived from the P380
original (http://msds.chem.ox.ac.uk/PE/perchloric_acid.
html) on 2 July 2008. Retrieved 24 February 2022. NFPA 704
(fire diamond)
0
3. Trummal, Aleksander; Lipping, Lauri; Kaljurand, Ivari; 3 3
Koppel, Ilmar A.; Leito, Ivo (6 May 2016). "Acidity of OX
Strong Acids in Water and Dimethyl Sulfoxide". The
Journal of Physical Chemistry A. American Chemical Flash point Non-flammable
Society (ACS). 120 (20): 3663–3669.
Bibcode:2016JPCA..120.3663T (https://ui.adsabs.harv Safety data ICSC 1006 (http://w
ard.edu/abs/2016JPCA..120.3663T). sheet (SDS) ww.inchem.org/doc
doi:10.1021/acs.jpca.6b02253 (https://doi.org/10.102 uments/icsc/icsc/eic
1%2Facs.jpca.6b02253). ISSN 1089-5639 (https://ww s1006.htm)
w.worldcat.org/issn/1089-5639). PMID 27115918 (http Related compounds
s://pubmed.ncbi.nlm.nih.gov/27115918).
S2CID 29697201 (https://api.semanticscholar.org/Corp Related Hydrochloric acid
usID:29697201). compounds Hypochlorous acid
Chlorous acid
4. http://www.sciencemadness.org/library/books/perchloric_acid_and_perchlorates.pdf
5. Helmut Vogt, Jan Balej, John E. Bennett, Peter Wintzer, Chloric acid
Saeed Akbar Sheikh, Patrizio Gallone "Chlorine Except where otherwise noted, data
Oxides and Chlorine Oxygen Acids" in Ullmann's are given for materials in their
Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, standard state (at 25 °C [77 °F],
Weinheim. doi:10.1002/14356007.a06_483 (https://doi. 100 kPa).
org/10.1002%2F14356007.a06_483).  verify (what is   ?)
6. Müler, W.; Jönck, P. (1963). "Herstellung von Infobox references
Perchlorsäure durch anodische Oxydation von Chlor".
Chemie Ingenieur Technik. 35 (2): 78.
doi:10.1002/cite.330350203 (https://doi.org/10.1002%2
Fcite.330350203).; German patent DE1031288B (http
s://depatisnet.dpma.de/DepatisNet/depatisnet?action=
bibdat&docid=DE000001031288B); US patent
US2846383A (https://patents.google.com/patent/US28
46383).
7. 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.
International Union of Crystallography (IUCr). 27 (5):
898–904. doi:10.1107/s0567740871003236 (https://do
i.org/10.1107%2Fs0567740871003236). ISSN 0567-
7408 (https://www.worldcat.org/issn/0567-7408).
8. 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.
 9. "Perchloric Acid" (https://web.archive.org/web/20150131093457/http://www.gfschemicals.co
m/statics/coreproducts/Perchloric_acid.html). GFS chemicals. Archived from the original (htt
p://www.gfschemicals.com/statics/coreproducts/Perchloric_acid.html) on 2015-01-31.
Retrieved 2014-01-14.
10. "Metal Etching" (http://engineering.dartmouth.edu/microeng/processing/etching/metal.etch.ht
ml). Thayer School of Engineering.
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. ISBN 0-8493-8081-2.
12. A. T. Balaban, C. D. Nenitzescu, K. Hafner and H. Kaiser (1973). "2,4,6-Trimethylpyrilium
Perchlorate" (http://www.orgsyn.org/demo.aspx?prep=cv5p1106). Organic Syntheses.;
Collective Volume, vol. 5, p. 1106
13. "Materials Safety Data Sheet - Perchloric Acid, 60%, GR" (https://web.archive.org/web/2012
0324083342/http://www.setonresourcecenter.com/msdshazcom/htdocs//MSDS/E/EMD/Doc
s/wcd00021/wcd0218c.pdf) (PDF). emd chemicals. 2003. Archived from the original (http://w
ww.setonresourcecenter.com/msdshazcom/htdocs//MSDS/E/EMD/Docs/wcd00021/wcd021
8c.pdf) (PDF) on 24 March 2012. Retrieved 24 February 2022.
14. R. C. Nester; G. F. Vander Voort (1992). Safety in the Metallographic Laboratory. ASTM
Standardization News. p. 34.
15. "CALIFORNIA: The Amazing Brew" (http://content.time.com/time/magazine/article/0,9171,85
4621,00.html). Time.com. March 3, 1947.

External links
International Chemical Safety Card 1006 (http://www.inchem.org/documents/icsc/icsc/eics10
06.htm)
Compounds containing perchlorate group
HClO4

LiClO4 Be(ClO4 )2

NaClO4 Mg(ClO4 )2

VO(ClO4 )3 Co(ClO4 )2 ,
KClO4 Ca(ClO4 )2 Sc(ClO4 )3 Ti(ClO4 )4 Cr(ClO4 )3 Mn(ClO4 )2 Fe(ClO4 )2 Ni(ClO
VO2 (ClO4 ) Co(ClO4 )3
RbClO4 Sr(ClO4 )2 Y(ClO4 )3 Zr(ClO4 )4 Nb(ClO4 )5 Mo Tc Ru Rh(ClO4 )3 Pd(Cl

CsClO4 Ba(ClO4 )2   Lu(ClO4 )3 Hf(ClO4 )4 Ta(ClO4 )5 W Re Os Ir P

FrClO4 Ra   Lr Rf Db Sg Bh Hs Mt D
↓
La Ce(ClO4 )x Pr(ClO4 )3 Nd(ClO4 )3 Pm Sm(ClO4 )3 Eu(ClO4 )3 Gd(Cl
Ac Th(ClO4 )4 Pa UO2 (ClO4 )2 Np Pu Am Cm

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