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Potassium permanganate

Potassium permanganate
IUPAC name Potassium manganate(VII)
Other names Potassium permanganate, Chameleon mineral, Condy's crystals
Identifiers
CAS number [7722-64-7]
PubChem 24400
KEGG D02053
SMILES O- [Mn](=O)(=O)=O.K+
InChI
Properties
Molecular formula KMnO4
Molar mass 158.04 g/mol
Appearance purplish-bronze-gray needles;
magenta–rose in solution
Density 2.703 g/cm³, solid
Melting point

270 °C decomp.

Solubility in water 6.38 g/100 ml at 20 °C
Structure
Crystal structure Orthorhombic
Thermochemistry
Std enthalpy of
formation
ΔfHo298
-813.4 kJ.mol-1
Standard molar
entropy
So298
171.7 J.K-1.mol-1
Hazards
MSDS External MSDS
Main hazards Oxidant (O), Harmful (Xn), Dangerous for the environment (N)
NFPA 704
0
1
0
OX
R-phrases R8, R22, R50/53
S-phrases (S2), S60, S61
Related compounds
Other cations Sodium permanganate
Related compounds Potassium manganate (K2MnO4); Manganese heptoxide;

Sodium permanganate

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

Infobox disclaimer and references

Potassium permanganate is the chemical compound KMnO4. In this salt, manganese is in the +7 oxidation state. The salt is also known as "permanganate of potash." The permanganate ion is a strong oxidizing agent. It dissolves in water to give deep purple solutions, evaporation of which gives prismatic purplish-black glistening crystals.[1] It has a sweet flavour.

Its crystal structure is orthorhombic with constants: a = 9.105, b = 5.720, c = 7.425 Å. Distance between Mn and O atoms in the tetrahedral anions is 1.629 Å.

Preparation

Potassium permanganate is manufactured on a large scale due to its manifold uses in the laboratory. In the first stage, pyrolusite, which is manganese dioxide in its natural form, is fused with potassium hydroxide and heated in air or with potassium nitrate (a source of oxygen). This leads to the formation of potassium manganate, which on electrolytic oxidation in alkaline solution gives potassium permanganate.

MnO2 + 2OH- + O2 → MnO42- + H2O
MnO42- + Cl2 → MnO4- + 2Cl-

Permanganates can also be prepared by treating a solution of Mn2+ ions with very strong oxidising agents like lead dioxide, PbO2, or sodium bismuthate, NaBiO3, and these reactions have been used to test for the presence of manganese due to the formation of the distinctly violet color of permanganate.

Uses

Almost all applications of potassium permanganate are derived from it being an oxidizing agent in diverse chemical reactions in the laboratory and in industry.[2]

Disinfectant and water treatment

As an oxidant, potassium permanganate can act as a disinfectant. For example, dilute solutions are used as a treatment for canker sores (ulcers), disinfectant for the hands and treatment for mild pompholyx, dermatitis, and fungal infections of the hands or feet.

High-grade potassium permanganate can be found at pool supply stores and is used in rural areas to remove iron and hydrogen sulfide (rotten egg smell) from well water by oxidation. Some degree of disinfection may also be achieved from this use. Potassium permanganate similarly removes hydrogen sulfide from waste water.

KMnO4 is often included in survival kits along with either glycerine or a glucose tablet for the purposes of making fire. The glucose tablet can be ground up, mixed with the potassium permanganate and caused to combust by applying friction. It can also be mixed with anti-freeze from a vehicle (a source of glycols) to produce flame, although this can be dangerous and should be done in a controlled manner, such as dipping some paper into the anti-freeze and then adding a small amount of potassium permanganate. The ability to sterilise water and wounds is another reason for inclusion in a survival kit.

Potassium permanganate can also be used to quantitatively determine the total oxidisable organic material in an aqueous sample. The value determined is known as the permanganate value.

Biomedical uses

Dilute solution introduced into the uterus have been used to self-induce abortions. Insertion of the crystalline form as an abortifacient into the vagina has also been attempted, often resulting in severe injury.[3]

A dilute solution of acidified potassium permanganate is used in histology to bleach melanin which obscures tissue detail. Potassium permanganate can also be used to differentiate amyloid AA from other types of amyloid pathologically deposited in body tissues. Incubation of fixed tissue with potassium permanganate will prevent amyloid AA from staining with congo red whereas other types of amyloid are unaffected.[4][5]

Medicinial uses

KMnO4 diluted to 0.01% solution can be used for cleansing and deodorising suppurating eczmatous reactions and wounds. It can also be used for treatment of atheletes foot at the same concentration. KMnO4 is however irritant to mucous membranes.

Wet dressings or baths of 0.01% should be used. Note: Causes staining of skin and clothing. Typically skin turns brown for approximately 48 hours.

Miscellaneous uses

A solution of KMnO4 in water, in a volumetric flask
A solution of KMnO4 in water, in a volumetric flask

Aqueous solutions of KMnO4 have been used together with T-Stoff (i.e. 80% hydrogen peroxide) as propellant for the rocket plane Messerschmitt Me 163. In this application, it was known as Z-Stoff. This combination of propellants is still used in torpedoes.

  • A dilute solution (10mg/l) of potassium permanganate can be used to eliminate snails from plants prior to placing them in a fresh-water aquarium.

In analytical chemistry, a standardized aqueous solution of KMnO4 is sometimes used as an oxidizing titrant for redox titrations due to its deep purple color. In a related way, it is used as a reagent to determine the Kappa number of wood pulp.

KMnO4 is employed to treat some parasitic diseases of fish, to get racing pigeons up to racing form (often referred to as the "fly or die" method as pioneered by the accomplished British racing pigeon breeder Kenny Johnson), in treatment of drinking water, as well as an antidote in phosphorus poisoning. In Africa, it has been used as a disinfectant for vegetables such as lettuce.

In biochemistry, permanganate footprinting is a technique that is applied.[clarify]

Reactions

Organic synthesis

Dilute solutions of KMnO4 convert alkenes into diols (glycols). This behaviour is also used as a qualitative test for the presence of double or triple bonds in a molecule, since the reaction decolorizes the permanganate solution; thus it is sometimes referred to as Baeyer's reagent. However, bromine serves better in measuring unsaturation (double or triple bonds) quantitatively, since KMnO4, being a very strong oxidising agent can react with impurities in a sample.

Under acidic conditions, the alkene double bond is cleaved to give the appropriate carboxylic acid:[6]

CH3(CH2)17CH=CH2 + [O] → CH3(CH2)17COOH

Potassium permanganate oxidizes aldehydes to carboxylic acids, such as with n-heptanal:[7]

C6H13CHO + [O] → C6H13COOH

Concentrated solutions oxidize a methyl group (or any other alkyl group with a benzylic hydrogen) on an aromatic ring, e.g. toluene to benzoic acid.

KMnO4 oxidizes pseudoephedrine hydrochloride to produce methcathinone, a Schedule I drug in the United States. Consequently the DEA has restricted its use and sale by classifying it as a List II controlled precursor. Potassium permanganate is listed as a Table I precursor under the United Nations Convention Against Illicit Traffic in Narcotic Drugs and Psychotropic Substances.[8]

KMnO4 is also used in removal of impurities from coca base in the production of cocaine. The purer base results in aesthetically pleasing white crystals.[9]

Acids and KMnO4

Concentrated sulfuric acid reacts with KMnO4 to give Mn2O7, which can be explosive.[10][11][12] Similarly concentrated hydrochloric acid gives chlorine. The Mn-containing products from redox reactions depend on the pH. Acidic solutions of permanganate are reduced to the faintly pink manganese(II) sulfate ([Mn(H2O)6]2+). In neutral solution, permanganate is only reduced by 3e to give MnO2, wherein Mn is in a +4 oxidation state. This is the material that stains one's skin when handling KMnO4. KMnO4 spontaneously reduced in an alkaline solution to green K2MnO4, wherein manganese is in the +6 oxidation state.

A curious reaction is produced by adding concentrated sulfuric acid to potassium permanganate. Although no reaction may be apparent, the vapor over the mixture will ignite paper impregnated with alcohol. Potassium permanganate and sulfuric acid react to produce some ozone, which has a high oxidising power and rapidly oxidises the alcohol, causing it to combust. As a similar reaction produces explosive Mn2O7, this should only be attempted with great care. An approximate equation for the ozone formation is shown below.

At room temperature
6 KMnO4(aq) + 9 H2SO4(aq) → 6 MnSO4(aq) + 3 K2SO4(aq) + 9 H2O(l) + 5 O3(v)

History

In 1659 a German chemist, J.R. Glauber, fused a mixture of the mineral pyrolusite and potassium carbonate to obtain a material that, when dissolved in water, gave a green solution (potassium manganate) which slowly shifted to violet potassium permanganate and then finally red. This report represents the first description of the production of potassium permanganate.[13]

Just under two hundred years later London chemist Henry Bollmann Condy had an interest in disinfectants, and marketed several products including ozonised water. He found that fusing pyrolusite with NaOH and dissolved it in water produced a solution with disinfectant properties. He patented this solution, and marketed it as Condy's Fluid. Although effective, the solution was not very stable. This was overcome by using KOH rather than NaOH. This was more stable, and had the advantage of easy conversion to the equally effective potassium permanganate crystals. This crystalline material was known as Condy’s crystals or Condy’s powder. Potassium permanganate was comparatively easy to manufacture so Condy was subsequently forced to spend considerable time in litigation in order to stop competitors from marketing products similar to Condy's Fluid or Condy's Crystals.

Early photographers used it as a component of flash powder. It is now replaced with other oxidizers, due to the instability of permanganate mixtures.

Safety

Solid KMnO4 is a strong oxidizer and in general it should be kept separated from oxidizable substances. Dilute aqueous solutions of KMnO4 are not dangerous. KMnO4 forms dangerous products upon contact with concentrated acids. For instance, a reaction with concentrated sulfuric acid produces the highly explosive manganese(VII) oxide (Mn2O7).

As an oxidizer, potassium permanganate stains the hand and clothing as it is reduced to MnO2. Clothing stains may be washed away using acetic acid. Skin stains, which are typically brown, disappear within 48 hours.

References

  1. ^ F. Burriel, F. Lucena, S. Arribas and J. Hernández, (1985), Química Analítica Cualitativa, page 688, ISBN 84-9732-140-5.
  2. ^ A. Fatiadi (1987). "The Classical Permanganate Ion: Still a Novel Oxidant in Organic Chemistry" (review). Synthesis 1987 (2): 85-127. doi:10.1055/s-1987-27859. 
  3. ^ Obeng, B. B. (1968). "The lay use of potassium permanganate as an abortifacient". Br J Clin Pract 22 (11): 465-9. PMID 5696512. 
  4. ^ Wright, J. R.; Calkins E.; Humphrey R. L. (1977). "Potassium permanganate reaction in amyloidosis. A histologic method to assist in differentiating forms of this disease.". Lab Invest. 36 (3): 274-81. PMID 839739. 
  5. ^ van Rijswijk, M. H.; van Heusden, C. W. (1979). "The potassium permanganate method. A reliable method for differentiating amyloid AA from other forms of amyloid in routine laboratory practice.". Am J Pathol. 97 (1): 43-58. PMID 495695. 
  6. ^ Donald G. Lee, Shannon E. Lamb, and Victor S. Chang (1990). "Carboxylic Acids from the Oxidation of Terminal Alkenes by Permanganate: Nonadecanoic Acid". Org. Synth.; Coll. Vol. 7: 397. 
  7. ^ John R. Ruhoff. "n-Heptanoic acid". Org. Synth.; Coll. Vol. 2: 315. 
  8. ^ Red list
  9. ^ Michele M. Leonhart (29 Sep 2006). Final Rule - Control of Sodium Permanganate as a List II Chemical. Drug Enforcement Administration.
  10. ^ F. A. Cotton, G. Wilkinson, C. A. Murillo, and M. Bochmann (April 1999). Advanced Inorganic Chemistry, 6th Edition. Wiley-VCH. ISBN 0-471-19957-5
  11. ^ Barthel, H. and Duvinage, B. (2000). "Clemens Winkler. His Experiments with Ozone in 1892". Praxis der Naturwissenschaften, Chemie 49: 18ff. 
  12. ^ Dzhabiev, T. S.; Denisov, N. N.; Moiseev, D. N. and Shilov, A. E. (2005). "Formation of Ozone During the Reduction of Potassium Permanganate in Sulfuric Acid Solutions". Russian Journal of Physical Chemistry 79: 1755-1760. 
  13. ^ Weeks, M. E. and Leicester, H. M.; Discovery of the Elements, Journal of Chemical Education 1968

External links

 

The content of this section is licensed under the GNU Free Documentation License (local copy). It uses material from the Wikipedia article "Potassium permanganate" modified December 22, 2007 with previous authors listed in its history.