Permanganate of potash
|Molar mass||158.034 g/mol|
magenta–rose in solution
|Melting point||240 °C (464 °F; 513 K) (decomposes)|
|63.8 g/L (20 °C)
250 g/L (65 °C)
|Solubility||decomposes in alcohol and organic solvents|
Refractive index (nD)
|119.2 J/mol K|
|171.7 J K−1 mol−1|
Std enthalpy of
Gibbs free energy (ΔfG˚)
|EU classification||Oxidant (O)
Dangerous for the environment (N)
|R-phrases||R8, R22, R50/53|
|S-phrases||(S2), S60, S61|
LD50 (Median lethal dose)
|1090 mg/kg (oral, rat)|
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
|what is: / ?)(|
Potassium permanganate is an inorganic chemical compound with the chemical formula KMnO4. It is a salt consisting of K+ and MnO−
4 ions. Formerly known as permanganate of potash or Condy's crystals, it is a strong oxidizing agent. It dissolves in water to give intensely pink or purple solutions, the evaporation of which leaves prismatic purplish-black glistening crystals. In 2000, worldwide production was estimated at 30,000 tonnes. In this compound, manganese is in the +7 oxidation state.
- 1 History
- 2 Preparation
- 3 Structure
- 4 Reactions
- 5 Uses
- 6 Safety and handling
- 7 References
- 8 External links
In 1659, Johann Rudolf Glauber fused a mixture of the mineral pyrolusite (manganese dioxide, MnO2) and potassium carbonate to obtain a material that, when dissolved in water, gave a green solution (potassium manganate) which slowly shifted to violet and then finally red. This report represents the first description of the production of potassium permanganate. Just under 200 years later, London chemist Henry Bollmann Condy had an interest in disinfectants; he found that fusing pyrolusite with sodium hydroxide (NaOH) and dissolving 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 potassium hydroxide (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 to stop competitors from marketing similar products.
Early photographers used it as a component of flash powder. It is now replaced with other oxidizers, due to the instability of permanganate mixtures. 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 sometimes still used in torpedoes.
Potassium permanganate is produced industrially from manganese dioxide, which also occurs as the mineral pyrolusite. The MnO2 is fused with potassium hydroxide and heated in air or with another source of oxygen, like potassium nitrate or potassium chlorate. This process gives potassium manganate:
- 2 MnO2 + 4 KOH + O2 → 2 K2MnO4 + 2 H2O
(Using sodium hydroxide the end product is not sodium manganate but an Mn(V) compound which is one reason the potassium permanganate is more commonly used than sodium permanganate. Furthermore the potassium salt crystallizes better).
The potassium manganate is then be converted into permanganate by electrolytic oxidation in alkaline media:
- K2MnO4 + H2O → KMnO4 + KOH + 1/2 H2
- 2 K2MnO4 + Cl2 → 2 KMnO4 + 2 KCl
And the acid-induced disproportionation reaction may be written:
- 3 K2MnO4 + 4 HCl → 2 KMnO4 + MnO2 + 2 H2O + 4 KCl
A weak acid such as carbonic acid is sufficient for this reaction:
- 3 K2MnO4 + 2 CO2 → 2 KMnO4 + 2 K2CO3 + MnO2
Potassium permanganate crystallizes from the concentrated reaction solution.
Permanganate salts can also be generated by treating a solution of Mn2+ ions with strong oxidants such as lead dioxide (PbO2), or sodium bismuthate (NaBiO3). Tests for the presence of manganese exploit the vivid violet color of permanganate produced by these reagents.
KMnO4 forms orthorhombic crystals with constants: a = 910.5 pm, b = 572.0 pm, c = 742.5 pm. The overall motif is similar to that for barium sulfate, with which it forms solid solutions. In the solid (as in solution), each MnO4− centres are tetrahedral. The Mn-O distances are 1.62 Å.
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 initially purple permanganate solution and generates a brown precipitate (MnO2). 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 oxidizing agent, can react with a variety of groups.
- CH3(CH2)17CH=CH2 + 2 KMnO4 + 3 H2SO4 → CH3(CH2)17COOH + CO2 + 4 H2O + K2SO4 + 2 MnSO4
- 5 C6H13CHO + 2 KMnO4 + 3 H2SO4 → 5 C6H13COOH + 3 H2O + K2SO4 + 2 MnSO4
- 5 C6H5CH3 + 6 KMnO4 + 9 H2SO4 → 5 C6H5COOH + 14 H2O + 3 K2SO4 + 6 MnSO4
Glycols and polyols are highly reactive toward KMnO4. For example, addition of potassium permanganate to an aqueous solution of sugar and sodium hydroxide produces the chemical chameleon reaction, which involves dramatic color changes associated with the various oxidation states of manganese. A related vigorous reaction is exploited as a fire starter in survival kits. For example, a mixture of potassium permanganate and glycerol or pulverized glucose ignites readily. Its sterilizing properties are another reason for inclusion of KMnO4 in a survival kit.
By itself, potassium permanganate does not dissolve in many organic solvents. If an organic solution of permanganate is desired, "purple benzene" may be prepared, either by treating a two phase mixture of aqueous potassium permanganate and benzene with a quaternary ammonium salt, or by sequestering the potassium cation with a crown ether.
Reaction with acids
Concentrated sulfuric acid reacts with KMnO4 to give Mn2O7, which can be explosive. Its reaction with 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) ion (Mn2+) and water. In neutral solution, permanganate is only reduced by three electrons 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 reduces in an alkaline solution to green K2MnO4, wherein manganese is in the +6 oxidation state.
A curious reaction occurs upon addition of 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 the reaction also produces explosive Mn2O7, this should only be attempted with great care.
Solid potassium permanganate decomposes when heated:
- 2KMnO4 → K2MnO4 + MnO2(s) + O2
Water treatment and disinfection
As an oxidant, potassium permanganate can act as an antiseptic. For example, dilute solutions are used to treat canker sores (ulcers), disinfectant for the hands and treatment for mild pompholyx, dermatitis, and fungal infections of the hands or feet.
Potassium permanganate is used extensively in the water treatment industry. It is used as a regeneration chemical to remove iron and hydrogen sulfide (rotten egg smell) from well water via a "Manganese Greensand" Filter. "Pot-Perm" is also obtainable at pool supply stores, is used additionally to treat waste water. Historically it was used to disinfect drinking water. It currently finds application in the control of nuisance organisms such as Zebra mussels in fresh water collection and treatment systems.
Synthesis of organic compounds
Aside from its use in water treatment, the other major application of KMnO4 is as a reagent for the synthesis of organic compounds. Significant amounts are required for the synthesis of ascorbic acid, chloramphenicol, saccharin, isonicotinic acid, and pyrazinoic acid.
Potassium permanganate can be used to quantitatively determine the total oxidisable organic material in an aqueous sample. The value determined is known as the permanganate value. In analytical chemistry, a standardized aqueous solution of KMnO4 is sometimes used as an oxidizing titrant for redox titrations (permanganometry). In a related way, it is used as a reagent to determine the Kappa number of wood pulp. For the standardization of KMnO4 solutions, reduction by oxalic acid is often used.
Ethylene absorbents extend storage time of bananas even at high temperatures. This effect can be exploited by packing bananas in polyethylene together with potassium permanganate. By removing ethylene by oxidation, the permanganate delays the ripening., increasing the fruit's shelf life up to 4 weeks without the need for refrigeration.
Potassium permanganate is typically included in survival kits: as a fire starter (mixed with antifreeze from a car radiator or glycerin), water sterilizer, and for creating distress signals on snow.
Potassium permanganate is used in the "plastic sphere dispensers" used to set backfires, burnouts, and prescribed fires. Polymer spheres resembling ping-pong balls containing small amounts of permanganate are injected with ethylene glycol and projected towards the area where ignition is desired, where they spontaneously ignite seconds later. Both handheld and helicopter- or boat-mounted plastic sphere dispensers are used.
Potassium permanganate is one of the principal chemicals used in the film and television industries to "age" props and set dressings. Its ready conversion to brown MnO2 create "hundred-year-old" or "ancient" looks on Hessian cloth, ropes, timber, and glass.
Safety and handling
As an oxidizer that generates the dark brown product MnO2, potassium permanganate rapidly stains virtually any organic material such as skin, paper, and clothing. Solid KMnO4 is a strong oxidizer, thus should be kept separated from oxidizable substances. Reaction with concentrated sulfuric acid produces the highly explosive manganese(VII) oxide (Mn2O7). When solid, KMnO4 mixed with pure glycerol or other simple alcohols will result in a violent combustion reaction.
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One of the techniques DeLor is known for among designers and clients is the special effects he creates with various chemical solutions. When applied to wood surfaces, these chemicals give a weathered appearance to new wood. ... To achieve the aesthetic on interior surfaces, DeLor often uses a mixture of water and potassium permanganate, a dry powder chemical.
- International Chemical Safety Card 0672
- National Pollutant Inventory: Manganese and compounds Fact Sheet
- The use of potassium permanganate in fish ponds
- Sugar, NaOH and KMnO4
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