Potassium hydroxide
{{Short description|Inorganic compound (KOH)}}
{{chembox
|Verifiedfields = changed
|Watchedfields = changed
|verifiedrevid = 464361974
|Name = Potassium hydroxide
|ImageFile1 = Potassium hydroxide.jpg
|ImageName1 = Pellets of potassium hydroxide
|ImageFile = Potassium-hydroxide-xtal-3D-vdW.png
|ImageClass = bg-transparent
|ImageName = Crystal structure of KOH
|ImageSize = 150px
|IUPACName = Potassium hydroxide
|OtherNames = {{Unbulleted list|Caustic potash|Lye|Potash lye|Potassia|Potassium hydrate|KOH}}
|Section1={{Chembox Identifiers
|UNII_Ref = {{fdacite|correct|FDA}}
|UNII = WZH3C48M4T
|InChI = 1/K.H2O/h;1H2/q+1;/p-1
|InChIKey = KWYUFKZDYYNOTN-REWHXWOFAT
|ChEBI_Ref = {{ebicite|correct|EBI}}
|ChEBI = 32035
|SMILES = [K+].[OH-]
|StdInChI_Ref = {{stdinchicite|correct|chemspider}}
|StdInChI = 1S/K.H2O/h;1H2/q+1;/p-1
|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
|StdInChIKey = KWYUFKZDYYNOTN-UHFFFAOYSA-M
|CASNo = 1310-58-3
|CASNo_Ref = {{cascite|correct|CAS}}
|PubChem = 14797
|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
|ChemSpiderID = 14113
|RTECS = TT2100000
|UNNumber = 1813
|EINECS = 215-181-3
}}
|Section2={{Chembox Properties
|Formula = KOH
|K=1|O=1|H=1
|Appearance = white solid, deliquescent
|Odor = odorless
|Density = 2.044 g/cm3 (20 °C)
2.12 g/cm3 (25 °C)
|Solubility = 85 g/100 mL (−23.2 °C)
97 g/100 mL (0 °C)
121 g/100 mL (25 °C)
138.3 g/100 mL (50 °C)
162.9 g/100 mL (100 °C){{RubberBible86th|page=4-80}}{{cite book|last1 = Seidell|first1 = Atherton|last2 = Linke|first2 = William F.|year = 1952|title = Solubilities of Inorganic and Organic Compounds|publisher = Van Nostrand|url = https://books.google.com/books?id=k2e5AAAAIAAJ|access-date = 2014-05-29}}
|SolubleOther = soluble in alcohol, glycerol
insoluble in ether, liquid ammonia
|Solubility2 = 55 g/100 g (28 °C)
|Solvent2 = methanol
|Solubility3 = ~14 g / 100 g (28 °C)
|Solvent3 = isopropanol
|MeltingPtC = 410
{{cite journal | last1=Otto | first1=H.W | last2=Seward | first2=R.P. | title=Phase equilibria in the potassium hydroxide-sodium hydroxide system. | journal=J. Chem. Eng. Data | volume=9 | pages=507–508 | url=https://doi.org/10.1021/je60023a009 | doi=10.1021/je60023a009 | year=1964 | issue=4 }}{{cite journal | last1=Seward | first1=R.P | last2=Martin | first2=K.E. | title=The melting point of potassium hydroxide. | journal=J. Am. Chem. Soc. | volume=71 | pages=3564–3565 | url=https://doi.org/10.1021/ja01178a530 | doi=10.1021/ja01178a530 | year=1949 | issue=10 }}
|BoilingPtC = 1327
|RefractIndex = 1.409 (20 °C)
|MagSus = −22.0·10−6 cm3/mol
}}
|Section3={{Chembox Thermochemistry
|DeltaHf = −425.8 kJ/mol{{cite web|url=http://chemister.ru/Database/properties-en.php?dbid=1&id=325|title=potassium hydroxide|website=chemister.ru|access-date=8 May 2018|url-status=live|archive-url=https://web.archive.org/web/20140518070658/http://chemister.ru/Database/properties-en.php?dbid=1&id=325|archive-date=18 May 2014}}{{cite book| author = Zumdahl, Steven S.|title =Chemical Principles 6th Ed.| publisher = Houghton Mifflin Company| year = 2009| isbn = 978-0-618-94690-7|page=A22}}
}}
|Section4={{Chembox Hazards
|ExternalSDS = [http://www.inchem.org/documents/icsc/icsc/eics0357.htm ICSC 0357]
|GHSPictograms = {{GHS05}}{{GHS07}}{{Sigma-Aldrich|id=757551|name=Potassium hydroxide|accessdate=2014-05-18}}
|GHSSignalWord = Danger
|HPhrases = {{H-phrases|290|302|314}}
|PPhrases = {{P-phrases|280|305+351+338|310}}
|NFPA-H = 3
|NFPA-F = 0
|NFPA-R = 1
|NFPA-S = ALK
|FlashPt = nonflammable
|PEL = none{{PGCH|0523}}
}}
|Section5={{Chembox Related
|OtherAnions = Potassium hydrosulfide
Potassium amide
|OtherCations = Lithium hydroxide
Sodium hydroxide
Rubidium hydroxide
Caesium hydroxide
|OtherCompounds = Potassium oxide
}}
}}
Potassium hydroxide is an inorganic compound with the formula KOH, and is commonly called caustic potash.
Along with sodium hydroxide (NaOH), KOH is a prototypical strong base. It has many industrial and niche applications, most of which utilize its caustic nature and its reactivity toward acids. An estimated 700,000 to 800,000 tonnes were produced in 2005. KOH is noteworthy as the precursor to most soft and liquid soaps, as well as numerous potassium-containing chemicals. It is a white solid that is dangerously corrosive.{{cite book| last1=Schultz | first1=Heinz | last2=Bauer | first2=Günter | last3=Schachl | first3=Erich | last4=Hagedorn | first4=Fritz | last5=Schmittinger | first5=Peter |title=Ullmann's Encyclopedia of Industrial Chemistry|publisher=Wiley-VCH|location=Weinheim, Germany| year=2005 | isbn=978-3-527-30673-2 | doi=10.1002/14356007.a22_039|chapter=Potassium Compounds}}
Properties and structure
KOH exhibits high thermal stability. Because of this high stability and relatively low melting point, it is often melt-cast as pellets or rods, forms that have low surface area and convenient handling properties. These pellets become tacky in air because KOH is hygroscopic. Most commercial samples are ca. 90% pure, the remainder being water and carbonates. Its dissolution in water is strongly exothermic. Concentrated aqueous solutions are sometimes called potassium lyes. Even at high temperatures, solid KOH does not dehydrate readily.{{cite book|last1=Holleman|first1=A. F|last2=Wiberg|first2=E. |title=Inorganic Chemistry |publisher=Academic Press|location=San Diego|year=2001|isbn=978-0-12-352651-9}}
=Structure=
At higher temperatures, solid KOH crystallizes in the NaCl crystal structure. The {{OH-}} group is either rapidly or randomly disordered so that it is effectively a spherical anion of radius 1.53 Å (between {{chem2|Cl-}} and {{chem2|F-}} in size). At room temperature, the {{chem2|OH-}} groups are ordered and the environment about the {{chem2|K+}} centers is distorted, with {{chem2|K+\sOH-}} distances ranging from 2.69 to 3.15 Å, depending on the orientation of the OH group. KOH forms a series of crystalline hydrates, namely the monohydrate {{chem2|KOH * H2O}}, the dihydrate {{chem2|KOH * 2H2O}} and the tetrahydrate {{chem2|KOH * 4H2O}}.{{cite book |last=Wells |first=A.F. |year=1984 |title=Structural Inorganic Chemistry |location=Oxford |publisher=Clarendon Press |isbn=978-0-19-855370-0}}
Reactions
=Solubility and desiccating properties=
About 112 g of KOH dissolve in 100 mL water at room temperature, which contrasts with 100 g/100 mL for NaOH.{{cite book|last1 = Seidell|first1 = Atherton|last2 = Linke|first2 = William F.|year = 1952|title = Solubilities of Inorganic and Organic Compounds|publisher = Van Nostrand|url = https://books.google.com/books?id=k2e5AAAAIAAJ|access-date = 2014-05-29}} Thus on a molar basis, KOH is slightly more soluble than NaOH. Lower molecular-weight alcohols such as methanol, ethanol, and propanols are also excellent solvents. They participate in an acid-base equilibrium. In the case of methanol the potassium methoxide (methylate) forms:{{Cite journal|last1=Platonov|first1=Andrew Y.|last2=Kurzin|first2=Alexander V.|last3=Evdokimov|first3=Andrey N.|date=2009|title=Composition of Vapor and Liquid Phases in the Potassium Hydroxide + Methanol Reaction System at 25 °С|journal=J. Solution Chem.|volume=39|issue=3|pages=335–342|doi=10.1007/s10953-010-9505-1|s2cid=97177429}}
: {{chem2|KOH + CH3OH -> CH3OK + H2O}}
Because of its high affinity for water, KOH serves as a desiccant in the laboratory. It is often used to dry basic solvents, especially amines and pyridines.
=As a nucleophile in organic chemistry=
KOH, like NaOH, serves as a source of {{chem2|OH-}}, a highly nucleophilic anion that attacks polar bonds in both inorganic and organic materials. Aqueous KOH saponifies esters:
: {{chem2|KOH + RCOOR' -> RCOOK + R'OH}}
When R is a long chain, the product is called a potassium soap. This reaction is manifested by the "greasy" feel that KOH gives when touched; fats on the skin are rapidly converted to soap and glycerol.
Molten KOH is used to displace halides and other leaving groups. The reaction is especially useful for aromatic reagents to give the corresponding phenols.{{OrgSynth|author = W. W. Hartman|title = p-Cresol| collvol = 1|collvolpages = 175|prep = CV1P0175|year = 1923|volume = 3|pages = 37|doi = 10.15227/orgsyn.003.0037}}
=Reactions with inorganic compounds=
Complementary to its reactivity toward acids, KOH attacks oxides. Thus, SiO2 is attacked by KOH to give soluble potassium silicates. KOH reacts with carbon dioxide to give potassium bicarbonate:
:{{chem2|KOH + CO2 -> KHCO3}}
Manufacture
Historically, KOH was made by adding potassium carbonate to a strong solution of calcium hydroxide (slaked lime). The salt metathesis reaction results in precipitation of solid calcium carbonate, leaving potassium hydroxide in solution:
:{{chem2|Ca(OH)2 + K2CO3 -> CaCO3 + 2 KOH}}
Filtering off the precipitated calcium carbonate and boiling down the solution gives potassium hydroxide ("calcinated or caustic potash"). This method of producing potassium hydroxide remained dominant until the late 19th century, when it was largely replaced by the current method of electrolysis of potassium chloride solutions. The method is analogous to the manufacture of sodium hydroxide (see chloralkali process):
:{{chem2|2 KCl + 2 H2O -> 2 KOH + Cl2 + H2}}
Hydrogen gas forms as a byproduct on the cathode; concurrently, an anodic oxidation of the chloride ion takes place, forming chlorine gas as a byproduct. Separation of the anodic and cathodic spaces in the electrolysis cell is essential for this process.Römpp Chemie-Lexikon, 9th Ed. (in German)
Uses
KOH and NaOH can be used interchangeably for a number of applications, although in industry, NaOH is preferred because of its lower cost.
= Catalyst for hydrothermal gasification process =
In industry, KOH is a good catalyst for hydrothermal gasification process. In this process, it is used to improve the yield of gas and amount of hydrogen in process. For example, production of coke (fuel) from coal often produces much coking wastewater. In order to degrade it, supercritical water is used to convert it to the syngas containing carbon monoxide, carbon dioxide, hydrogen and methane. Using pressure swing adsorption, we could separate various gases and then use power-to-gas technology to convert them to fuel.{{Cite journal |date=2020-01-13 |title=Gasification of coking wastewater in supercritical water adding alkali catalyst |journal=International Journal of Hydrogen Energy |language=en |volume=45 |issue=3 |pages=1608–1614 |doi=10.1016/j.ijhydene.2019.11.033 |issn=0360-3199|last1=Chen |first1=Fu |last2=Li |first2=Xiaoxiao |last3=Qu |first3=Junfeng |last4=Ma |first4=Jing |last5=Zhu |first5=Qianlin |last6=Zhang |first6=Shaoliang |s2cid=213336330 |doi-access=free |bibcode=2020IJHE...45.1608C }} On the other hand, the hydrothermal gasification process could degrade other waste such as sewage sludge and waste from food factories.
=Precursor to other potassium compounds=
Many potassium salts are prepared by neutralization reactions involving KOH. The potassium salts of carbonate, cyanide, permanganate, phosphate, and various silicates are prepared by treating either the oxides or the acids with KOH. The high solubility of potassium phosphate is desirable in fertilizers.
=Manufacture of soft soaps=
The saponification of fats with KOH is used to prepare the corresponding "potassium soaps", which are softer than the more common sodium hydroxide-derived soaps. Because of their softness and greater solubility, potassium soaps require less water to liquefy, and can thus contain more cleaning agent than liquefied sodium soaps.{{cite book |author=K. Schumann |author2=K. Siekmann |chapter=Soaps|title=Ullmann's Encyclopedia of Industrial Chemistry |year=2005|publisher=Wiley-VCH |location=Weinheim|doi=10.1002/14356007.a24_247|isbn=978-3527306732 }}
=As an electrolyte=
Aqueous potassium hydroxide is employed as the electrolyte in alkaline batteries based on nickel-cadmium, nickel-hydrogen, and manganese dioxide-zinc. Potassium hydroxide is preferred over sodium hydroxide because its solutions are more conductive.{{cite book |author=D. Berndt |author2=D. Spahrbier |chapter=Batteries |title=Ullmann's Encyclopedia of Industrial Chemistry |year=2005 |publisher=Wiley-VCH |location=Weinheim |doi=10.1002/14356007.a03_343|isbn=978-3527306732 }} The nickel–metal hydride batteries in the Toyota Prius use a mixture of potassium hydroxide and sodium hydroxide.{{Cite web |title=Toyota Prius Hybrid 2010 Model Emergency Response Guide |publisher=Toyota Motor Corporation |year=2009 |url=http://www.toyota-tech.eu/HYBRID/ERG/EN/Prius%20ZVW30%20ERG.pdf |archive-url=https://web.archive.org/web/20120320175142/http://www.toyota-tech.eu/HYBRID/ERG/EN/Prius%20ZVW30%20ERG.pdf |archive-date=2012-03-20 |url-status=dead }} Nickel–iron batteries also use potassium hydroxide electrolyte.
=Food industry=
In food products, potassium hydroxide acts as a food thickener, pH control agent and food stabilizer. The FDA considers it generally safe as a direct food ingredient when used in accordance with Good Manufacturing Practices.{{cite web |title=Compound Summary for CID 14797 - Potassium Hydroxide |url=https://pubchem.ncbi.nlm.nih.gov/compound/potassium_hydroxide |publisher=PubChem}} It is known in the E number system as E525.
=Niche applications=
Like sodium hydroxide, potassium hydroxide attracts numerous specialized applications, virtually all of which rely on its properties as a strong chemical base with its consequent ability to degrade many materials. For example, in a process commonly referred to as "chemical cremation" or "resomation", potassium hydroxide hastens the decomposition of soft tissues, both animal and human, to leave behind only the bones and other hard tissues.{{cite journal|last=Green|first=Margaret|title=A RAPID METHOD FOR CLEARING AND STAINING SPECIMENS FOR THE DEMONSTRATION OF BONE|journal=The Ohio Journal of Science|date=January 1952|volume=52|issue=1|pages=31–33|hdl=1811/3896}} Entomologists wishing to study the fine structure of insect anatomy may use a 10% aqueous solution of KOH to apply this process.{{cite book |author=Thomas Eisner |title=For the Love of Insects |publisher=Harvard University Press |year=2003 |page=71}}
In chemical synthesis, the choice between the use of KOH and the use of NaOH is guided by the solubility or keeping quality of the resulting salt.
The corrosive properties of potassium hydroxide make it a useful ingredient in agents and preparations that clean and disinfect surfaces and materials that can themselves resist corrosion by KOH.
KOH is also used for semiconductor chip fabrication (for example anisotropic wet etching).
Potassium hydroxide is often the main active ingredient in chemical "cuticle removers" used in manicure treatments.
Because aggressive bases like KOH damage the cuticle of the hair shaft, potassium hydroxide is used to chemically assist the removal of hair from animal hides. The hides are soaked for several hours in a solution of KOH and water to prepare them for the unhairing stage of the tanning process. This same effect is also used to weaken human hair in preparation for shaving. Preshave products and some shave creams contain potassium hydroxide to force open the hair cuticle and to act as a hygroscopic agent to attract and force water into the hair shaft, causing further damage to the hair. In this weakened state, the hair is more easily cut by a razor blade.
Potassium hydroxide is used to identify some species of fungi. A 3–5% aqueous solution of KOH is applied to the flesh of a mushroom and the researcher notes whether or not the color of the flesh changes. Certain species of gilled mushrooms, boletes, polypores, and lichens{{cite book|last1=Elix|first1=J.A.|title=Lichen Biology|last2=Stocker-Wörgötter|first2=Elfie|date=2008|publisher=Cambridge University Press|isbn=978-0-521-69216-8|editor-last=Nash III|editor-first=Thomas H.|edition=2nd|location=New York|pages=118–119|chapter=Chapter 7: Biochemistry and secondary metabolites|author-link=John Alan Elix}} are identifiable based on this color-change reaction.[http://www.mushroomexpert.com/macrochemicals.html Testing Chemical Reactions] {{webarchive|url=https://web.archive.org/web/20091015000955/http://www.mushroomexpert.com/macrochemicals.html |date=2009-10-15 }} at MushroomExpert.com
Safety
Potassium hydroxide is a caustic alkali and its solutions range from irritating to skin and other tissue in low concentrations, to highly corrosive in high concentrations. Eyes are particularly vulnerable, and dust or mist is severely irritating to lungs and can cause pulmonary edema.{{Cite web |title=Hazardous Substance Fact Sheet: Potassium Hydroxide |url=https://nj.gov/health/eoh/rtkweb/documents/fs/1571.pdf |access-date=7 October 2024 |website=New Jersey Department of Health}} Safety considerations are similar to those of sodium hydroxide.
The caustic effects arise from being highly alkaline, but if potassium hydroxide is neutralised with a non-toxic acid then it becomes a non-toxic potassium salt. It is approved as a food additive under the code E525.
See also
- Potash
- Soda lime
- Saltwater soap – sailors' soap
References
{{reflist|30em}}
External links
{{Commons category}}
- [http://www.newscientistspace.com/article/dn10104 Newscientist article dn10104]
- [http://hazard.com/msds/mf/baker/baker/files/p5884.htm MSDS from JTBaker]
- [https://www.cdc.gov/niosh/npg/npgd0523.html CDC - NIOSH Pocket Guide to Chemical Hazards]
{{Potassium compounds}}
{{Hydroxides}}
{{Authority control}}
{{DEFAULTSORT:Potassium Hydroxide}}
Category:Deliquescent materials