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Potassium nitrate

From Wikipedia, the free encyclopedia
"Saltpeter" redirects here. For other uses, seeSaltpeter (disambiguation).
Potassium nitrate[1]
Potassium nitrate
Names
IUPAC name
Potassium nitrate
Other names
  • Saltpeter
  • Saltpetre
  • Nitrate of potash
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.028.926Edit this at Wikidata
EC Number
  • 231-818-8
E number E252(preservatives)
KEGG
RTECS number
  • TT3700000
UNII
UN number 1486
  • InChI=1S/K.NO3/c;2-1(3)4/q+1;-1checkY
    Key: FGIUAXJPYTZDNR-UHFFFAOYSA-NcheckY
  • InChI=1/K.NO3/c;2-1(3)4/q+1;-1
    Key: FGIUAXJPYTZDNR-UHFFFAOYAM
  • [K+].[O-][N+]([O-])=O
Properties
KNO3
Molar mass 101.1032 g/mol
Appearance white solid
Odor odorless
Density 2.109 g/cm3(16 °C)
Melting point 334 °C (633 °F; 607 K)
Boiling point 400 °C (752 °F; 673 K) (decomposes)
133 g/1000 g water (0 °C)
316 g/1000 g water (20 °C)
383 g/1000 g water (25 °C)
2439 g/1000 g water (100 °C)[2]
Solubility slightly soluble inethanol
soluble inglycerol,ammonia
Basicity(pKb) 15.3[3]
−33.7·10−6cm3/mol
1.335, 1.5056, 1.5604
Structure
Orthorhombic,Aragonite
Thermochemistry
95.06 J/mol K
-494.00 kJ/mol
Hazards
Occupational safety and health(OHS/OSH):
Main hazards
 Oxidant, harmful if swallowed, inhaled, or absorbed on skin. Causes irritation to skin and eye area.
GHSlabelling:
GHS03: OxidizingGHS07: Exclamation mark
H272,H315,H319,H335
P102,P210,P220,P221,P280
NFPA 704(fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazard OX: Oxidizer. E.g. potassium perchlorate
1
0
0
OX
Flash point non-flammable (oxidizer)
Lethal doseor concentration (LD, LC):
1901 mg/kg (oral, rabbit)
3750 mg/kg (oral, rat)[4]
Safety data sheet(SDS) ICSC 0184
Related compounds
Otheranions
 Potassium nitrite
Othercations
 Lithium nitrate
Sodium nitrate
Rubidium nitrate
Caesium nitrate
Related compounds
 Potassium sulfate
Potassium chloride
Supplementary data page
Potassium nitrate (data page)
Except where otherwise noted, data are given for materials in theirstandard state(at 25 °C [77 °F], 100 kPa).

Potassium nitrateis achemical compoundwith a sharp, salty, bitter taste and thechemical formulaKNO
3.It is anionic saltofpotassium ionsK+andnitrate ionsNO3−,and is therefore analkali metal nitrate.It occurs in nature as a mineral,niter(ornitreoutside the US).[5]It is a source ofnitrogen,and nitrogen was named after niter. Potassium nitrate is one of several nitrogen-containing compounds collectively referred to assaltpeter(orsaltpetreoutside the US).[5]

Major uses of potassium nitrate are infertilizers,tree stump removal,rocket propellantsandfireworks.It is one of the major constituents ofgunpowder(black powder).[6]Inprocessed meats,potassium nitrate reacts withhemoglobinandmyoglobingenerating a red color.[7]

Etymology[edit]

Nitre, or potassium nitrate, because of its early and global use and production, has many names.

As for nitrate, Hebrew and Egyptian words for it had the consonants n-t-r, indicating likelycognationin the Greeknitron,which was Latinised tonitrumornitrium.Thence Old French hadniterand Middle Englishnitre.By the 15th century, Europeans referred to it assaltpetre,[8]specifically Indian saltpetre (Chilean saltpetre is sodium nitrate[9]) and later asnitrate of potash,as the chemistry of the compound was more fully understood.

The Arabs called it "Chinese snow" (Arabic:ثلج الصين,romanized:thalj al-ṣīn) as well asbārūd(بارود), a term of uncertain origin that later came to meangunpowder.It was called "Chinese salt" by the Iranians/Persians[10][11][12]or "salt from Chinese salt marshes" (Persian:نمک شوره چينیnamak shūra chīnī).[13]: 335 [14]TheTiangong Kaiwu,published in the 17th century by members of theQing dynasty,detailed the production of gunpowder and other useful products from nature.

Historical production[edit]

See also:Nitre § Availability

From mineral sources[edit]

InMauryan Indiasaltpeter manufacturers formed the Nuniya & Labana caste.[15]Saltpeter finds mention inKautilya'sArthashastra(compiled 300BC – 300AD), which mentions using its poisonous smoke as a weapon of war,[16]although its use for propulsion did not appear until medieval times.

A purification process for potassium nitrate was outlined in 1270 by the chemist and engineerHasan al-RammahofSyriain his bookal-Furusiyya wa al-Manasib al-Harbiyya(The Book ofMilitary Horsemanshipand Ingenious War Devices). In this book, al-Rammah describes first the purification ofbarud(crude saltpeter mineral) by boiling it with minimal water and using only the hot solution, then the use ofpotassium oxide(in the form ofwood ashes) to remove calcium and magnesium by precipitation of their carbonates from this solution, leaving a solution of purified potassium nitrate, which could then be dried.[17]This was used for the manufacture of gunpowder and explosive devices. The terminology used by al-Rammah indicated the gunpowder he wrote about originated in China.[18]

At least as far back as 1845,nitratitedeposits were exploited in Chile and California.

From caves[edit]

Major natural sources of potassium nitrate were the deposits crystallizing from cave walls and the accumulations ofbat guanoin caves.[19]Extraction is accomplished by immersing the guano in water for a day, filtering, and harvesting the crystals in the filtered water. Traditionally, guano was the source used inLaosfor the manufacture of gunpowder forBang Fairockets.[20]

Calcium nitrate,orlime saltpetre,was discovered on the walls of stables, from the urine of barnyard animals.[9]

Nitraries[edit]

See also:Saltpetre works

Potassium nitrate was produced in anitraryor "saltpetre works".[21]The process involved burial of excrements (human or animal) in a field beside the nitraries, watering them and waiting until leaching allowed saltpeter to migrate to the surface byefflorescence.Operators then gathered the resulting powder and transported it to be concentrated byebullitionin the boiler plant.[22][23]

Besides "Montepellusanus",during the thirteenth century (and beyond) the only supply of saltpeter across Christian Europe (according to" De Alchimia "in 3 manuscripts of Michael Scot, 1180–1236) was" found in Spain in Aragon in a certain mountain near the sea ".[13]: 89, 311 [24]

In 1561,Elizabeth I,Queen of England and Ireland, who was at war withPhilip II of Spain,became unable to import saltpeter (of which theKingdom of Englandhad no home production), and had to pay "300 pounds gold" to the German captain Gerrard Honrik for the manual "Instructions for making saltpeter to growe" (the secret of the "Feuerwerkbuch"-the nitraries-).[25]

Nitre bed[edit]

Anitre bedis a similar process used to produce nitrate from excrement. Unlike the leaching-based process of the nitrary, however, one mixes the excrements with soil and waits for soil microbes to convert amino-nitrogen into nitrates bynitrification.The nitrates are extracted from soil with water and then purified into saltpeter by adding wood ash. The process was discovered in the early 15th century and was very widely used until the Chilean mineral deposits were found.[26]

The Confederate side of the American Civil War had a significant shortage of saltpeter. As a result, theNitre and Mining Bureauwas set up to encourage local production, including by nitre beds and by providing excrement to government nitraries. On November 13, 1862, the government advertised in the Charleston Daily Courier for 20 or 30 "able bodied Negro men" to work in the new nitre beds at Ashley Ferry, S.C. The nitre beds were large rectangles of rotted manure and straw, moistened weekly with urine, "dung water", and liquid from privies, cesspools and drains, and turned over regularly. The National Archives published payroll records that account for more than 29,000 people compelled to such labor in the state of Virginia. The South was so desperate for saltpeter for gunpowder that one Alabama official reportedly placed a newspaper ad asking that the contents of chamber pots be saved for collection. In South Carolina, in April 1864, the Confederate government forced 31 enslaved people to work at the Ashley Ferry Nitre Works, outside Charleston.[27]

Perhaps the most exhaustive discussion of the niter-bed production is the 1862LeContetext.[28]He was writing with the express purpose of increasing production in theConfederate Statesto support their needs during theAmerican Civil War.Since he was calling for the assistance of rural farming communities, the descriptions and instructions are both simple and explicit. He details the "French Method", along with several variations, as well as a "Swiss method". N.B. Many references have been made to a method using only straw and urine, but there is no such method in this work.

French method[edit]

TurgotandLavoisiercreated theRégie des Poudres et Salpêtresa few years before theFrench Revolution.Niter-beds were prepared by mi xingmanurewith eithermortaror wood ashes, common earth and organic materials such asstrawto give porosity to a compost pile typically 4 feet (1.2 m) high, 6 feet (1.8 m) wide, and 15 feet (4.6 m) long.[28]The heap was usually under a cover from the rain, kept moist withurine,turned often to accelerate the decomposition, then finallyleachedwith water after approximately one year, to remove the solublecalcium nitratewhich was then converted to potassium nitrate by filtering throughpotash.

Swiss method[edit]

Joseph LeContedescribes a process using only urine and not dung, referring to it as theSwiss method.Urine is collected directly, in a sandpit under a stable. The sand itself is dug out and leached for nitrates which are then converted to potassium nitrate using potash, as above.[29]

From nitric acid[edit]

From 1903 until theWorld War Iera, potassium nitrate for black powder and fertilizer was produced on an industrial scale from nitric acid produced using theBirkeland–Eyde process,which used an electric arc to oxidize nitrogen from the air. During World War I the newly industrializedHaber process(1913) was combined with theOstwald processafter 1915, allowing Germany to produce nitric acid for the war after being cut off from its supplies of mineral sodium nitrates from Chile (seenitratite).

Modern production[edit]

Potassium nitrate can be made by combiningammonium nitrateandpotassium hydroxide.

NH4NO3+ KOH → NH3+ KNO3+ H2O

An alternative way of producing potassium nitrate without a by-product of ammonia is to combine ammonium nitrate, found ininstant ice packs,[30]andpotassium chloride,easily obtained as a sodium-freesalt substitute.

NH4NO3+ KCl → NH4Cl + KNO3

Potassium nitrate can also be produced by neutralizingnitric acidwith potassium hydroxide. This reaction is highly exothermic.

KOH + HNO3→ KNO3+ H2O

On industrial scale it is prepared by the double displacement reaction betweensodium nitrateand potassium chloride.

NaNO3+ KCl → NaCl + KNO3

Properties[edit]

Potassium nitrate has anorthorhombiccrystal structure at room temperature,[31]which transforms to a trigonal system at 128 °C (262 °F). On cooling from 200 °C (392 °F), another trigonal phase forms between 124 °C (255 °F) and 100 °C (212 °F).[32][33]

Sodium nitrateis isomorphous withcalcite,the most stable form ofcalcium carbonate,whereas room-temperature potassium nitrate isisomorphouswitharagonite,a slightly less stablepolymorphof calcium carbonate. The difference is attributed to the similarity in size betweennitrate(NO−3) andcarbonate(CO2−3) ions and the fact that the potassium ion (K+) is larger than sodium (Na+) and calcium (Ca2+) ions.[34]

In the room-temperature structure of potassium nitrate, each potassium ion is surrounded by 6 nitrate ions. In turn, each nitrate ion is surrounded by 6 potassium ions.[31]

Room temperaturecrystal structureandcoordination geometryof potassium nitrate[31]
Unit cell Potassium coordination Nitrate coordination

Potassium nitrate is moderately soluble in water, but its solubility increases with temperature. The aqueous solution is almost neutral, exhibitingpH6.2 at 14 °C (57 °F) for a 10% solution of commercial powder. It is not veryhygroscopic,absorbing about 0.03% water in 80%relative humidityover 50 days. It is insoluble in alcohol and is not poisonous; it can react explosively withreducing agents,but it is not explosive on its own.[2]

Thermal decomposition[edit]

Between 550–790 °C (1,022–1,454 °F), potassium nitrate reaches a temperature-dependent equilibrium withpotassium nitrite:[35]

2 KNO3⇌ 2 KNO2+ O2

Uses[edit]

Potassium nitrate has a wide variety of uses, largely as a source of nitrate.

Nitric acid production[edit]

Historically,nitric acidwas produced by combining sulfuric acid with nitrates such as saltpeter. In modern times this is reversed: nitrates are produced from nitric acid produced via theOstwald process.

Oxidizer[edit]

A demonstration of the oxidation of a piece ofcharcoalin molten potassium nitrate

The most famous use of potassium nitrate is probably as the oxidizer inblackpowder.From the most ancient times until the late 1880s, blackpowder provided the explosive power for all the world's firearms. After that time, small arms and large artillery increasingly began to depend oncordite,asmokeless powder.Blackpowder remains in use today inblack powder rocket motors,but also in combination with other fuels like sugars in "rocket candy"(a popular amateur rocket propellant). It is also used in fireworks such assmoke bombs.[36]It is also added to cigarettes to maintain an even burn of the tobacco[37]and is used to ensure complete combustion ofpaper cartridgesfor cap and ball revolvers.[38]It can also be heated to several hundred degrees to be used forniter bluing,which is less durable than other forms of protective oxidation, but allows for specific and often beautiful coloration of steel parts, such as screws, pins, and other small parts of firearms.

Meat processing[edit]

Potassium nitrate has been a common ingredient of salted meat sinceantiquity[39]or theMiddle Ages.[40]The widespread adoption of nitrate use is more recent and is linked to the development of large-scale meat processing.[6]The use of potassium nitrate has been mostly discontinued because it gives slow and inconsistent results compared withsodium nitritepreparations such as "Prague powder" or pink "curing salt".Even so, potassium nitrate is still used in some food applications, such as salami, dry-cured ham,charcuterie,and (in some countries) in thebrineused to makecorned beef(sometimes together with sodium nitrite).[41]When used as a food additive in the European Union,[42]the compound is referred to asE252;it is also approved for use as a food additive in the United States[43]and Australia and New Zealand[44](where it is listed under itsINS number252).[2]

Possible cancer risk[edit]

Since October 2015,WHOclassifies processed meat as Group 1 carcinogen (based on epidemiological studies, convincinglycarcinogenicto humans).[45]

In April 2023 the French Court of Appeals of Limoges confirmed that food-watch NGO Yuka was legally legitimate in describing Potassium NitrateE249 to E252as a "cancer risk", and thus rejected an appeal by the Frenchcharcuterieindustry against the organisation.[46]

Food preparation[edit]

In West African cuisine, potassium nitrate (saltpetre) is widely used as a thickening agent in soups and stews such asokra soup[47]andisi ewu.It is also used to soften food and reduce cooking time when boilingbeansand tough meat. Saltpetre is also an essential ingredient in making special porridges, such askunun kanwa[48]literally translated from theHausa languageas "saltpetre porridge".

In the Shetland Islands (UK) it is used in the curing of mutton to makereestit mutton,a local delicacy.[49]

Fertilizer[edit]

Potassium nitrate is used infertilizersas a source of nitrogen and potassium – two of themacronutrientsfor plants. When used by itself, it has anNPK ratingof 13-0-44.[50][51]

Pharmacology[edit]

Other uses[edit]

In folklore and popular culture[edit]

Potassium nitrate was once thought to induceimpotence,and is still rumored to be in institutional food (such as military fare) as ananaphrodisiac;however, there is no scientific evidence for such properties.[66][67]

InBank Shot,El (Joanna Cassidy) propositions Walter Ballantine (George C. Scott), who tells her that he has been fed saltpeter in prison. "You know why they feed you saltpeter in prison?" Ballantine asks her. She shakes her head no. They kiss. He glances down at his crotch, making a gesture that reveals his body has not responded to her advances, and says, "That's why they feed you saltpeter in prison."

InOne Flew Over the Cuckoo's Nest,Randle is asked by the nurses to take his medications, but not knowing what they are, he mentions he does not want anyone to "slip me saltpeter". He then proceeds to imitate the motions of masturbation in reference to its supposed effects as ananaphrodisiac.

In1776,John Adams asks his wife Abigail to make saltpeter for the Continental Army. She, eventually, is able to do so in exchange for pins for sewing.[68]

In theStar Trekepisode "Arena",Captain Kirkinjures agornusing a rudimentary cannon that he constructs using potassium nitrate as a key ingredient ofgunpowder.

In21 Jump Street,Jenko, played byChanning Tatum,gives a rhyming presentation about potassium nitrate for his chemistry class.

InEating Raoul,Paul hires adominatrixto impersonate a nurse and trick Raoul into consuming saltpeter in a ploy to reduce his sexual appetite for his wife.

InThe Simpsonsepisode "El Viaje Misterioso de Nuestro Jomer (The Mysterious Voyage of Our Homer)",Mr. Burns is seen pouring saltpeter into his chili entry, titled Old Elihu's Yale-Style Saltpeter Chili.

In theSharpenovel seriesbyBernard Cornwell,numerous mentions are made of an advantageous supply of saltpeter from India being a crucial component of British military supremacy in the Napoleonic Wars. InSharpe's Havoc,the French Captain Argenton laments that France needs to scrape its supply fromcesspits.

In theDr Stoneanime and manga series, the struggle for control over a natural saltpeter source from guano features prominently in the plot.

In the farming lore from theCorn Beltof the 1800s, drought-killed corn[69]in manured fields could accumulate saltpeter to the extent that upon opening the stalk for examination it would "fall as a fine powder upon the table".[70]

See also[edit]

References[edit]

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  2. ^abcB. J. Kosanke; B. Sturman; K. Kosanke; et al. (2004)."2".Pyrotechnic Chemistry.Journal of Pyrotechnics. pp. 5–6.ISBN978-1-889526-15-7.Archivedfrom the original on 2016-05-05.
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  10. ^Peter Watson (2006).Ideas: A History of Thought and Invention, from Fire to Freud.HarperCollins. p. 304.ISBN978-0-06-093564-1.Archivedfrom the original on 2015-10-17.
  11. ^Cathal J. Nolan (2006).The age of wars of religion, 1000–1650: an encyclopedia of global warfare and civilization.Vol. 1 of Greenwood encyclopedias of modern world wars. Greenwood Publishing Group. p. 365.ISBN978-0-313-33733-8.Archivedfrom the original on 2014-01-01.Retrieved2011-11-28.In either case, there is linguistic evidence of Chinese origins of the technology: in Damascus, Arabs called the saltpeter used in making gunpowder "Chinese snow," while in Iran it was called "Chinese salt."
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