Pyrophoric
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A substance is pyrophoric (from grc-gre, πυροφόρος, , 'fire-bearing') if it ignites spontaneously in air at or below (for gases) or within 5 minutes after coming into contact with air (for liquids and solids). Examples are organolithium compounds and
triethylborane Triethylborane (TEB), also called triethylboron, is an organoborane (a compound with a B–C bond). It is a colorless pyrophoric liquid. Its chemical formula is or , abbreviated . It is soluble in organic solvents tetrahydrofuran and hexane. Pr ...
. Pyrophoric materials are often
water-reactive Water-reactive substances are those that spontaneously undergo a chemical reaction with water, as they are highly reducing in nature. Notable examples include alkali metals, lithium through caesium, and alkaline earth metals, magnesium through bar ...
as well and will ignite when they contact water or humid air. They can be handled safely in atmospheres of
argon Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice as ...
or (with a few exceptions)
nitrogen Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
. Class D
fire extinguishers A fire extinguisher is a handheld active fire protection device usually filled with a dry or wet chemical used to extinguish or control small fires, often in emergencies. It is not intended for use on an out-of-control fire, such as one which ha ...
are designated for use in fires involving pyrophoric materials. A related concept is hypergolicity, in which two compounds spontaneously ignite when mixed.


Uses

The creation of sparks from metals is based on the pyrophoricity of small metal particles, and pyrophoric alloys are made for this purpose. The sparking mechanisms in
lighter A lighter is a portable device which creates a flame, and can be used to ignite a variety of items, such as cigarettes, gas lighter, fireworks, candles or campfires. It consists of a metal or plastic container filled with a flammable liquid or ...
s and various toys, using ferrocerium; starting fires without matches, using a
firesteel A fire striker is a piece of carbon steel from which sparks are struck by the sharp edge of flint, chert or similar rock. It is a specific tool used in fire making. History In early times, percussion fire making was often used to start fir ...
; the
flintlock Flintlock is a general term for any firearm that uses a flint-striking ignition mechanism, the first of which appeared in Western Europe in the early 16th century. The term may also apply to a particular form of the mechanism itself, also know ...
mechanism in firearms; and spark testing ferrous metals.


Handling

Small amounts of pyrophoric liquids are often supplied in a glass bottle with a polytetrafluoroethylene-lined septum. Larger amounts are supplied in metal tanks similar to gas cylinders, designed so a needle can fit through the valve opening. A syringe, carefully dried and flushed of air with an
inert gas An inert gas is a gas that does not readily undergo chemical reactions with other chemical substances and therefore does not readily form chemical compounds. The noble gases often do not react with many substances and were historically referred to ...
, is used to extract the liquid from its container. When working with pyrophoric solids, researchers often employ a sealed
glove box A glovebox (or glove box) is a sealed container that is designed to allow one to manipulate objects where a separate atmosphere is desired. Built into the sides of the glovebox are gloves arranged in such a way that the user can place their hand ...
flushed with inert gas. Since these specialized glove boxes are expensive and require specialized and frequent maintenance, many pyrophoric solids are sold as solutions, or dispersions in mineral oil or lighter
hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...
solvents, so they can be handled in the atmosphere of the laboratory, while still maintaining an oxygen- and moisture-free environment. Mildly pyrophoric solids such as
lithium aluminum hydride Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic compound with the chemical formula Li Al H4. It is a white solid, discovered by Finholt, Bond and Schlesinger in 1947. This compound is used as a reducing agent in organic sy ...
and sodium hydride can be handled in the air for brief periods of time, but the containers must be flushed with inert gas before the material is returned to the container for storage.


Pyrophoric materials


Solids

*
White phosphorus Elemental phosphorus can exist in several allotropes, the most common of which are white and red solids. Solid violet and black allotropes are also known. Gaseous phosphorus exists as diphosphorus and atomic phosphorus. White phosphorus White ...
* Alkali metals, especially
potassium Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosph ...
, rubidium, caesium, including the alloy NaK * Finely divided metals (
iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundanc ...
,
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
,
magnesium Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ta ...
,
calcium Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar t ...
,
zirconium Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'' ...
,
uranium Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
,
titanium Titanium is a chemical element with the Symbol (chemistry), symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resista ...
,
tungsten Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isol ...
,
bismuth Bismuth is a chemical element with the symbol Bi and atomic number 83. It is a post-transition metal and one of the pnictogens, with chemical properties resembling its lighter group 15 siblings arsenic and antimony. Elemental bismuth occurs ...
,
hafnium Hafnium is a chemical element with the symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dmitri M ...
,
thorium Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high ...
, osmium,
neodymium Neodymium is a chemical element with the symbol Nd and atomic number 60. It is the fourth member of the lanthanide series and is considered to be one of the rare-earth metals. It is a hard, slightly malleable, silvery metal that quickly tarnishe ...
) * Some metals and alloys in bulk form (
cerium Cerium is a chemical element with the symbol Ce and atomic number 58. Cerium is a soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it often shows the +3 ...
,
plutonium Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exhibi ...
) *
Alkylate An alkylation unit (alky) is one of the conversion processes used in petroleum refineries. It is used to convert isobutane and low-molecular-weight alkenes (primarily a mixture of propene and butene) into alkylate, a high octane gasoline componen ...
d metal alkoxides or nonmetal
halides In chemistry, a halide (rarely halogenide) is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a fluor ...
(diethylethoxyaluminium, dichloro(methyl)silane) *
Potassium graphite Graphite intercalation compounds are complex materials having a formula where the ion or is inserted ( intercalated) between the oppositely charged carbon layers. Typically ''m'' is much less than 1. These materials are deeply colored solids t ...
(KC8) * Metal
hydride In chemistry, a hydride is formally the anion of hydrogen( H−). The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride ...
s ( sodium hydride, lithium aluminium hydride, uranium trihydride) * Partially or fully alkylated derivatives of metal and nonmetal hydrides (diethylaluminium hydride, trimethylaluminium,
triethylaluminium Triethylaluminium is one of the simplest examples of an organoaluminium compound. Despite its name it has the formula Al2( C2H5)6 (abbreviated as Al2Et6 or TEA), as it exists as a dimer. This colorless liquid is pyrophoric. It is an industrially ...
,
butyllithium Butyllithium may refer to one of 5 isomeric organolithium reagents of which 3 are commonly used in chemical synthesis: * ''n''-Butyllithium, abbreviated BuLi or nBuLi * ''sec''-Butyllithium, abbreviated ''sec''-BuLi or sBuLi, has 2 stereoisomers, ...
), with a few exceptions (i.e. dimethylmercury and
tetraethyllead Tetraethyllead (commonly styled tetraethyl lead), abbreviated TEL, is an organolead compound with the formula Pb( C2H5)4. It is a fuel additive, first being mixed with gasoline beginning in the 1920s as a patented octane rating booster that ...
) *
Copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkis ...
fuel cell catalysts (
zinc oxide Zinc oxide is an inorganic compound with the formula . It is a white powder that is insoluble in water. ZnO is used as an additive in numerous materials and products including cosmetics, food supplements, rubbers, plastics, ceramics, glass, cement ...
, aluminium oxide) *
Grignard reagents A Grignard reagent or Grignard compound is a chemical compound with the general formula , where X is a halogen and R is an organic group, normally an alkyl or aryl. Two typical examples are methylmagnesium chloride and phenylmagnesium bromide . ...
(compounds of the form RMgX) * Used
hydrogenation Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate organ ...
catalysts Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
such as palladium on carbon or Raney nickel (especially hazardous because of the adsorbed hydrogen) * Iron sulfide: often encountered in oil and gas facilities, where corrosion products in steel plant equipment can ignite if exposed to air *
Lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
and
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon mak ...
powders produced from decomposition of
lead citrate Lead citrate is a compound of lead and citrate that is primarily used as an enhancer for heavy metal staining in electron microscopy. It binds to osmium and uranyl acetate Uranyl acetate is the acetate salt of uranium oxide, a toxic yellow-gr ...
*
Uranium Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
, as shown in the disintegration of depleted uranium penetrator rounds into burning dust upon impact with their targets; in finely divided form it is readily ignitable, and uranium scrap from machining operations is subject to spontaneous ignition *
Neptunium Neptunium is a chemical element with the symbol Np and atomic number 93. A radioactive actinide metal, neptunium is the first transuranic element. Its position in the periodic table just after uranium, named after the planet Uranus, led to it bein ...
* Several compounds of
plutonium Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exhibi ...
are pyrophoric, and they cause some of the most serious fires occurring in
United States Department of Energy The United States Department of Energy (DOE) is an executive department of the U.S. federal government that oversees U.S. national energy policy and manages the research and development of nuclear power and nuclear weapons in the United Stat ...
facilitiesDOE , Office of Health, Safety and Security , Nuclear Safety and Environment , Plutonium
, retrieved 3 September 2013

on 28 September 2010.
*Petroleum hydrocarbon (PHC) sludge


Liquids

*
Diphosphane Diphosphane, or diphosphine, is an inorganic compound with the chemical formula P2H4. This colourless liquid is one of several binary phosphorus hydrides. It is the impurity that typically causes samples of phosphine to ignite in air. Propert ...
*
Metalorganics Metal-organic compounds (jargon: metalorganics, metallo-organics) are a class of chemical compounds that contain metals and organic ligands, which confer solubility in organic solvents or volatility. Compounds with these properties find applicatio ...
of main group metals (e.g.
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
, gallium,
indium Indium is a chemical element with the symbol In and atomic number 49. Indium is the softest metal that is not an alkali metal. It is a silvery-white metal that resembles tin in appearance. It is a post-transition metal that makes up 0.21 parts ...
,
zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
,
cadmium Cadmium is a chemical element with the symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12, zinc and mercury. Like zinc, it demonstrates oxidation state +2 in most of ...
, etc.) *
Triethylborane Triethylborane (TEB), also called triethylboron, is an organoborane (a compound with a B–C bond). It is a colorless pyrophoric liquid. Its chemical formula is or , abbreviated . It is soluble in organic solvents tetrahydrofuran and hexane. Pr ...
* ''tert''-Butyllithium *
Diethylzinc Diethylzinc (C2H5)2Zn, or DEZ, is a highly pyrophoric and reactive organozinc compound consisting of a zinc center bound to two ethyl groups. This colourless liquid is an important reagent in organic chemistry. It is available commercially as a ...
*
Triethylaluminium Triethylaluminium is one of the simplest examples of an organoaluminium compound. Despite its name it has the formula Al2( C2H5)6 (abbreviated as Al2Et6 or TEA), as it exists as a dimer. This colorless liquid is pyrophoric. It is an industrially ...
* Linseed oil; rags soaked in linseed oil can self-ignite Hydrazine is
hypergolic A hypergolic propellant is a rocket propellant combination used in a rocket engine, whose components spontaneously ignite when they come into contact with each other. The two propellant components usually consist of a fuel and an oxidizer. T ...
with oxidants like dinitrogen tetroxide or
hydrogen peroxide Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3% ...
, but not truly pyrophoric.


Gases

* Nonmetal
hydride In chemistry, a hydride is formally the anion of hydrogen( H−). The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride ...
s ( arsine,
phosphine Phosphine (IUPAC name: phosphane) is a colorless, flammable, highly toxic compound with the chemical formula , classed as a pnictogen hydride. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like rotting ...
,
diborane Diborane(6), generally known as diborane, is the chemical compound with the formula B2H6. It is a toxic, colorless, and pyrophoric gas with a repulsively sweet odor. Diborane is a key boron compound with a variety of applications. It has attracte ...
, germane,
silane Silane is an inorganic compound with chemical formula, . It is a colourless, pyrophoric, toxic gas with a sharp, repulsive smell, somewhat similar to that of acetic acid. Silane is of practical interest as a precursor to elemental silicon. Sila ...
) *
Metal carbonyl Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe c ...
s ( dicobalt octacarbonyl,
nickel carbonyl Nickel carbonyl (IUPAC name: tetracarbonylnickel) is a nickel(0) organometallic compound with the formula Ni(CO)4. This colorless liquid is the principal carbonyl of nickel. It is an intermediate in the Mond process for producing very high-pu ...
)


Explanatory notes


References


External links


US Dept. of Energy Handbook, "Primer on Spontaneous Heating and Pyrophoricity"
(archived) * *{{cite web , title=Pyrophoric Chemicals Guide , url=http://www.dehs.umn.edu/PDFs/PyrophoricMaterialsListAppendix.pdf , website=Environmental Health and Safety , publisher=University of Minnesota , access-date=27 March 2021 , archive-url=https://web.archive.org/web/20141031032636/http://www.dehs.umn.edu/PDFs/PyrophoricMaterialsListAppendix.pdf , archive-date=31 October 2014 , language=English , url-status=dead Chemical properties Firelighting sv:Självantändning#Pyrofora ämnen zh:自燃