Nitric acid
 Pure nitric acid
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| Names | |||
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| IUPAC name
Nitric acid
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Other names
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| Identifiers | |||
3D model (JSmol)
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| 3DMet | |||
| ChEBI | |||
| ChEMBL | |||
| ChemSpider | |||
| ECHA InfoCard | 100.028.832 | ||
| EC Number |
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| 1576 | |||
| KEGG | |||
| MeSH | Nitric+acid | ||
PubChemCID
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| RTECS number |
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| UNII | |||
| UN number | 2031 | ||
CompTox Dashboard(EPA)
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| Properties | |||
| HNO3 | |||
| Molar mass | 63.012g·mol−1 | ||
| Appearance | Colorless liquid[1] | ||
| Odor | Acrid, suffocating[1] | ||
| Density | 1.51 g/cm3,1.41 g/cm3[68% w/w] | ||
| Melting point | −42 °C (−44 °F; 231 K) | ||
| Boiling point | 83 °C (181 °F; 356 K) 68% solution boils at 121 °C (250 °F; 394 K) | ||
| Miscible | |||
| logP | −0.13[2] | ||
| Vapor pressure | 48 mmHg (20 °C)[1] | ||
| Acidity(pKa) | −1.4[3] | ||
| Conjugate base | Nitrate | ||
| −1.99×10−5cm3/mol | |||
Refractive index(nD)
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1.397 (16.5 °C) | ||
| 2.17 ± 0.02 D | |||
| Thermochemistry | |||
Std molar
entropy(S⦵298) |
146 J/(mol·K)[4] | ||
Std enthalpy of
formation(ΔfH⦵298) |
−207 kJ/mol[4] | ||
| Hazards | |||
| GHSlabelling: | |||
  
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| Danger | |||
| H272,H290,H314,H331 | |||
| P210,P220,P280,P303+P361+P353,P304+P340+P310,P305+P351+P338 | |||
| NFPA 704(fire diamond) | |||
| Flash point | Non-flammable | ||
| Lethal doseor concentration (LD, LC): | |||
LC50(median concentration)
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138 ppm (rat, 30 min)[1] | ||
| NIOSH(US health exposure limits): | |||
PEL(Permissible)
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TWA 2 ppm (5 mg/m3)[1] | ||
REL(Recommended)
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TWA 2 ppm (5 mg/m3) ST 4 ppm (10 mg/m3)[1] | ||
IDLH(Immediate danger)
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25 ppm[1] | ||
| Safety data sheet(SDS) | ICSC 0183 | ||
| Related compounds | |||
Otheranions
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Nitrous acid | ||
Othercations
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Related compounds
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Except where otherwise noted, data are given for materials in theirstandard state(at 25 °C [77 °F], 100 kPa).
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Nitric acidis aninorganic compoundwith the formulaHNO3.It is a highlycorrosivemineral acid.[6]The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition intooxides of nitrogen.Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86%HNO3,it is referred to asfuming nitric acid.Depending on the amount ofnitrogen dioxidepresent, fuming nitric acid is further characterized asred fuming nitric acidat concentrations above 86%, orwhite fuming nitric acidat concentrations above 95%.
Nitric acid is the primary reagent used fornitration– the addition of anitro group,typically to anorganic molecule.While some resultingnitro compoundsare shock- and thermally-sensitiveexplosives,a few are stable enough to be used in munitions and demolition, while others are still more stable and used as synthetic dyes and medicines (e.gmetronidazole). Nitric acid is also commonly used as astrong oxidizing agent.
History
Medieval alchemy
The discovery ofmineral acidssuch as nitric acid is generally believed to go back to 13th-century Europeanalchemy.[7]The conventional view is that nitric acid was first described inpseudo-Geber'sDe inventione veritatis( "On the Discovery of Truth", afterc. 1300).[8]
However, according toEric John HolmyardandAhmad Y. al-Hassan,the nitric acid also occurs in various earlierArabic workssuch as theṢundūq al-ḥikma( "Chest of Wisdom" ) attributed toJabir ibn Hayyan(8th century) or theTaʿwīdh al-Ḥākimattributed to the Fatimid caliphal-Hakim bi-Amr Allah(985–1021).[9]
The recipe in theṢundūq al-ḥikmaattributed to Jabir has been translated as follows:[10][11]
Take five parts ofpure flowers of nitre,three parts ofCyprus vitrioland two parts of Yemenalum.Powder them well, separately, until they are like dust and then place them in a flask. Plug the latter with a palm fibre and attach a glass receiver to it. Then invert the apparatus and heat the upper portion (i.e. the flask containing the mixture) with a gentle fire. There will flow down by reason of the heat an oil like cow's butter.
Nitric acid is also found in post-1300 worksfalsely attributedtoAlbert the GreatandRamon Llull(both 13th century). These works describe the distillation of a mixture containing niter andgreen vitriol,which they call "eau forte" (aqua fortis).[12][13][14]
Modern era
In the 17th century,Johann Rudolf Glauberdevised a process to obtain nitric acid by distilling potassium nitrate with sulfuric acid. In 1776Antoine LavoisiercitedJoseph Priestley's work to point out that it can be converted from nitric oxide (which he calls "nitrous air" ), "combined with an approximately equal volume of the purest part of common air, and with a considerable quantity of water."[15][a]In 1785Henry Cavendishdetermined its precise composition and showed that it could be synthesized by passing a stream ofelectric sparksthrough moistair.[12]In 1806,Humphry Davyreported the results of extensive distilled water electrolysis experiments concluding that nitric acid was produced at the anode from dissolved atmospheric nitrogen gas. He used a high voltage battery and non-reactive electrodes and vessels such as gold electrode cones that doubled as vessels bridged by damp asbestos.[16]
The industrial production of nitric acid from atmospheric air began in 1905 with theBirkeland–Eyde process,also known as the arc process.[17]This process is based upon the oxidation of atmospheric nitrogen by atmospheric oxygen to nitric oxide with a very high temperature electric arc. Yields of up to approximately 4–5% nitric oxide were obtained at 3000 °C, and less at lower temperatures.[17][18]The nitric oxide was cooled and oxidized by the remaining atmospheric oxygen to nitrogen dioxide, and this was subsequently absorbed in water in a series ofpacked columnorplate columnabsorption towers to produce dilute nitric acid. The first towers bubbled the nitrogen dioxide through water and non-reactive quartz fragments. About 20% of the produced oxides of nitrogen remained unreacted so the final towers contained an alkali solution to neutralize the rest.[19]The process was very energy intensive and was rapidly displaced by the Ostwald process once cheap ammonia became available.
Another early production method was invented by French engineer Albert Nodon around 1913. His method produced nitric acid from electrolysis of calcium nitrate converted by bacteria from nitrogenous matter in peat bogs. An earthenware pot surrounded by limestone was sunk into the peat and staked with tarred lumber to make a compartment for the carbon anode around which the nitric acid is formed. Nitric acid was pumped out from an earthenware[20]pipe that was sunk down to the bottom of the pot. Fresh water was pumped into the top through another earthenware pipe to replace the fluid removed. The interior was filled withcoke.Cast iron cathodes were sunk into the peat surrounding it. Resistance was about 3 ohms per cubic meter and the power supplied was around 10 volts. Production from one deposit was 800 tons per year.[20][21]
Once theHaber processfor the efficient production of ammonia was introduced in 1913, nitric acid production from ammonia using theOstwald processovertook production from the Birkeland–Eyde process. This method of production is still in use today.
Physical and chemical properties
Commercially available nitric acid is anazeotropewith water at a concentration of 68%HNO3.This solution has a boiling temperature of 120.5 °C (249 °F) at 1 atm. It is known as "concentrated nitric acid". The azeotrope of nitric acid and water is a colourless liquid at room temperature.
Two solid hydrates are known: the monohydrateHNO3·H2Oor oxonium nitrate[H3O]+[NO3]−and the trihydrateHNO3·3H2O.
An older density scale is occasionally seen, with concentrated nitric acid specified as 42Baumé.[22]
Contamination with nitrogen dioxide
Nitric acid is subject tothermalor light decomposition and for this reason it was often stored in brown glass bottles:
- 4 HNO3→ 2 H2O + 4 NO2+ O2
This reaction may give rise to some non-negligible variations in the vapor pressure above the liquid because the nitrogen oxides produced dissolve partly or completely in the acid.
The nitrogen dioxide (NO2) and/or dinitrogen tetroxide (N2O4) remains dissolved in the nitric acid coloring it yellow or even red at higher temperatures. While the pure acid tends to give off white fumes when exposed to air, acid with dissolved nitrogen dioxide gives off reddish-brown vapors, leading to the common names "red fuming nitric acid" and "white fuming nitric acid". Nitrogen oxides (NOx) are soluble in nitric acid.
Fuming nitric acid
Commercial-grade fuming nitric acid contains 98%HNO3and has a density of 1.50 g/cm3.This grade is often used in the explosives industry. It is not as volatile nor as corrosive as the anhydrous acid and has the approximate concentration of 21.4 M.
Red fuming nitric acid,or RFNA, contains substantial quantities of dissolved nitrogen dioxide (NO2) leaving the solution with a reddish-brown color. Due to the dissolved nitrogen dioxide, the density of red fuming nitric acid is lower at 1.490 g/cm3.
Aninhibitedfuming nitric acid, either white inhibited fuming nitric acid (IWFNA), or red inhibited fuming nitric acid (IRFNA), can be made by the addition of 0.6 to 0.7%hydrogen fluoride(HF). This fluoride is added forcorrosion resistancein metal tanks. The fluoride creates a metal fluoride layer that protects the metal.
Anhydrous nitric acid
White fuming nitric acid, pure nitric acid or WFNA, is very close to anhydrous nitric acid. It is available as 99.9% nitric acid by assay, or about 24molar.One specification for white fuming nitric acid is that it has a maximum of 2% water and a maximum of 0.5% dissolvedNO2.Anhydrousnitric acid is a colorless, low-viscosity(mobile) liquid with a density of 1.512–3 g/cm3that solidifies at −42 °C (−44 °F) to form white crystals.[citation needed]Its dynamic viscosity under standard conditions is 0.76 cP.[23]As it decomposes toNO2and water, it obtains a yellow tint. It boils at 83 °C (181 °F). It is usually stored in a glass shatterproof amber bottle with twice the volume of head space to allow for pressure build up, but even with those precautions the bottle must be vented monthly to release pressure.
Structure and bonding
The two terminal N–O bonds are nearly equivalent and relatively short, at 1.20 and 1.21 Å.[24]This can be explained by theories ofresonance;the two majorcanonical formsshow somedouble bondcharacter in these two bonds, causing them to be shorter than N–Osingle bonds.The third N–O bond is elongated because its O atom is bonded to H atom,[25][26]with abond lengthof 1.41 Å in the gas phase.[24]The molecule is slightly aplanar (theNO2and NOH planes are tilted away from each other by 2°) and there isrestricted rotationabout the N–OH single bond.[6][27]
Reactions
Acid-base properties
Nitric acid is normally considered to be astrong acidat ambient temperatures. There is some disagreement over the value of the acid dissociation constant, though thepKavalue is usually reported as less than −1. This means that the nitric acid in diluted solution is fully dissociated except in extremely acidic solutions. The pKavalue rises to 1 at a temperature of 250 °C.[28]
Nitric acid can act as a base with respect to an acid such assulfuric acid:
- HNO3+ 2 H2SO4⇌ [NO2]++ [H3O]++ 2 HSO−4;Equilibrium constant:K≈ 22
Thenitronium ion,[NO2]+,is the active reagent inaromatic nitrationreactions. Since nitric acid has both acidic and basic properties, it can undergo an autoprotolysis reaction, similar to theself-ionization of water:
- 2 HNO3⇌ [NO2]++ NO−3+ H2O
Reactions with metals
Nitric acid reacts with most metals, but the details depend on the concentration of the acid and the nature of the metal. Dilute nitric acid behaves as a typicalacidin its reaction with most metals.Magnesium,manganese,andzincliberateH2:
Nitric acid can oxidize non-active metals such ascopperandsilver.With these non-active or less electropositive metals the products depend on temperature and the acid concentration. For example, copper reacts with dilute nitric acid at ambient temperatures with a 3:8 stoichiometry:
- 3 Cu + 8 HNO3→ 3 Cu(NO3)2+ 2 NO + 4 H2O
Thenitric oxideproduced may react with atmosphericoxygento givenitrogen dioxide.With more concentrated nitric acid, nitrogen dioxide is produced directly in a reaction with 1:4 stoichiometry:
- Cu + 4 H++ 2 NO−3→ Cu2++ 2 NO2+ 2 H2O
Upon reaction with nitric acid, most metals give the correspondingnitrates.Somemetalloidsandmetalsgive theoxides;for instance,Sn,As,Sb,andTiare oxidized intoSnO2,As2O5,Sb2O5,andTiO2respectively.[29]
Someprecious metals,such as puregoldand platinum-group metals do not react with nitric acid, though pure gold does react withaqua regia,a mixture of concentrated nitric acid andhydrochloric acid.However, some less noble metals (Ag,Cu,...) present in somegold alloysrelatively poor in gold such ascolored goldcan be easily oxidized and dissolved by nitric acid, leading to colour changes of the gold-alloy surface. Nitric acid is used as a cheap means injewelryshops to quickly spot low-gold alloys (< 14karats) and to rapidly assess the gold purity.
Being a powerful oxidizing agent, nitric acid reacts with many non-metallic compounds, sometimes explosively. Depending on the acid concentration, temperature and thereducing agentinvolved, the end products can be variable. Reaction takes place with all metals except thenoble metalsseries and certainalloys.As a general rule, oxidizing reactions occur primarily with the concentrated acid, favoring the formation of nitrogen dioxide (NO2). However, the powerful oxidizing properties of nitric acid arethermodynamicin nature, but sometimes its oxidation reactions are ratherkineticallynon-favored. The presence of small amounts ofnitrous acid(HNO2) greatly increases the rate of reaction.[29]
Althoughchromium(Cr),iron(Fe), andaluminium(Al) readily dissolve in dilute nitric acid, the concentrated acid forms a metal-oxide layer that protects the bulk of the metal from further oxidation. The formation of this protective layer is calledpassivation.[29]Typical passivation concentrations range from 20% to 50% by volume.[30][full citation needed]Metals that are passivated by concentrated nitric acid areiron,cobalt,chromium,nickel,andaluminium.[29]
Reactions with non-metals
Being a powerfuloxidizing acid,nitric acid reacts with many organic materials, and the reactions may be explosive. Thehydroxylgroup will typically strip a hydrogen from the organic molecule to form water, and the remaining nitro group takes the hydrogen's place. Nitration of organic compounds with nitric acid is the primary method of synthesis of many common explosives, such asnitroglycerinandtrinitrotoluene(TNT). As very many less stable byproducts are possible, these reactions must be carefully thermally controlled, and the byproducts removed to isolate the desired product.
Reaction with non-metallic elements, with the exceptions of nitrogen, oxygen,noble gases,silicon,andhalogensother than iodine, usually oxidizes them to their highestoxidation statesas acids with the formation of nitrogen dioxide for concentrated acid andnitric oxidefor dilute acid.
- C (graphite) + 4 HNO3→ CO2+ 4 NO2+ 2 H2O
- 3 C (graphite) + 4 HNO3→ 3 CO2+ 4 NO + 2 H2O
Concentrated nitric acid oxidizesI2,P4,andS8intoHIO3,H3PO4,andH2SO4,respectively.[29]Although it reacts with graphite and amorphous carbon, it does not react with diamond; it can separate diamond from the graphite that it oxidizes.[31]
Xanthoproteic test
Nitric acid reacts withproteinsto form yellow nitrated products. This reaction is known as thexanthoproteic reaction.This test is carried out by adding concentrated nitric acid to the substance being tested, and then heating the mixture. If proteins that containamino acidswitharomaticrings are present, the mixture turns yellow. Upon adding a base such asammonia,the color turns orange. These color changes are caused by nitrated aromatic rings in the protein.[32][33]Xanthoproteic acidis formed when the acid contactsepithelial cells.Respective local skin color changes are indicative of inadequate safety precautions when handling nitric acid.
Production
Industrial nitric acid production uses theOstwald process.The combined Ostwald andHaber processesare extremely efficient, requiring only air and natural gasfeedstocks.[34]
The Ostwald process' technical innovation is the proper conditions under which anhydrousammoniaburns tonitric oxide(NO) instead ofdinitrogen(N2).[34][35]The nitric oxide is then oxidized, often withatmospheric oxygen,tonitrogen dioxide(NO2):
- 2 NO + O2→ 2 NO2
The dioxide then disproportionates inwaterto nitric acid and the nitric oxide feedstock:
- 3 NO2+ H2O → 2 HNO3+ NO
The net reaction is maximal oxidation of ammonia:
- NH3+ 2 O2→ HNO3+ H2O
Dissolved nitrogen oxides are either stripped (in the case of white fuming nitric acid) or remain in solution to formred fuming nitric acid.
Commercial grade nitric acid solutions are usually between 52% and 68% nitric acid by mass, themaximum distillable concentration.Furtherdehydrationto 98% can be achieved with concentratedH2SO4.[34][36]Historically, higher acid concentrations were also produced by dissolving additional nitrogen dioxide in the acid, but the last plant in theUnited Statesceased using that process in 2012.[36]
More recently, electrochemical means have been developed to produce anhydrous acid from concentrated nitric acid feedstock.[37]
Laboratory synthesis
Laboratory-scale nitric acid syntheses abound. Most take inspiration from the industrial techniques.
A wide variety ofnitratesalts metathesize withsulfuric acid(H2SO4) — for example,sodium nitrate:
- NaNO3+ H2SO4→ HNO3+ NaHSO4
Distillationat nitric acid's 83 °C boiling point then separates the solid metal-salt residue.[26]The resulting acid solution is the 68.5% azeotrope, and can be further concentrated (as in industry) with eithersulfuric acidormagnesium nitrate.[36]
Alternatively, thermal decomposition ofcopper(II) nitrategives nitrogen dioxide and oxygen gases; these are then passed through water orhydrogen peroxide[38]as in the Ostwald process:
- 2 Cu(NO3)2→ 2 CuO + 4 NO2+ O2
- 2 NO2+ H2O → HNO2+ HNO3or2 NO2+ H2O2→ 2 HNO3
Uses
The main industrial use of nitric acid is for the production offertilizers.Nitric acid is neutralized with ammonia to giveammonium nitrate.This application consumes 75–80% of the 26 million tonnes produced annually (1987). The other main applications are for the production of explosives, nylon precursors, and specialty organic compounds.[39]
Precursor to organic nitrogen compounds
Inorganic synthesis,industrial and otherwise, the nitro group is a versatilefunctional group.A mixture of nitric and sulfuric acids introduces a nitrosubstituentonto variousaromatic compoundsbyelectrophilic aromatic substitution.Many explosives, such asTNT,are prepared this way:
- C6H5CH3+ 3 HNO3→C6H2(NO2)3CH3+ 3H2O
Either concentrated sulfuric acid or oleum absorbs the excess water.
The nitro group can bereducedto give anamine group,allowing synthesis ofanilinecompounds from variousnitrobenzenes:
Use as an oxidant
The precursor tonylon,adipic acid,is produced on a large scale by oxidation of "KA oil" —a mixture ofcyclohexanoneandcyclohexanol—with nitric acid.[39]
Rocket propellant
Nitric acid has been used in various forms as theoxidizerinliquid-fueled rockets.These forms include red fuming nitric acid, white fuming nitric acid, mixtures with sulfuric acid, and these forms with HF inhibitor.[40]IRFNA (inhibitedred fuming nitric acid) was one of three liquid fuel components for theBOMARCmissile.[41]
Niche uses
Metal processing
Nitric acid can be used to convert metals to oxidized forms, such as converting copper metal tocupric nitrate.It can also be used in combination withhydrochloric acidasaqua regiato dissolve noble metals such asgold(aschloroauric acid). These salts can be used to purify gold and other metals beyond 99.9% purity by processes ofrecrystallizationandselective precipitation.Its ability to dissolve certain metals selectively or be a solvent for many metal salts makes it useful ingold partingprocesses.
Analytical reagent
Inelemental analysisbyICP-MS,ICP-AES,GFAA, and Flame AA, dilute nitric acid (0.5–5.0%) is used as a matrix compound for determining metal traces in solutions.[42]Ultrapure trace metal grade acid is required for such determination, because small amounts of metal ions could affect the result of the analysis.
It is also typically used in the digestion process of turbid water samples, sludge samples, solid samples as well as other types of unique samples which require elemental analysis viaICP-MS,ICP-OES,ICP-AES,GFAA and flameatomic absorption spectroscopy.Typically these digestions use a 50% solution of the purchasedHNO3mixed with Type 1 DI Water.
Inelectrochemistry,nitric acid is used as a chemical doping agent fororganic semiconductors,and in purification processes for rawcarbon nanotubes.
Woodworking
In a low concentration (approximately 10%), nitric acid is often used to artificially agepineandmaple.The color produced is a grey-gold very much like very old wax- or oil-finished wood (wood finishing).[43]
Etchant and cleaning agent
The corrosive effects of nitric acid are exploited for some specialty applications, such asetchingin printmaking,pickling stainless steelor cleaning silicon wafers in electronics.[44]
A solution of nitric acid, water and alcohol,nital,is used for etching metals to reveal the microstructure. ISO 14104 is one of the standards detailing this well known procedure.[45]
Nitric acid is used either in combination with hydrochloric acid or alone to clean glass cover slips and glass slides for high-end microscopy applications.[46]It is also used to clean glass before silvering when making silver mirrors.[47]
Commercially available aqueous blends of 5–30% nitric acid and 15–40%phosphoric acidare commonly used for cleaning food and dairy equipment primarily to remove precipitated calcium and magnesium compounds (either deposited from the process stream or resulting from the use of hard water during production and cleaning). The phosphoric acid content helps to passivateferrous alloysagainst corrosion by the dilute nitric acid.[citation needed]
Nitric acid can be used as a spot test foralkaloidslikeLSD,giving a variety of colours depending on the alkaloid.[48]
Nuclear fuel reprocessing
Nitric acid plays a key role inPUREXand othernuclear fuel reprocessingmethods, where it can dissolve many differentactinides.The resulting nitrates are converted to various complexes that can be reacted and extracted selectively in order to separate the metals from each other.
Safety
Nitric acid is acorrosiveacidand a powerfuloxidizing agent.The major hazard posed by it ischemical burns,as it carries outacid hydrolysiswithproteins(amide) and fats (ester), which consequently decomposesliving tissue(e.g.skinandflesh). Concentrated nitric acid stainshuman skinyellow due to its reaction with thekeratin.These yellow stains turn orange when neutralized.[49]Systemic effects are unlikely, and the substance is not considered a carcinogen or mutagen.[50]
The standard first-aid treatment for acid spills on the skin is, as for other corrosive agents, irrigation with large quantities of water. Washing is continued for at least 10–15 minutes to cool the tissue surrounding the acid burn and to prevent secondary damage. Contaminated clothing is removed immediately and the underlying skin washed thoroughly.
Being a strong oxidizing agent, nitric acid can react violently with many compounds.
Use in acid attacks
Nitric acid is one of the most common types of acid used inacid attacks.[51]
Notes
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External links
- NIOSH Pocket Guide to Chemical Hazards
- National Pollutant Inventory – Nitric Acid Fact Sheet
- Calculators:surface tensions,anddensities, molarities and molalitiesof aqueous nitric acid