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Nitric acid

Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid.[6] The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into oxides 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 as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.

Nitric acid

Pure nitric acid
Ball-and-stick model of nitric acid
Resonance space-filling model of nitric acid
Names
IUPAC name
Nitric acid
Other names
  • Aqua fortis
  • Spirit of niter
  • Eau forte
  • Hydrogen nitrate
  • Acidum nitricum
Identifiers
  • 7697-37-2 Y
3D model (JSmol)
  • Interactive image
  • Interactive image
3DMet
  • B00068
ChEBI
  • CHEBI:48107 Y
ChEMBL
  • ChEMBL1352 Y
ChemSpider
  • 919 Y
ECHA InfoCard 100.028.832
EC Number
  • 231-714-2
1576
KEGG
  • D02313 Y
MeSH Nitric+acid
  • 944
RTECS number
  • QU5775000
UNII
  • 411VRN1TV4 Y
UN number 2031
  • DTXSID5029685
  • InChI=1S/HNO3/c2-1(3)4/h(H,2,3,4) Y
    Key: GRYLNZFGIOXLOG-UHFFFAOYSA-N Y
  • InChI=1/HNO3/c2-1(3)4/h(H,2,3,4)
    Key: GRYLNZFGIOXLOG-UHFFFAOYAO
  • [N+](=O)(O)[O-]
  • ON(=O)=O
Properties
HNO3
Molar mass 63.012 g·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
log P −0.13[2]
Vapor pressure 48 mmHg (20 °C)[1]
Acidity (pKa) −1.4[3]
Conjugate base Nitrate
−1.99×10−5 cm3/mol
1.397 (16.5 °C)
2.17 ± 0.02 D
Thermochemistry
146 J/(mol·K)[4]
−207 kJ/mol[4]
Hazards
GHS labelling:
Danger
H272, H300, H310, H330, H373, H411
P210, P220, P260, P305+P351+P338, P310, P370+P378
NFPA 704 (fire diamond)
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
138 ppm (rat, 30 min)[1]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 2 ppm (5 mg/m3)[1]
REL (Recommended)
TWA 2 ppm (5 mg/m3)
ST 4 ppm (10 mg/m3)[1]
IDLH (Immediate danger)
25 ppm[1]
Safety data sheet (SDS) ICSC 0183
Related compounds
Other anions
Nitrous acid
Other cations
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)

Nitric acid is the primary reagent used for nitration – the addition of a nitro group, typically to an organic molecule. While some resulting nitro compounds are shock- and thermally-sensitive explosives, a few are stable enough to be used in munitions and demolition, while others are still more stable and used as pigments in inks and dyes. Nitric acid is also commonly used as a strong oxidizing agent.

History

Medieval alchemy

The discovery of mineral acids such as nitric acid is generally believed to go back to 13th-century European alchemy.[7] The conventional view is that nitric acid was first described in pseudo-Geber's De inventione veritatis ("On the Discovery of Truth", after c. 1300).[8]

However, according to Eric John Holmyard and Ahmad Y. al-Hassan, the nitric acid also occurs in various earlier Arabic works such as the Ṣundūq al-ḥikma ("Chest of Wisdom") attributed to Jabir ibn Hayyan (8th century) or the Taʿwīdh al-Ḥākim attributed to the Fatimid caliph al-Hakim bi-Amr Allah (985–1021).[9]

The recipe in the Ṣundūq al-ḥikma attributed to Jabir has been translated as follows:[10][11]

Take five parts of pure flowers of nitre, three parts of Cyprus vitriol and two parts of Yemen alum. 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 works falsely attributed to Albert the Great and Ramon Llull (both 13th century). These works describe the distillation of a mixture containing niter and green vitriol, which they call "eau forte" (aqua fortis).[12][13][14]

Modern era

In the 17th century, Johann Rudolf Glauber devised a process to obtain nitric acid by distilling potassium nitrate with sulfuric acid. In 1776 Antoine Lavoisier cited Joseph 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 1785 Henry Cavendish determined its precise composition and showed that it could be synthesized by passing a stream of electric sparks through moist air.[16] In 1806, Humphry Davy reported 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.[17]

The industrial production of nitric acid from atmospheric air began in 1905 with the Birkeland–Eyde process, also known as the arc process.[18] 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.[18][19] 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 of packed column or plate column absorption 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.[20] 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[21] 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 with coke. 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.[21][22]

Once the Haber process for the efficient production of ammonia was introduced in 1913, nitric acid production from ammonia using the Ostwald process overtook production from the Birkeland–Eyde process. This method of production is still in use today.

Physical and chemical properties

Commercially available nitric acid is an azeotrope with 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 monohydrate HNO3·H2O or oxonium nitrate [H3O]+[NO3] and the trihydrate HNO3·3H2O.

An older density scale is occasionally seen, with concentrated nitric acid specified as 42 Baumé.[23]

Contamination with nitrogen dioxide

 
Fuming nitric acid contaminated with yellow nitrogen dioxide

Nitric acid is subject to thermal or 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% HNO3 and 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.

An inhibited fuming 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 for corrosion resistance in 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. One specification for white fuming nitric acid is that it has a maximum of 2% water and a maximum of 0.5% dissolved NO2. Anhydrous nitric acid has a density of 1.513 g/cm3 and has the approximate concentration of 24 molar. Anhydrous nitric acid is a colorless, low-viscosity (mobile) liquid with a density of 1.512 g/cm3 that solidifies at −42 °C (−44 °F) to form white crystals[clarification needed]. As it decomposes to NO2 and 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

 
Two major resonance representations of HNO3

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 of resonance; the two major canonical forms show some double bond character in these two bonds, causing them to be shorter than N–O single bonds. The third N–O bond is elongated because its O atom is bonded to H atom,[25][26] with a bond length of 1.41 Å in the gas phase.[24] The molecule is slightly aplanar (the NO2 and NOH planes are tilted away from each other by 2°) and there is restricted rotation about the N–OH single bond.[6][27]

Reactions

Acid-base properties

Nitric acid is normally considered to be a strong acid at ambient temperatures. There is some disagreement over the value of the acid dissociation constant, though the pKa value 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 pKa value rises to 1 at a temperature of 250 °C.[28]

Nitric acid can act as a base with respect to an acid such as sulfuric acid:

HNO3 + 2 H2SO4 ⇌ [NO2]+ + [H3O]+ + 2 HSO4; Equilibrium constant: K ≈ 22

The nitronium ion, [NO2]+, is the active reagent in aromatic nitration reactions. Since nitric acid has both acidic and basic properties, it can undergo an autoprotolysis reaction, similar to the self-ionization of water:

2 HNO3 ⇌ [NO2]+ + NO3 + 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 typical acid in its reaction with most metals. Magnesium, manganese, and zinc liberate H2:

Mg + 2 HNO3Mg(NO3)2 + H2
Mn + 2 HNO3Mn(NO3)2 + H2
Zn + 2 HNO3Zn(NO3)2 + H2

Nitric acid can oxidize non-active metals such as copper and silver. 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

The nitric oxide produced may react with atmospheric oxygen to give nitrogen dioxide. With more concentrated nitric acid, nitrogen dioxide is produced directly in a reaction with 1:4 stoichiometry:

Cu + 4 H+ + 2 NO3 → Cu2+ + 2 NO2 + 2 H2O

Upon reaction with nitric acid, most metals give the corresponding nitrates. Some metalloids and metals give the oxides; for instance, Sn, As, Sb, and Ti are oxidized into SnO2, As2O5, Sb2O5, and TiO2 respectively.[29]

Some precious metals, such as pure gold and platinum-group metals do not react with nitric acid, though pure gold does react with aqua regia, a mixture of concentrated nitric acid and hydrochloric acid. However, some less noble metals (Ag, Cu, ...) present in some gold alloys relatively poor in gold such as colored gold can 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 in jewelry shops to quickly spot low-gold alloys (< 14 karats) 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 the reducing agent involved, the end products can be variable. Reaction takes place with all metals except the noble metals series and certain alloys. 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 are thermodynamic in nature, but sometimes its oxidation reactions are rather kinetically non-favored. The presence of small amounts of nitrous acid (HNO2) greatly increases the rate of reaction.[29]

Although chromium (Cr), iron (Fe), and aluminium (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 called passivation. Typical passivation concentrations range from 20% to 50% by volume (see ASTM A967-05[where?][clarification needed]). Metals that are passivated by concentrated nitric acid are iron, cobalt, chromium, nickel, and aluminium.[29]

Reactions with non-metals

Being a powerful oxidizing acid, nitric acid reacts with many organic materials, and the reactions may be explosive. The hydroxyl group 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 as nitroglycerin and trinitrotoluene (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, and halogens other than iodine, usually oxidizes them to their highest oxidation states as acids with the formation of nitrogen dioxide for concentrated acid and nitric oxide for 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 oxidizes I2, P4, and S8 into HIO3, H3PO4, and H2SO4, 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.[30]

Xanthoproteic test

Nitric acid reacts with proteins to form yellow nitrated products. This reaction is known as the xanthoproteic reaction. This test is carried out by adding concentrated nitric acid to the substance being tested, and then heating the mixture. If proteins that contain amino acids with aromatic rings are present, the mixture turns yellow. Upon adding a base such as ammonia, the color turns orange. These color changes are caused by nitrated aromatic rings in the protein.[31][32] Xanthoproteic acid is formed when the acid contacts epithelial cells. Respective local skin color changes are indicative of inadequate safety precautions when handling nitric acid.

Production

Nitric acid is made by reaction of nitrogen dioxide (NO2) with water.

4 NO2 + 2 H2O → 2 HNO3 + NO + NO2 + H2O

The net reaction is:

3 NO2 + H2O → 2 HNO3 + NO

Normally, the nitric oxide produced by the reaction is reoxidized by the oxygen in air to produce additional nitrogen dioxide.

Bubbling nitrogen dioxide through hydrogen peroxide can help to improve acid yield.

2 NO2 + H2O2 → 2 HNO3

Commercial grade nitric acid solutions are usually between 52% and 68% nitric acid. Production of nitric acid is via the Ostwald process, named after German chemist Wilhelm Ostwald. In this process, anhydrous ammonia is oxidized to nitric oxide, in the presence of platinum or rhodium gauze catalyst at a high temperature of about 500 K (227 °C; 440 °F) and a pressure of 9 standard atmospheres (910 kPa).

4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g) (ΔH = −905.2 kJ/mol)

Nitric oxide is then reacted with oxygen in air to form nitrogen dioxide.

2 NO(g) + O2(g) → 2 NO2(g) (ΔH = −114 kJ/mol)

This is subsequently absorbed in water to form nitric acid and nitric oxide.

3 NO2(g) + H2O(l) → 2 HNO3(aq) + NO(g) (ΔH = −135.74 kJ/mol)

The nitric oxide is cycled back for reoxidation. Alternatively, if the last step is carried out in air:

4 NO2(g) + O2(g) + 2 H2O(l) → 4 HNO3(aq)

The aqueous HNO3 obtained can be concentrated by distillation up to about 68% by mass. Further concentration to 98% can be achieved by dehydration with concentrated H2SO4. By using ammonia derived from the Haber process, the final product can be produced from nitrogen, hydrogen, and oxygen which are derived from air and natural gas as the sole feedstocks.[33]

Laboratory synthesis

In the laboratory, nitric acid can be made by thermal decomposition of copper(II) nitrate, producing nitrogen dioxide and oxygen gases, which are then passed through water to give nitric acid.

2 Cu(NO3)2 → 2 CuO + 4 NO2 + O2

Then, following the Ostwald process:

2 NO2 + H2O → HNO2 + HNO3

Alternatively, the reaction of equal moles of any nitrate salt such as sodium nitrate with sulfuric acid (H2SO4), and distilling this mixture at nitric acid's boiling point of 83 °C. A nonvolatile residue of the metal hydrogen sulfate remains in the distillation vessel.[26]

NaNO3 + H2SO4 → HNO3 + NaHSO4

Dilute nitric acid may be concentrated by distillation up to 68.5 % acid, which is a maximum boiling azeotrope. Further concentrating nitric acid involves distillation with either sulfuric acid or magnesium nitrate, which serve as dehydrating agents in an extractive process, lowering the volatility of water. This method is used by both industry and laboratory.[34]

Industrially, higher concentrations of nitric acid were also produced by dissolving additional nitrogen dioxide in nitric acid in an absorption tower in a process called DSN (Direct Strong Nitric acid). This process is uncommon today, the last DSN plant that produced highly concentrated nitric acid in the United States stopped production in 2012 and was replaced by a weak nitric acid plant with an additional extractive distillation unit.[34]

Dissolved nitrogen oxides are either stripped in the case of white fuming nitric acid, or remain in solution to form red fuming nitric acid. More recently, electrochemical means have been developed to produce anhydrous acid from concentrated nitric acid feedstock.[35]

Uses

 
Nitric acid in a laboratory

The main industrial use of nitric acid is for the production of fertilizers. Nitric acid is neutralized with ammonia to give ammonium 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.[36]

Precursor to organic nitrogen compounds

In organic synthesis, industrial and otherwise, the nitro group is a versatile functional group. A mixture of nitric and sulfuric acids introduces a nitro substituent onto various aromatic compounds by electrophilic aromatic substitution. Many explosives, such as TNT, are prepared this way:

C6H5CH3 + 3 HNO3C6H2(NO2)3CH3 + 3 H2O

Either concentrated sulfuric acid or oleum absorbs the excess water.

H2S2O7 + H2O → 2 H2SO4

The nitro group can be reduced to give an amine group, allowing synthesis of aniline compounds from various nitrobenzenes:

 

Use as an oxidant

The precursor to nylon, adipic acid, is produced on a large scale by oxidation of "KA oil"—a mixture of cyclohexanone and cyclohexanol—with nitric acid.[36]

Rocket propellant

Nitric acid has been used in various forms as the oxidizer in liquid-fueled rockets. These forms include red fuming nitric acid, white fuming nitric acid, mixtures with sulfuric acid, and these forms with HF inhibitor.[37] IRFNA (inhibited red fuming nitric acid) was one of three liquid fuel components for the BOMARC missile.[38]

Niche uses

Metal processing

Nitric acid can be used to convert metals to oxidized forms, such as converting copper metal to cupric nitrate. It can also be used in combination with hydrochloric acid as aqua regia to dissolve noble metals such as gold (as chloroauric acid). These salts can be used to purify gold and other metals beyond 99.9% purity by processes of recrystallization and selective precipitation. Its ability to dissolve certain metals selectively or be a solvent for many metal salts makes it useful in gold parting processes.

Analytical reagent

In elemental analysis by ICP-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.[39] 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 via ICP-MS, ICP-OES, ICP-AES, GFAA and flame atomic absorption spectroscopy. Typically these digestions use a 50% solution of the purchased HNO3 mixed with Type 1 DI Water.

In electrochemistry, nitric acid is used as a chemical doping agent for organic semiconductors, and in purification processes for raw carbon nanotubes.

Woodworking

In a low concentration (approximately 10%), nitric acid is often used to artificially age pine and maple. The color produced is a grey-gold very much like very old wax- or oil-finished wood (wood finishing).[40]

Etchant and cleaning agent

The corrosive effects of nitric acid are exploited for some specialty applications, such as etching in printmaking, pickling stainless steel or cleaning silicon wafers in electronics.[41]

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.[42]

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.[43] It is also used to clean glass before silvering when making silver mirrors.[44]

Commercially available aqueous blends of 5–30% nitric acid and 15–40% phosphoric acid are 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 passivate ferrous alloys against corrosion by the dilute nitric acid.[citation needed]

Nitric acid can be used as a spot test for alkaloids like LSD, giving a variety of colours depending on the alkaloid.[45]

Nuclear fuel reprocessing

Nitric acid plays a key role in PUREX and other nuclear fuel reprocessing methods, where it can dissolve many different actinides. 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 a corrosive acid and a powerful oxidizing agent. The major hazard posed by it is chemical burns, as it carries out acid hydrolysis with proteins (amide) and fats (ester), which consequently decomposes living tissue (e.g. skin and flesh). Concentrated nitric acid stains human skin yellow due to its reaction with the keratin. These yellow stains turn orange when neutralized.[46] Systemic effects are unlikely, and the substance is not considered a carcinogen or mutagen.[47]

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 in acid attacks.[48]

Notes

  1. ^ He goes on to point out that "nitrous air" is the reverse, or "nitric acid deprived of air and water."[15]

References

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  2. ^ "nitric acid_msds".
  3. ^ Bell, R. P. (1973), The Proton in Chemistry (2nd ed.), Ithaca, NY: Cornell University Press
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  7. ^ Multhauf, Robert P. (1966). The Origins of Chemistry. London: Oldbourne. pp. 140-141, quote: "But among them we find the rudiments of processes which were finally to lead to the discovery of the mineral acids, sulphuric, hydrochloric and nitric. The mineral acids manifest themselves clearly only about three centuries after al-Razi, in the works of Europeans [...]". Needham, Joseph; Ping-Yü, Ho; Gwei-Djen, Lu; Sivin, Nathan (1980). Science and Civilisation in China. Volume 5, Chemistry and Chemical Technology. Part IV, Spagyrical Discovery and Invention: Apparatus, Theories and Gifts. Cambridge: Cambridge University Press. ISBN 978-0-521-08573-1. p. 195, quote: "It is generally accepted that mineral acids were quite unknown both to the ancients in the West and to the Arabic alchemists." Al-Hassan, Ahmad Y. (2001). Science and Technology in Islam: Technology and applied sciences. UNESCO. ISBN 978-92-3-103831-0. p. 59, quote: "The text is given here in full because of the prevailing notion that Islamic chemists did not produce mineral acids." Karpenko, Vladimír; Norris, John A. (2002). "Vitriol in the History of Chemistry". Chemické listy. 96 (12): 997–1005. p. 1002, quote: "[...] dating the discovery of nitric acid is likewise uncertain. It is estimated that this discovery took place after 1300 [...] A passage from the second part of Pseudo-Geber's Summa perfectionis [...] was long considered to be the earliest known recipe for sulfuric acid [...]". Newman, William R. (2006). Atoms and Alchemy: Chymistry and the Experimental Origins of the Scientific Revolution. Chicago: University of Chicago Press. ISBN 978-0226576961. p. 98, quote: "[...] between the time when the Summa perfectionis was written and the seventeenth century, the mineral acids–sulfuric, hydrochloric, nitric, and the mixture of the latter two, called aqua regia, had been discovered."
  8. ^ Karpenko & Norris 2002, p. 1002. As Karpenko & Norris note, the uncertain dating of the pseudo-Geber corpus (which was probably written by more than one author) renders the date of its description of nitric acid equally uncertain. According to Al-Hassan 2001, p. 62, recipes for the preparation of nitric acid also occur in the Liber Luminis luminum, a Latin treatise usually attributed to Michael Scot (died before 1236) but perhaps translated by him from the Arabic. One of the manuscripts of the Liber Luminis luminum mentions that it was translated by Michael Scot; see Moureau, Sébastien (2020). "Min al-kīmiyāʾ ad alchimiam. The Transmission of Alchemy from the Arab-Muslim World to the Latin West in the Middle Ages". Micrologus. 28: 87–141. hdl:2078.1/211340. p. 115 (no. 22). Al-Hassan 2001 mentions Abu Bakr al-Razi as the work's author, but this is likely a conflation with several other Latin treatises called Liber Luminis luminum that were sometimes attributed to al-Razi; see Moureau 2020, p. 107 (no. 5), p. 114 (no. 20), pp. 114–115 (no. 21).
  9. ^ For the claims regarding the Ṣundūq al-ḥikma, see Al-Hassan 2001, p. 62; Holmyard, John Eric (1931). Makers Of Chemistry. Oxford: Clarendon Press. p. 60. For the claim regarding the Taʿwīdh al-Ḥākim, see Al-Hassan 2001, p. 62.
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  13. ^ Thomson, Thomas (1830). The history of chemistry. Vol. 1. Cushing/Whitney Medical Library, Yale University. London, H. Colburn, and R. Bentley. p. 40.
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External links

  • NIOSH Pocket Guide to Chemical Hazards
  • National Pollutant Inventory – Nitric Acid Fact Sheet
  • Calculators: surface tensions, and densities, molarities and molalities of aqueous nitric acid

nitric, acid, confused, with, nitrous, acid, inorganic, compound, with, formula, hno3, highly, corrosive, mineral, acid, compound, colorless, samples, tend, acquire, yellow, cast, over, time, decomposition, into, oxides, nitrogen, most, commercially, available. Not to be confused with nitrous acid Nitric acid is the inorganic compound with the formula HNO3 It is a highly corrosive mineral acid 6 The compound is colorless but samples tend to acquire a yellow cast over time due to decomposition into oxides 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 as fuming nitric acid Depending on the amount of nitrogen dioxide present fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86 or white fuming nitric acid at concentrations above 95 Nitric acid Pure nitric acidBall and stick model of nitric acid Resonance space filling model of nitric acidNamesIUPAC name Nitric acidOther names Aqua fortisSpirit of niterEau forteHydrogen nitrateAcidum nitricumIdentifiersCAS Number 7697 37 2 Y3D model JSmol Interactive imageInteractive image3DMet B00068ChEBI CHEBI 48107 YChEMBL ChEMBL1352 YChemSpider 919 YECHA InfoCard 100 028 832EC Number 231 714 2Gmelin Reference 1576KEGG D02313 YMeSH Nitric acidPubChem CID 944RTECS number QU5775000UNII 411VRN1TV4 YUN number 2031CompTox Dashboard EPA DTXSID5029685InChI InChI 1S HNO3 c2 1 3 4 h H 2 3 4 YKey GRYLNZFGIOXLOG UHFFFAOYSA N YInChI 1 HNO3 c2 1 3 4 h H 2 3 4 Key GRYLNZFGIOXLOG UHFFFAOYAOSMILES N O O O ON O OPropertiesChemical formula HNO3Molar mass 63 012 g mol 1Appearance 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 Solubility in water Misciblelog P 0 13 2 Vapor pressure 48 mmHg 20 C 1 Acidity pKa 1 4 3 Conjugate base NitrateMagnetic susceptibility x 1 99 10 5 cm3 molRefractive index nD 1 397 16 5 C Dipole moment 2 17 0 02 DThermochemistryStd molarentropy S 298 146 J mol K 4 Std enthalpy offormation DfH 298 207 kJ mol 4 HazardsGHS labelling PictogramsSignal word DangerHazard statements H272 H300 H310 H330 H373 H411Precautionary statements P210 P220 P260 P305 P351 P338 P310 P370 P378NFPA 704 fire diamond 5 302OXFlash point Non flammableLethal dose or concentration LD LC LC50 median concentration 138 ppm rat 30 min 1 NIOSH US health exposure limits PEL Permissible TWA 2 ppm 5 mg m3 1 REL Recommended TWA 2 ppm 5 mg m3 ST 4 ppm 10 mg m3 1 IDLH Immediate danger 25 ppm 1 Safety data sheet SDS ICSC 0183Related compoundsOther anions Nitrous acidOther cations Sodium nitratePotassium nitrateAmmonium nitrateRelated compounds Dinitrogen trioxideDinitrogen tetroxideDinitrogen pentoxideNitrogen oxideNitrogen monoxideNitrogen dioxideExcept where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Y verify what is Y N Infobox references Nitric acid is the primary reagent used for nitration the addition of a nitro group typically to an organic molecule While some resulting nitro compounds are shock and thermally sensitive explosives a few are stable enough to be used in munitions and demolition while others are still more stable and used as pigments in inks and dyes Nitric acid is also commonly used as a strong oxidizing agent Contents 1 History 1 1 Medieval alchemy 1 2 Modern era 2 Physical and chemical properties 2 1 Contamination with nitrogen dioxide 2 2 Fuming nitric acid 2 3 Anhydrous nitric acid 2 4 Structure and bonding 3 Reactions 3 1 Acid base properties 3 2 Reactions with metals 3 3 Reactions with non metals 3 4 Xanthoproteic test 4 Production 4 1 Laboratory synthesis 5 Uses 5 1 Precursor to organic nitrogen compounds 5 2 Use as an oxidant 5 3 Rocket propellant 5 4 Niche uses 5 4 1 Metal processing 5 4 2 Analytical reagent 5 4 3 Woodworking 5 4 4 Etchant and cleaning agent 5 4 5 Nuclear fuel reprocessing 6 Safety 6 1 Use in acid attacks 7 Notes 8 References 9 External linksHistoryMedieval alchemy The discovery of mineral acids such as nitric acid is generally believed to go back to 13th century European alchemy 7 The conventional view is that nitric acid was first described in pseudo Geber s De inventione veritatis On the Discovery of Truth after c 1300 8 However according to Eric John Holmyard and Ahmad Y al Hassan the nitric acid also occurs in various earlier Arabic works such as the Ṣunduq al ḥikma Chest of Wisdom attributed to Jabir ibn Hayyan 8th century or the Taʿwidh al Ḥakim attributed to the Fatimid caliph al Hakim bi Amr Allah 985 1021 9 The recipe in the Ṣunduq al ḥikma attributed to Jabir has been translated as follows 10 11 Take five parts of pure flowers of nitre three parts of Cyprus vitriol and two parts of Yemen alum 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 works falsely attributed to Albert the Great and Ramon Llull both 13th century These works describe the distillation of a mixture containing niter and green vitriol which they call eau forte aqua fortis 12 13 14 Modern era In the 17th century Johann Rudolf Glauber devised a process to obtain nitric acid by distilling potassium nitrate with sulfuric acid In 1776 Antoine Lavoisier cited Joseph 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 1785 Henry Cavendish determined its precise composition and showed that it could be synthesized by passing a stream of electric sparks through moist air 16 In 1806 Humphry Davy reported 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 17 The industrial production of nitric acid from atmospheric air began in 1905 with the Birkeland Eyde process also known as the arc process 18 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 18 19 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 of packed column or plate column absorption 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 20 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 21 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 with coke 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 21 22 Once the Haber process for the efficient production of ammonia was introduced in 1913 nitric acid production from ammonia using the Ostwald process overtook production from the Birkeland Eyde process This method of production is still in use today Physical and chemical propertiesCommercially available nitric acid is an azeotrope with 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 monohydrate HNO3 H2O or oxonium nitrate H3O NO3 and the trihydrate HNO3 3H2O An older density scale is occasionally seen with concentrated nitric acid specified as 42 Baume 23 Contamination with nitrogen dioxide nbsp Fuming nitric acid contaminated with yellow nitrogen dioxideNitric acid is subject to thermal or light decomposition and for this reason it was often stored in brown glass bottles 4 HNO3 2 H2O 4 NO2 O2This 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 Main article Red fuming nitric acid Commercial grade fuming nitric acid contains 98 HNO3 and 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 An inhibited fuming 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 for corrosion resistance in 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 One specification for white fuming nitric acid is that it has a maximum of 2 water and a maximum of 0 5 dissolved NO2 Anhydrous nitric acid has a density of 1 513 g cm3 and has the approximate concentration of 24 molar Anhydrous nitric acid is a colorless low viscosity mobile liquid with a density of 1 512 g cm3 that solidifies at 42 C 44 F to form white crystals clarification needed As it decomposes to NO2 and 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 nbsp Two major resonance representations of HNO3The two terminal N O bonds are nearly equivalent and relatively short at 1 20 and 1 21 A 24 This can be explained by theories of resonance the two major canonical forms show some double bond character in these two bonds causing them to be shorter than N O single bonds The third N O bond is elongated because its O atom is bonded to H atom 25 26 with a bond length of 1 41 A in the gas phase 24 The molecule is slightly aplanar the NO2 and NOH planes are tilted away from each other by 2 and there is restricted rotation about the N OH single bond 6 27 ReactionsAcid base properties Nitric acid is normally considered to be a strong acid at ambient temperatures There is some disagreement over the value of the acid dissociation constant though the pKa value 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 pKa value rises to 1 at a temperature of 250 C 28 Nitric acid can act as a base with respect to an acid such as sulfuric acid HNO3 2 H2SO4 NO2 H3O 2 HSO 4 Equilibrium constant K 22The nitronium ion NO2 is the active reagent in aromatic nitration reactions Since nitric acid has both acidic and basic properties it can undergo an autoprotolysis reaction similar to the self ionization of water 2 HNO3 NO2 NO 3 H2OReactions 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 typical acid in its reaction with most metals Magnesium manganese and zinc liberate H2 Mg 2 HNO3 Mg NO3 2 H2 Mn 2 HNO3 Mn NO3 2 H2 Zn 2 HNO3 Zn NO3 2 H2Nitric acid can oxidize non active metals such as copper and silver 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 H2OThe nitric oxide produced may react with atmospheric oxygen to give nitrogen 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 H2OUpon reaction with nitric acid most metals give the corresponding nitrates Some metalloids and metals give the oxides for instance Sn As Sb and Ti are oxidized into SnO2 As2O5 Sb2O5 and TiO2 respectively 29 Some precious metals such as pure gold and platinum group metals do not react with nitric acid though pure gold does react with aqua regia a mixture of concentrated nitric acid and hydrochloric acid However some less noble metals Ag Cu present in some gold alloys relatively poor in gold such as colored gold can 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 in jewelry shops to quickly spot low gold alloys lt 14 karats 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 the reducing agent involved the end products can be variable Reaction takes place with all metals except the noble metals series and certain alloys 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 are thermodynamic in nature but sometimes its oxidation reactions are rather kinetically non favored The presence of small amounts of nitrous acid HNO2 greatly increases the rate of reaction 29 Although chromium Cr iron Fe and aluminium 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 called passivation Typical passivation concentrations range from 20 to 50 by volume see ASTM A967 05 where clarification needed Metals that are passivated by concentrated nitric acid are iron cobalt chromium nickel and aluminium 29 Reactions with non metals Being a powerful oxidizing acid nitric acid reacts with many organic materials and the reactions may be explosive The hydroxyl group 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 as nitroglycerin and trinitrotoluene 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 and halogens other than iodine usually oxidizes them to their highest oxidation states as acids with the formation of nitrogen dioxide for concentrated acid and nitric oxide for dilute acid C graphite 4 HNO3 CO2 4 NO2 2 H2O 3 C graphite 4 HNO3 3 CO2 4 NO 2 H2OConcentrated nitric acid oxidizes I2 P4 and S8 into HIO3 H3PO4 and H2SO4 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 30 Xanthoproteic test Nitric acid reacts with proteins to form yellow nitrated products This reaction is known as the xanthoproteic reaction This test is carried out by adding concentrated nitric acid to the substance being tested and then heating the mixture If proteins that contain amino acids with aromatic rings are present the mixture turns yellow Upon adding a base such as ammonia the color turns orange These color changes are caused by nitrated aromatic rings in the protein 31 32 Xanthoproteic acid is formed when the acid contacts epithelial cells Respective local skin color changes are indicative of inadequate safety precautions when handling nitric acid ProductionNitric acid is made by reaction of nitrogen dioxide NO2 with water 4 NO2 2 H2O 2 HNO3 NO NO2 H2OThe net reaction is 3 NO2 H2O 2 HNO3 NONormally the nitric oxide produced by the reaction is reoxidized by the oxygen in air to produce additional nitrogen dioxide Bubbling nitrogen dioxide through hydrogen peroxide can help to improve acid yield 2 NO2 H2O2 2 HNO3Commercial grade nitric acid solutions are usually between 52 and 68 nitric acid Production of nitric acid is via the Ostwald process named after German chemist Wilhelm Ostwald In this process anhydrous ammonia is oxidized to nitric oxide in the presence of platinum or rhodium gauze catalyst at a high temperature of about 500 K 227 C 440 F and a pressure of 9 standard atmospheres 910 kPa 4 NH3 g 5 O2 g 4 NO g 6 H2O g DH 905 2 kJ mol Nitric oxide is then reacted with oxygen in air to form nitrogen dioxide 2 NO g O2 g 2 NO2 g DH 114 kJ mol This is subsequently absorbed in water to form nitric acid and nitric oxide 3 NO2 g H2O l 2 HNO3 aq NO g DH 135 74 kJ mol The nitric oxide is cycled back for reoxidation Alternatively if the last step is carried out in air 4 NO2 g O2 g 2 H2O l 4 HNO3 aq The aqueous HNO3 obtained can be concentrated by distillation up to about 68 by mass Further concentration to 98 can be achieved by dehydration with concentrated H2SO4 By using ammonia derived from the Haber process the final product can be produced from nitrogen hydrogen and oxygen which are derived from air and natural gas as the sole feedstocks 33 Laboratory synthesis In the laboratory nitric acid can be made by thermal decomposition of copper II nitrate producing nitrogen dioxide and oxygen gases which are then passed through water to give nitric acid 2 Cu NO3 2 2 CuO 4 NO2 O2Then following the Ostwald process 2 NO2 H2O HNO2 HNO3Alternatively the reaction of equal moles of any nitrate salt such as sodium nitrate with sulfuric acid H2SO4 and distilling this mixture at nitric acid s boiling point of 83 C A nonvolatile residue of the metal hydrogen sulfate remains in the distillation vessel 26 NaNO3 H2SO4 HNO3 NaHSO4Dilute nitric acid may be concentrated by distillation up to 68 5 acid which is a maximum boiling azeotrope Further concentrating nitric acid involves distillation with either sulfuric acid or magnesium nitrate which serve as dehydrating agents in an extractive process lowering the volatility of water This method is used by both industry and laboratory 34 Industrially higher concentrations of nitric acid were also produced by dissolving additional nitrogen dioxide in nitric acid in an absorption tower in a process called DSN Direct Strong Nitric acid This process is uncommon today the last DSN plant that produced highly concentrated nitric acid in the United States stopped production in 2012 and was replaced by a weak nitric acid plant with an additional extractive distillation unit 34 Dissolved nitrogen oxides are either stripped in the case of white fuming nitric acid or remain in solution to form red fuming nitric acid More recently electrochemical means have been developed to produce anhydrous acid from concentrated nitric acid feedstock 35 Uses nbsp Nitric acid in a laboratoryThe main industrial use of nitric acid is for the production of fertilizers Nitric acid is neutralized with ammonia to give ammonium 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 36 Precursor to organic nitrogen compounds See also Nitration In organic synthesis industrial and otherwise the nitro group is a versatile functional group A mixture of nitric and sulfuric acids introduces a nitro substituent onto various aromatic compounds by electrophilic aromatic substitution Many explosives such as TNT are prepared this way C6H5CH3 3 HNO3 C6H2 NO2 3CH3 3 H2OEither concentrated sulfuric acid or oleum absorbs the excess water H2S2O7 H2O 2 H2SO4The nitro group can be reduced to give an amine group allowing synthesis of aniline compounds from various nitrobenzenes nbsp Use as an oxidant The precursor to nylon adipic acid is produced on a large scale by oxidation of KA oil a mixture of cyclohexanone and cyclohexanol with nitric acid 36 Rocket propellant Nitric acid has been used in various forms as the oxidizer in liquid fueled rockets These forms include red fuming nitric acid white fuming nitric acid mixtures with sulfuric acid and these forms with HF inhibitor 37 IRFNA inhibited red fuming nitric acid was one of three liquid fuel components for the BOMARC missile 38 Niche uses Metal processing Nitric acid can be used to convert metals to oxidized forms such as converting copper metal to cupric nitrate It can also be used in combination with hydrochloric acid as aqua regia to dissolve noble metals such as gold as chloroauric acid These salts can be used to purify gold and other metals beyond 99 9 purity by processes of recrystallization and selective precipitation Its ability to dissolve certain metals selectively or be a solvent for many metal salts makes it useful in gold parting processes Analytical reagent In elemental analysis by ICP 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 39 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 via ICP MS ICP OES ICP AES GFAA and flame atomic absorption spectroscopy Typically these digestions use a 50 solution of the purchased HNO3 mixed with Type 1 DI Water In electrochemistry nitric acid is used as a chemical doping agent for organic semiconductors and in purification processes for raw carbon nanotubes Woodworking In a low concentration approximately 10 nitric acid is often used to artificially age pine and maple The color produced is a grey gold very much like very old wax or oil finished wood wood finishing 40 Etchant and cleaning agent The corrosive effects of nitric acid are exploited for some specialty applications such as etching in printmaking pickling stainless steel or cleaning silicon wafers in electronics 41 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 42 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 43 It is also used to clean glass before silvering when making silver mirrors 44 Commercially available aqueous blends of 5 30 nitric acid and 15 40 phosphoric acid are 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 passivate ferrous alloys against corrosion by the dilute nitric acid citation needed Nitric acid can be used as a spot test for alkaloids like LSD giving a variety of colours depending on the alkaloid 45 Nuclear fuel reprocessing Nitric acid plays a key role in PUREX and other nuclear fuel reprocessing methods where it can dissolve many different actinides The resulting nitrates are converted to various complexes that can be reacted and extracted selectively in order to separate the metals from each other SafetyNitric acid is a corrosive acid and a powerful oxidizing agent The major hazard posed by it is chemical burns as it carries out acid hydrolysis with proteins amide and fats ester which consequently decomposes living tissue e g skin and flesh Concentrated nitric acid stains human skin yellow due to its reaction with the keratin These yellow stains turn orange when neutralized 46 Systemic effects are unlikely and the substance is not considered a carcinogen or mutagen 47 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 in acid attacks 48 Notes He goes on to point out that nitrous air is the reverse or nitric acid deprived of air and water 15 References a b c d e f g NIOSH Pocket Guide to Chemical Hazards 0447 National Institute for Occupational Safety and Health NIOSH nitric acid msds Bell R P 1973 The Proton in Chemistry 2nd ed Ithaca NY Cornell University Press a b Zumdahl Steven S 2009 Chemical Principles 6th Ed Houghton Mifflin Company p A22 ISBN 978 0 618 94690 7 Safety Data Sheet PDF fishersci com Fisher Scientific International 23 March 2015 p 2 Archived PDF from the original on 10 September 2022 Retrieved 4 October 2022 a b Greenwood Norman N Earnshaw Alan 1997 Chemistry of the Elements 2nd ed Butterworth Heinemann pp 465 471 ISBN 978 0 08 037941 8 Multhauf Robert P 1966 The Origins of Chemistry London Oldbourne pp 140 141 quote But among them we find the rudiments of processes which were finally to lead to the discovery of the mineral acids sulphuric hydrochloric and nitric The mineral acids manifest themselves clearly only about three centuries after al Razi in the works of Europeans Needham Joseph Ping Yu Ho Gwei Djen Lu Sivin Nathan 1980 Science and Civilisation in China Volume 5 Chemistry and Chemical Technology Part IV Spagyrical Discovery and Invention Apparatus Theories and Gifts Cambridge Cambridge University Press ISBN 978 0 521 08573 1 p 195 quote It is generally accepted that mineral acids were quite unknown both to the ancients in the West and to the Arabic alchemists Al Hassan Ahmad Y 2001 Science and Technology in Islam Technology and applied sciences UNESCO ISBN 978 92 3 103831 0 p 59 quote The text is given here in full because of the prevailing notion that Islamic chemists did not produce mineral acids Karpenko Vladimir Norris John A 2002 Vitriol in the History of Chemistry Chemicke listy 96 12 997 1005 p 1002 quote dating the discovery of nitric acid is likewise uncertain It is estimated that this discovery took place after 1300 A passage from the second part of Pseudo Geber s Summa perfectionis was long considered to be the earliest known recipe for sulfuric acid Newman William R 2006 Atoms and Alchemy Chymistry and the Experimental Origins of the Scientific Revolution Chicago University of Chicago Press ISBN 978 0226576961 p 98 quote between the time when the Summa perfectionis was written and the seventeenth century the mineral acids sulfuric hydrochloric nitric and the mixture of the latter two called aqua regia had been discovered Karpenko amp Norris 2002 p 1002 As Karpenko amp Norris note the uncertain dating of the pseudo Geber corpus which was probably written by more than one author renders the date of its description of nitric acid equally uncertain According to Al Hassan 2001 p 62 recipes for the preparation of nitric acid also occur in the Liber Luminis luminum a Latin treatise usually attributed to Michael Scot died before 1236 but perhaps translated by him from the Arabic One of the manuscripts of the Liber Luminis luminum mentions that it was translated by Michael Scot see Moureau Sebastien 2020 Min al kimiyaʾ ad alchimiam The Transmission of Alchemy from the Arab Muslim World to the Latin West in the Middle Ages Micrologus 28 87 141 hdl 2078 1 211340 p 115 no 22 Al Hassan 2001 mentions Abu Bakr al Razi as the work s author but this is likely a conflation with several other Latin treatises called Liber Luminis luminum that were sometimes attributed to al Razi see Moureau 2020 p 107 no 5 p 114 no 20 pp 114 115 no 21 For the claims regarding the Ṣunduq al ḥikma see Al Hassan 2001 p 62 Holmyard John Eric 1931 Makers Of Chemistry Oxford Clarendon Press p 60 For the claim regarding the Taʿwidh al Ḥakim see Al Hassan 2001 p 62 Discovery A Monthly Popular Journal of Knowledge John Murray 1924 Ḥasan Aḥmad Yusuf Hill Donald Routledge 1986 Islamic Technology An Illustrated History Cambridge University Press p 147 ISBN 978 92 3 102294 4 Chisholm Hugh ed 1911 Nitric Acid Encyclopaedia Britannica Vol 19 11th ed Cambridge University Press pp 711 712 Thomson Thomas 1830 The history of chemistry Vol 1 Cushing Whitney Medical Library Yale University London H Colburn and R Bentley p 40 Katz David A 2008 An Illustrated History of Alchemy and Early Chemistry PDF p 23 Retrieved 21 October 2023 a b Gillispie Charles Coulston 1960 The Edge of Objectivity An Essay in the History of Scientific Ideas Princeton NJ Princeton University Press pp 223 24 ISBN 0 691 02350 6 Chisholm Hugh ed 1911 Nitric Acid Encyclopaedia Britannica Vol 19 11th ed Cambridge University Press pp 711 712 Davy John ed 1839 On Some Chemical Agencies of Electricity The Collected Works of Sir Humphry Davy Vol 5 pp 1 12 a b Mellor J W 1918 Modern Inorganic Chemistry Longmans Green and Co p 509 Martin Geoffrey Barbour William 1915 Industrial Nitrogen Compounds and Explosives Crosby Lockwood and Son p 21 Knox Joseph 1914 The Fixation of Atmospheric Nitrogen D Van Nostrand Company pp 45 50 a b Dary G 1913 The Production of Nitrates by the Direct Electrolysis of Peat Deposits London Electrical Review 73 1020 1021 Hale Arthur 1919 The Manufacture of Chemicals by Electrolysis D Van Nostrand Co pp 30 32 Retrieved 2019 09 15 Dean John 1992 Lange s Handbook of Chemistry 14 ed McGraw Hill pp 2 79 2 80 ISBN 978 0 07 016194 8 a b Cox A P Ellis M C Attfield C J Ferris A C 1994 Microwave spectrum of DNO3 and average structures of nitric and nitrous acids J Mol Struct 320 1 2 91 106 Bibcode 1994JMoSt 320 91C doi 10 1016 0022 2860 93 08008 R Luzzati V 1951 Structure cristalline de l acide nitrique anhydre Acta Crystallographica in French 4 2 120 131 Bibcode 1951AcCry 4 120L doi 10 1107 S0365110X51000404 a b Allan D R Marshall W G Francis D J Oswald I D H Pulham C R Spanswick C 2010 The crystal structures of the low temperature and high pressure polymorphs of nitric acid PDF Dalton Trans Submitted manuscript 39 15 3736 3743 doi 10 1039 B923975H PMID 20354626 Cox A P Riveros J M 1965 Microwave Spectrum and Structure of Nitric Acid The Journal of Chemical Physics 42 9 3106 Bibcode 1965JChPh 42 3106C doi 10 1063 1 1696387 IUPAC SC Database A comprehensive database of published data on equilibrium constants of metal complexes and ligands a b c d Catherine E Housecroft Alan G Sharpe 2008 Chapter 15 The group 15 elements Inorganic Chemistry 3rd ed Pearson ISBN 978 0 13 175553 6 Ōsawa Eiji December 2007 Recent progress and perspectives in single digit nanodiamond Diamond and Related Materials 16 12 2018 2022 Bibcode 2007DRM 16 2018O doi 10 1016 j diamond 2007 08 008 Sherman Henry Clapp 2007 Methods of organic analysis Read Books p 315 ISBN 978 1 4086 2802 7 Knowles Frank 2007 A practical course in agricultural chemistry Read Books p 76 ISBN 978 1 4067 4583 2 Considine Douglas M ed 1974 Chemical and process technology encyclopedia New York McGraw Hill pp 769 72 ISBN 978 0 07 012423 3 a b Wiley 2020 Nitric acid Kirk Othmer Encyclopedia of Chemical Technology pp 1 37 doi 10 1002 0471238961 1409201803120118 a01 pub3 ISBN 9780471484943 S2CID 260923593 Retrieved 2023 08 09 US 6200456 Harrar Jackson E Quong Roland amp Rigdon Lester P et al Large scale production of anhydrous nitric acid and nitric acid solutions of dinitrogen pentoxide published April 13 1987 issued March 13 2001 assigned to United States Department of Energy a b Thiemann Michael Scheibler Erich Wiegand Karl Wilhelm Nitric Acid Nitrous Acid and Nitrogen Oxides Ullmann s Encyclopedia of Industrial Chemistry Weinheim Wiley VCH doi 10 1002 14356007 a17 293 ISBN 978 3527306732 Clark John D 1972 Ignition Rutgers University Press ISBN 978 0 8135 0725 5 BOMARC Summary BILLONY COM Retrieved 2009 05 28 Eaton Andrew D Greenberg Arnold E Rice Eugene W Clesceri Lenore S Franson Mary Ann H eds 2005 Standard Methods For the Examination of Water and Wastewater 21 ed American Public Health Association ISBN 978 0 87553 047 5 Also available on CD ROM and online by subscription page needed Jewitt Jeff 1997 Hand applied finishes Taunton Press ISBN 978 1 56158 154 2 Retrieved 2009 05 28 Muraoka Hisashi 1995 Silicon wafer cleaning fluid with HNO3 HF HCl surfactant and water U S patent 5 635 463 ISO 14104 2017 Gears Surface temper etch inspection after grinding chemical method Fischer A H Jacobson K A Rose J Zeller R 1 May 2008 Preparation of Slides and Coverslips for Microscopy Cold Spring Harbor Protocols 2008 6 pdb prot4988 doi 10 1101 pdb prot4988 PMID 21356831 Curtis Heber D February 1911 Methods of Silvering Mirrors Publications of the Astronomical Society of the Pacific 23 135 13 Bibcode 1911PASP 23 13C doi 10 1086 122040 hdl 2027 mdp 39015018047608 S2CID 120665136 O Neal Carol L Crouch Dennis J Fatah Alim A April 2000 Validation of twelve chemical spot tests for the detection of drugs of abuse Forensic Science International 109 3 189 201 doi 10 1016 S0379 0738 99 00235 2 PMID 10725655 May Paul November 2007 Nitric acid Retrieved 2009 05 28 Nitric acid Toxicological overview Health Protection Agency Retrieved 2011 12 07 Rees Anna 1 October 2013 Freeze mob to highlight the issue of acid attacks RESET to Retrieved 25 June 2021 External linksNIOSH Pocket Guide to Chemical Hazards National Pollutant Inventory Nitric Acid Fact Sheet Calculators surface tensions and densities molarities and molalities of aqueous nitric acid Retrieved from https en wikipedia org w index php title Nitric acid amp oldid 1206556422, wikipedia, wiki, book, books, library,

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