Picric acid

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Picric acid
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UN number UN1344
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Template:Longitem Template:Chembox Elements/molecular formula
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Appearance Colorless to yellow solid
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Solubility in sulfuric acid Template:Ubl (in 100% Template:Chem2)[2]
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log P 1.33[3]
Vapor pressure Template:Ubl
Acidity (pKa) 0.38
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Friction sensitivity Very slight (produces weak burning odor)
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Picric acid is an organic compound with the formula (O2N)3C6H2OH. Its IUPAC name is 2,4,6-trinitrophenol (TNP). The name "picric" comes from Template:Langx (pikros), meaning "bitter", due to its bitter taste. It is one of the most acidic phenols. Like other strongly nitrated organic compounds, picric acid is an explosive, which is its primary use. It has also been used as medicine (antiseptic, burn treatments) and as a dye.

History

Picric acid was probably first mentioned in the 17th-century alchemical writings of Johann Rudolf Glauber. Initially, it was made by nitrating substances such as animal horn, silk, indigo, and natural resin, the synthesis from indigo first being performed by Peter Woulfe in 1771.[5]

The German chemist Justus von Liebig had named picric acid Script error: No such module "Lang". (rendered in French as Script error: No such module "Lang".).Script error: No such module "Unsubst". Picric acid was given that name by the French chemist Jean-Baptiste Dumas in 1841.[6] Its synthesis from phenol, and the correct determination of its formula, were accomplished during 1841.[7] In 1799, French chemist Jean-Joseph Welter (1763–1852) produced picric acid by treating silk with nitric acid; he found that potassium picrate could explode.[8] Not until 1830 did chemists think to use picric acid as an explosive. Before then, chemists assumed that only the salts of picric acid were explosive, not the acid itself.Script error: No such module "Unsubst".

A theory to explain why picrate salts detonated whereas picric acid itself didn't, was proposed by the French chemists Antoine Fourcroy and Louis Vauquelin in 1806 and reiterated by the French chemist Michel Chevreul in 1809. Picric acid evidently contained enough oxygen within itself—i.e. it was "super-oxygenated" (suroxigéné)—to combust completely even in the absence of air (because even in the absence of air, heat could transform it completely into gases, leaving no carbon). However, when picric acid was burned, the heat that was generated caused some of the acid to evaporate, dissipating so much heat that only burning, not detonation, occurred. In contrast, picrate salts were solids that did not sublimate, thus did not dissipate heat; hence, they did detonate.[9][10]

In 1871 Hermann Sprengel proved it could be detonated at the gunpowder works of John Hall & Sons in Faversham in Kent, England. Sprengel filed patents in Britain for "safety explosives" (i.e., stable explosives) on April 6, 1871 (no. 921),Script error: No such module "Unsubst". and on October 5, 1871 (no. 2642); in the latter patent, Sprengel proposed using picric acid dissolved in nitric acid as an explosive.Script error: No such module "Unsubst".[11][12]Script error: No such module "Unsubst". Afterwards most military powers used picric acid as their main high explosive material.Script error: No such module "Unsubst". A full synthesis was later found by Leonid Valerieovich Kozakov.Script error: No such module "Unsubst".

Picric acid was the first strongly explosive nitrated organic compound widely considered suitable to withstand the shock of firing in conventional artillery. Nitroglycerine and nitrocellulose (guncotton) were available earlier, but shock sensitivity sometimes caused detonation in an artillery barrel at the time of firing. In 1885, based on research of Hermann Sprengel, French chemist Eugène Turpin patented the use of pressed and cast picric acid in blasting charges and artillery shells. Script error: No such module "Unsubst".

In 1887 the French government adopted a mixture of picric acid and guncotton with the name Melinite. In 1888, Britain started manufacturing a very similar mixture in Lydd, Kent, with the name Lyddite. Japan followed with an alternative stabilization approach known as Shimose powder which, instead of attempting to stabilize the material itself, removed its contact with metal by coating the inside of the shells with layer(s) of resin and wax.[13]

By 1894 Russia was manufacturing artillery shells filled with picric acid. However, shells filled with picric acid become unstable if the compound reacts with the metal shell or fuze casings to form metal picrates which are more sensitive than the parent phenol. The sensitivity of picric acid was demonstrated by the Halifax Explosion.Script error: No such module "Unsubst".

File:The French Munitions Industry, 1914-1918 Q19175.jpg
Workers filling shells with liquid melinite at a French munitions factory during WWI

Picric acid was used in the Battle of Omdurman, the Second Boer War, the Russo-Japanese War, and World War I.[14][15][16][17]

Germany began filling artillery shells with trinitrotoluene (TNT) in 1902. Toluene was less readily available than phenol, and TNT is slightly less powerful than picric acid, but the improved safety of munitions manufacturing and storage caused the replacement of picric acid by TNT for most military purposes between the World Wars.[14]Script error: No such module "Unsubst".

Efforts to control the availability of phenol, the precursor to picric acid, emphasize its importance in World War I. Germans are reported to have bought US supplies of phenol and converted it to acetylsalicylic acid (aspirin) to keep it from the Allies. At the time, phenol was obtained from coal as a co-product of coke ovens and the manufacture of gas for gas lighting. Laclede Gas reports being asked to expand production of phenol (and toluene) to assist the war effort.[18] Both Monsanto and Dow Chemical began manufacturing synthetic phenol in 1915, with Dow being the main producer.[19][20] Dow describes picric acid as "the main battlefield explosive used by the French. Large amounts [of phenol] also went to Japan, where it was made into picric acid sold to the Russians."[20]

File:Stumps and rocks on farms shown here being removed by Picric acid LCCN2016891950.jpg
Photograph showing the use of picric acid on a farm to remove stumps and rocks.

Synthesis

The aromatic ring of phenol is activated towards electrophilic substitution reactions, and attempted nitration of phenol, even with dilute nitric acid, results in the formation of high molecular weight tars. In order to minimize these side reactions, anhydrous phenol is sulfonated with fuming sulfuric acid, and the resulting sulfonic acid is then nitrated with concentrated nitric acid. During this reaction, nitro groups are introduced, and the sulfonic acid group is displaced. The reaction is highly exothermic, and careful temperature control is required. Synthesis routes that nitrate aspirin or salicylic acid can also be used to mitigate tar formation. Carbon dioxide is lost from the former via decarboxylation, while both acetic acid and carbon dioxide are lost from the latter.[21]Template:Better source needed Another method of picric acid synthesis is direct nitration of 2,4-dinitrophenol with nitric acid.[22][23]

Uses

By far the greatest use of picric acid has been in ammunition and explosives.

Derivatives

Ammonium picrate (Explosive D, also known as Dunnite), is the ammonium salt of picric acid. It is notably less sensitive to impact than either picric acid or TNT (Template:Cvt initiation drop height using the Picatinny Arsenal apparatus, vs. Template:Cvt for TNT and Template:Cvt for PA), which allowed its use in armor piercing ammunition. Ammonium picrate was used by the United States army beginning in 1901 and the navy in 1907.[2]

Picramide, formed by aminating picric acid (typically beginning with Dunnite), can be further aminated to produce the very stable explosive TATB.Script error: No such module "Unsubst". It has found some use in organic chemistry for the preparation of crystalline salts of organic bases (picrates) for the purpose of identification and characterization.Script error: No such module "Unsubst".

Optical metallography

In metallurgy, a 4% picric acid in ethanol etch, termed "picral", has been commonly used in optical metallography to reveal prior austenite grain boundaries in ferritic steels. The hazards associated with picric acid have meant it has largely been replaced with other chemical etchants. However, it is still used to etch magnesium alloys, such as AZ31.Script error: No such module "Unsubst".[24]

Histology

Bouin solution is a common picric-acid–containing fixative solution used for histology specimens.[25] It improves the staining of acid dyes, but it can also result in hydrolysis of any DNA in the sample.[26]

Picric acid is used in the preparation of Picrosirius red, a histological stain for collagen.[27][28]

Blood tests

Clinical chemistry laboratory testing utilizes picric acid for the Jaffe reaction to test for creatinine. It forms a colored complex that can be measured using spectroscopy.[29]

Picric acid forms red isopurpurate with hydrogen cyanide (HCN). By photometric measurement of the resulting dye, picric acid can be used to quantify hydrogen cyanide.[30]

During the early 20th century, picric acid was used to measure blood glucose levels. When glucose, picric acid and sodium carbonate are combined and heated, a characteristic red color forms. With a calibrating glucose solution, the red color can be used to measure the glucose levels added. This is known as the Lewis and Benedict method of measuring glucose.[31]

Skin dye

Much less commonly, wet picric acid has been used as a skin dye, or temporary branding agent.Script error: No such module "Unsubst". It reacts with proteins in the skin to give a dark brown color that may last as long as a month.Script error: No such module "Unsubst".

Antiseptic

During the early 20th century, picric acid was stocked in pharmacies as an antiseptic and as a treatment for burns, malaria, herpes, and smallpox. Picric-acid–soaked gauze was commonly stocked in first aid kits from that period as a burn treatment.Script error: No such module "Unsubst". It was notably used for the treatment of burns suffered by victims of the Hindenburg disaster in 1937.[32]

Picric acid was used as a treatment for trench foot suffered by soldiers on the Western Front during World War I.[33]

Picric acid has been used for many years by fly tyers to dye mole skins and feathers a dark olive green for use as fishing lures. Its popularity has been tempered by its toxic nature.Script error: No such module "Unsubst".

Safety

Modern safety precautions recommend storing picric acid wet, to minimize the danger of explosion. Glass or plastic bottles are required, as picric acid forms metal picrate salts that can be more sensitive and hazardous than the acid, and which are powerful enough to initiate detonation in the acid.[2] The buildup of picrates on exposed metal surfaces can constitute an explosion hazard.[34]

Picric acid gauze, if found in antique first aid kits, presents a safety hazard because picric acid of that vintage (60–90 years old) will have become crystallized and unstable, or it may have formed metal picrates from long storage in a metal first aid case.[35]

Bomb disposal units are often called to dispose of picric acid if it has dried out.[36][37] In the United States there was an effort to remove dried picric acid containers from high school laboratories during the 1980s.Script error: No such module "Unsubst".

Munitions containing picric acid may be found in sunken warships. The buildup of metal picrates over time renders them shock-sensitive and extremely hazardous. It is recommended that shipwrecks that contain such munitions not be disturbed. The hazard may subside when the shells become corroded enough to admit seawater as these materials are water-soluble.[38] There are fluorescent probes to detect picric acid in very minute quantities.[39]

See also

References

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