1

PICRIC ACID
Picric Acid (a.k.a. 2-hydroxy-1,3,5-trinitrobenzene, CAS Number 88-89-1) can be
a useful laboratory reagent; however, dry picric acid is a shock-sensitive
explosive capable of releasing energy on a level similar to dynamite. In a
confined area such as a lab, the force of a picric acid explosion could be
devastating; due to its unstable nature, dry picric acid is forbidden from being
transported in the U.S.

The bottle of picric acid shown at right was recently discovered in a University
building - the material was very old, very dry, and potentially unstable; the bottle
also had a metal lid which introduced the possibility of metal picrate formation,
another explosive.
In addition to picric acid, other potential bombs may be found in containers of
peroxide forming chemicals such as ethyl ether, tetrahydrofuran, dioxane, and
others. Implementing strong inventory controls within your laboratory can
minimize nasty surprises and the expenditure of thousands of dollars to have
explosives stabilized and removed.

If you possess picric acid, you have a responsibility to keep the material wet, in
good condition, and have EH&S remove it when you no longer plan to use it.

If you purchase peroxide forming chemicals, you have a responsibility to apply a

peroxide former label (free from EH&S) and dispose of the material through
EH&S within the recommended time limit.

Picric acid

IUPAC name 2,4,6-Trinitrophenol

Other names Carbazotic Acid; phenol trinitrate; picronitric acid; trinitrophenol;
2,4,6-trinitro-1-phenol; 2-hydroxy-1,3,5-trinitrobenzene; TNP
CAS number [88-89-1]
RTECS number TJ7875000
Properties
Molecular formula C6H3N3O7
Molar mass 229.10 g/mol
Appearance Colorless to yellow solid
Density 1.763 g/cm³, solid
Melting point 122.5 °C
Boiling point > 300 °C (Explodes)
Solubility in water 1.40 g/100 mL
Acidity (pKa) 0.38
HazardsNFPA 704 334
R-phrases R1 R10 R36 R37 R38
S-phrases S28 S35 S37 S45
 2

Explosive data
Explosive velocity 7,350 m/s at ρ 1.70
Picric acid is the chemical compound more formally called 2,4,6-trinitrophenol
(TNP). This, a yellow crystalline solid, is one of the most acidic phenols. Like
other highly nitrated compounds such as TNT, picric acid is an explosive. Its
name comes from Greek πικρος—"bitter", reflecting the bitter taste of picric
acid.Contents

History
Picric acid was probably first mentioned in the alchemical writings of Johann
Rudolf Glauber in 1742. Initially, it was made by nitrating substances such as
animal horn, silk, indigo, and natural resin. Its synthesis from phenol, and the
correct determination of its formula, were successfully accomplished in 1841. 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. In 1873 Hermann Sprengel proved it could be detonated and by 1894 the
Russian workers had worked out a method of manufacture for artillery shells.
Soon after, most military powers used picric acid as their primary high explosive
material. However, shells filled with picric acid become highly unstable as the
compound corrodes bomb casings to form metal picrates which are more
sensitive than the parent phenol. The sensitivity of picric acid was demonstrated
in the Halifax Explosion. Picric was used in World War I [1], but the 20th century
saw picric acid largely replaced by TNT and/or cordite. Picric acid is also used in
the analytical chemistry of metals, ores, and minerals.
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. In 1887 the French government adopted it under the name
melinite, with addition of gun cotton. Since 1888, Britain started manufacturing a
very similar mixture in Lydd, Kent, under the name lyddite. Japan followed with
an improved formula known as schimose. In 1889, a similar material, a mixture of
ammonium cresylate with trinitrocresol, or an ammonium salt of trinitrocresol,
started to be manufactured under the name ecrasite.

Synthesis
The aromatic ring of phenol is highly activated towards electrophilic 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 sulphonated with oleum, and the resulting p-phenolsulfonic
acid is then nitrated with concentrated nitric acid. During this reaction, nitro
groups are introduced, and sulfonic acid groups are displaced. The reaction is
highly exothermic, and careful temperature control is required.

Uses
By far the largest use has been in munitions and explosives, as discussed above.
 3

In microscopy, picric acid is a reagent for staining samples, e.g. Gram staining. 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.
Bouin's picro-formol is a preservative solution used for biological specimens.
Workplace drug testing utilizes picric acid for the Jaffe Reaction to test for
creatinine. It forms a colored complex that can be measured using spectroscopy.
Much less commonly, wet picric acid has been used as a skin dye or temporary
branding agent. It reacts with proteins in the skin to give a dark brown color that
may last as long as a month.
In the early 20th century, picric acid was stocked in pharmacies as an antiseptic
and as a treatment for burns, malaria, herpes, and smallpox.

Safety
Modern safety precautions recommend storing picric acid wet. Dry picric acid is
relatively sensitive to shock and friction, so laboratories that use it store it in
bottles under a layer of water, rendering it safe. Glass or plastic bottles are
required, as picric acid can easily form metal picrate salts that are even more
sensitive and hazardous than the acid itself. Industrially, picric acid is especially
hazardous because it is volatile and slowly sublimes even at room temperature.
Over time, the buildup of picrates on exposed metal surfaces can constitute a
grave hazard.
In 2007, a bomb squad removed a World War I-era bottle containing two ounces
of picric acid in Columbus, Wisconsin.[2] In another 2007 incident, a bomb squad
detonated a sample in Hayward, California.[3] In 2008, bomb disposal experts
removed and later detonated a 200 g (7 oz) sample found at the Marling School
(Stroud, Gloucestershire) science department.[4] [5] In the same year, 1-lb. bottle
of the acid was removed and later detonated by a bomb squad from an old
pharmacy in Jerseyville, Illinois.[6] In Summer 2008 German police blasted at
least about 50 picric acid bottles they found in schools (34 bottles), pharmacies
and industry. [7] The official justification given in news media was that dry picric
acid would be too dangerous to handle in order to add water and that picric acid
might detonate when the bottle is opened.
Picric acid
Picric acid or 2,4,6-trinitrophenol , C 6 H 2 (NO 2 ) 3 OH, a toxic yellow crystalline
solid that melts at 122°C and is soluble in most organic solvents. Picric acid is a
derivative of phenol . It reacts with metals to form metal picrates, which like picric
acid itself are highly sensitive explosives that can be detonated by heat, flame,
shock, or friction. The high explosives lyddite and melinite are composed mostly
of compressed or fused picric acid. Picric acid is often used as a booster to
detonate another, less sensitive explosive, such as TNT ( trinitrotoluene ).
Although picric acid can be synthesized by nitration of phenol, higher yields are
obtained if chlorobenzene is used as a starting material; the latter method
involves several steps and the formation of several intermediate products. In
addition to its use in explosives, picric acid has been used as a yellow dye, as an
antiseptic, and in the synthesis of chloropicrin, or nitrotrichloromethane, CCl 3
NO 2 , a powerful insecticide