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Picric Acid

melting point boiling point molecular mass density

Picric Acid
122 °C explodes over 300 °C 229.11 g/mol 1.763 g/mL
sensitivity chemical formula explosive velocity estimated cost
table key
medium C6H3N3O7 7480 m/s $?.00/g

Picric acid, or 2,4,6-trinitrophenol, has also been called picronitric acid; carbazotic acid;
nitroxanthic acid; melinite; lyddite; pertite; shimose; melinit; granatfullung; sprengkorper 88;
pertit; picrinit; ekrasit; TNF; and shimoza. Picric acid is both a useful explosive compound and a
precursor to other explosives. It does not see much use now a days as a laboratory reagent or
explosive. It is too dangerous for the lab and too costly for the battlefield. I found a very old bottle
in the lab once, the bottle had not been used for 5 years and should not have been there. It is
stable unless old, it will form a very unstable crystalline structure after many years. I have three
different methods of synthesizing picric acid. The first is a laboratory procedure using fairly
common chemical reagents, it will provide a better and cheaper product. The second is a lesser
used, but economical, catalytic process for possible large scale manufacture, its chemicals are
more difficult to get. The third is one of those improvisational procedures using aspirin tablets, it
sounds feasible. Picric acid was first mentioned in the alchemical writings of Glauber in 1742. The
old timers made it from nitrating animal horn, silk, indigo, natural resin, and the like. Its synthesis
from phenol, and the correct determination of its formula, was in 1841. It was not until 1830 did
anybody think to use picric acid as an explosive. Before then it was assumed that only the salts of
picric acid were explosive, not the acid itself. In 1873 H. Sprengel proved it could be detonated and
by 1894 the Russians had worked out a method of manufacture for artillery shells. Soon after,
every military power used picric acid as their primary high explosive material. The 20th century
saw the decline of picric acid, the replacement being TNT. The downfall was partially due to the
acidic nature and the sensitivity of picric acid. Today picric acid is more suited to detonators or
booster charges.

aspirin 1000-mL beaker
benzene 500-mL Erlenmeyer flask
ethyl alcohol 100-mL Florence flask
mercuric nitrate 2-L Florence flask
nitric acid glass filter paper
phenol graduated cylinder
potassium nitrate pipet/buret
sodium nitrate stirrer/stirring rod
sulfuric acid thermometer

Add 24 mL of phenol and 14 mL of 98-100% sulfuric acid to a round-bottomed 100-mL Florence

flask and reflux for 6 hours at 120°C on an oil bath. After the material has cooled, it is diluted with
46 mL of 72% sulfuric acid. Pour the solution from the round bottomed flask into a 500-mL
Erlenmeyer flask. 175 mL of 70% nitric acid is added dropwise, with a pipet or buret, add the acid
very slowly, a drop at a time. The addition of nitric acid will cause a vigorous reaction and release
toxic gas, use a fume hood or go outside. When all of the acid has been added and the reaction has
subsided, the mixture is heated for 2 hours on a steam bath to complete the nitration. After 8 to 12
hours the picric acid crystals should have separated. These crystals will need to be filtered with
glass filter paper because of the solutions high acidity. Otherwise, pour off most of the acid, dilute
with water, and filter with regular filter paper. Wash the crystals with several small portions of
water and allow to dry in the open air. To purify, dissolve the picric acid in 1 L of boiling water per
15 g of crystals, filter while hot and allow to cool slowly. Any heavy droplets of brown oil which
dissolve slowly during this boiling should be discarded. You will need a graduated cylinder for
measuring liquids, and a thermometer to monitor the temperature.

This catalytic process skips the roundabout way above and converts benzene directly into picric
acid in one step. The reagents of this reaction may be a bit hard to come by, however. Prepare a
solution of 10 g of mercuric nitrate in 600 mL of 70% nitric acid. Add this solution to a round-
bottomed 2-L Florence flask with 228 mL of benzene. Reflux the mixture for 7 hours on a sand
bath. Transfer the contents of the flask to another flask and distill it with a steam bath (not steam
distillation, simple or fractional will suffice). Benzene will distill over first, then nitrobenzene, and
finally a mixture of dinitrobenzene and dinitrophenol will come over slowly. The distillation is
continued until these volatile organics are removed. The remaining residue is filtered while hot to
remove any impurities and allowed to crystallize. the picric acid that should have crystallized can
be purified by recrystallizing from hot water.

This procedure uses aspirin tablets instead of phenol. Crush 100 aspirin tablets to a fine
powder. Put 500 mL of 95% ethyl alcohol in a 1000-mL beaker then add the aspirin powder. Gently
heat the alcohol while stirring to dissolve the acetylsalicylic acid within the tablets for 15 minutes.
Acetylsalicylic acid is the active ingredient in aspirin and a phenol derivative. Filter the still hot
alcohol to remove any excess tablet filler. Now heat the solution to evaporate off all of the alcohol,
leaving behind crystals of acetylsalicylic acid. When the crystals have dried, add them to a 1000-
mL beaker with 700 mL of 95-100% sulfuric acid. Heat the acid and stir to dissolve the
acetylsalicylic crystals. When all of the crystals have been dissolved, add 90 g of sodium nitrate or
potassium nitrate. Add a few grams at a time then wait for the reaction to subside before adding
more. The nitrate addition must be done in a well ventilated area as it produces deadly nitrogen
dioxide gas. When all of the nitrate has been added, allow the mix to cool to room temperature,
stirring it every few minutes. Pour it into 1500 mL of ice water to precipitate the picric acid. Decant
about 1000 mL of the acid water mix then add another 1000 mL of water. Filter the solution to
collect the picric acid crystals. You may purify the crystals as per method one. You will need a
stirring rod or magnetic stirrer for mixing.

This explosive is a phenol derivative. It is toxic and explosive compounds made from picric acid are
poisonous if inhaled, ingested, or handled and absorbed through the skin. The toxicity of this
explosive restricts its use due to the fact that over exposure in most cases causes liver and kidney
failure and sometimes death if immediate treatment is not obtained.

This explosive is a cousin to T.N.T. but is more powerful than it's cousin. It's the first explosive
used militarily and was adopted in 1888 as an artillery shell filler. Originally this explosive was
derived from coal tar but thanks to modern chemistry you can make this explosive easily in
approximately three hours from acetylsalicylic acid (aspirin purified).

This procedure involves dissolving the acetylsalicylic acid in warm sulfuric acid and adding sodium
or potassium nitrate which nitrates the purified aspirin and the whole mixture drowned in water
and filtered to obtain the final product. This explosive is called trinitrophenol. Care should be taken
to ensure that this explosive is stored in glass containers. Picric acid will form dangerous salts
when allowed to contact all metals except tin and aluminum. These salts are primary explosive and
are super sensitive. They also will cause the detonation of the picric acid.

Next needed is aspirin. The cheaper brands work best but buffered brands should be avoided.
Powder these tablets to a fine consistency. To extract the acetylsalicylic acid from this powder
place this powder in methyl alcohol and stir vigorously. Not all of the powder will dissolve. Filter
this powder out of the alcohol. Again wash this powder that was filtered out of the alcohol with
more alcohol but with a lesser amount than the first extraction. Again filter the remaining powder
out of the alcohol. Combine the now clear alcohol and allow it to evaporate in a pyrex dish. When
the alcohol has evaporated there will be a surprising amount of crystals in the bottom of the pyrex

Take forty grams of these purified acetylsalicylic acid crystals and dissolve them in 150 ml. of
sulfuric acid (98%, specify gravity 1.8) and heat to dissolve all the crystals. This heating can be
done in a common electric frying pan with the thermostat set on 150 deg. F. and filled with a good
cooking oil.

When all the crystals have dissolved in the sulfuric acid take the beaker, that you've done all this
dissolving in (600 ml.), out of the oil bath. This next step will need to be done with a very good
ventilation system (it is a good idea to do any chemistry work such as the whole procedure and
any procedure in this file with good ventilation or outside). Slowly start adding 58 g. of sodium
nitrate or 77 g. of potassium nitrate to the acid mixture in the beaker very slowly in small portions
with vigorous stirring. A red gas (nitrogen trioxide) will be formed and this should be avoided. The
mixture is likely to foam up and the addition should be stopped until the foaming goes down to
prevent the overflow of the acid mixture in the beaker. When the sodium or potassium nitrate has
been added, the mixture is allowed to cool somewhat (30-40 deg. C.). The solution should then be
dumped slowly into twice it's volume of crushed ice and water. The brilliant yellow crystals will
form in the water. These should be filtered out and placed in 200 ml. of boiling distilled water. This
water is allowed to cool and then the crystals are then filtered out of the water. These crystals are
a very, very pure trinitrophenol. These crystals are then placed in a pyrex dish and placed in an oil
bath and heated to 80 deg. C. and held there for 2 hours. This temperature is best maintained and
checked with a thermometer. The crystals are then powdered in small quantities to a face powder
consistency. These powdered crystals are then mixed with 10% by weight wax and 5% vaseline
which are to melting temperature and poured into the crystals. The mixing is best done by
kneading together with gloved hands. This explosive should have a useful plasticity range of 0-40
deg. C.. The detonation velocity should be around 7000 m/sec.. It is toxic to handle but simply
made from common ingredients and is suitable for most demolition work requiring a moderately
high detonation velocity. It is very suitable for shaped charges and some steel cutting charges. It is
not as good an explosive as C-4 or other R.D.X. based explosives but it is much easier to make.
Again this explosive is very toxic and should be treated with great care.



TNP Synthese
In my endless hunger for new experiences in the field of energetic materials,
I tried to make some trinitrophenol, also known as picric acid.
So I went out of my cosey little house, and got me 20 aspirines,
(each containing 0.5 grams of acetylsalicylic acid) from the good people at bayer.
Once I got home I purified these using warm acetone.

Since many people asked me:"How do you purify aspirines with warm acetone?"
Here's how:

Heat up acetone to around 50°C, while it's heating, crush the aspirine tablets
and add them to the acetone. Stir well so all that remain is a very fine dust
on the bottom of your beaker. Then filter with a coffee filter, and save the liquid.
Rinse the filter with a little more warm acetone. Now let all the acetone evaporate.
What is left should be nice white pure acetylsalicylic acid crystals.

Now what would you need for making this into TNP ?
- 140 ml of >95% H2SO4 (sulfuric acid)
- 20 grams of KNO3 (potassium nitrate)
- 10 grams of acetylsalicylic acid (ASA)

First dissolve the ASA in hot sulfuric acid, then add the KNO3. You might want to
easy on the addition of KNO3, because this tends to heat the mixture quite a bit.
I don't think there is risk for an explosion when the TNP is in solution, but I don't
recommend you try to find out!!
And definately don't complain with me when it blows up in your face, leaving you
bleeding and full of acid (ouch).
Anyway, once the KNO3 is all added to the acid, you let is cool down nice and
not applying extra cooling or anything, and give it an occasional stir,
so gasses can escape the liquid. (wich should be nice red by now)

Now dump this red liquid (when at lower temperature) in 0.5 liter of ice water.
You'll immedialty notice the change if you're not colorblind, it turns nice yellow !!
Leave it a bit, with good stirring, so all the yellow TNP comes out,
but while keeping the mixture as cold as possible.

Then filter this mixture (normal filter paper should be okay when you used enough
of ice-water).

Don't forget to rinse with as cold as possible water (barely liquid)

Not too much, but make sure most of the H2SO4 is rinsed off.

Now you can sqeeze this out, and put it in the sun for drying,
which is going to be very difficult if there is still some sulfuric acid present.

From 10 grams of ASA, I got 10 grams of TNP, and I did it in 2 steps,

so you should be able to get some more out of it

Picric acid
Picric acid or Trinitrophenol is, by far, one of the more dangerous chemicals being used today.
Classified as a flammable solid when wetted with more than 30% water (UN1344, class 4.1) and a
class A high explosive with less than 30% water (UN0154, class 1.1D), it has some very interesting
properties. It is explosive but also highly shock, heat and friction sensitive. In fact, detonation with
a speed and power superior to that of TNTcan occur by a 2 kg weight falling onto solid picric acid
from a height of 36 cm. Picric acid is toxic by all routes of entry, it’s also a skin irritant and allergen
and will produce toxic pro-ducts on decomposition.

Picric acid is used primarily in the manufacture of explosives and as an intermediate in dye
manufacturing. It is also present in many laboratories, for use as a chemical reagent. Water is
added to picric acid to act as a desensitizer. The wetted product is significantly less shock sensitive
than the dry acid. Picric acid is highly reactive with a wide variety of chemicals and extremely
susceptible to the formation of picrate salts. Many of these salts are even more reactive and shock
sensitive than the acid itself.

Picrate Salts
Picrate salts are formed by the reaction of picric acid with any of the following: metals, metal salts,
bases, ammonia and concrete. Particular attention must be paid in order to prevent the formation
of picrate salts during normal use of picric acid. Picric acid must never be allowed to dry out but
even more importantly, it should never be allowed to dry out on metal or concrete surfaces. Metal
picrates are particularly sensitive and can be formed with metals such as copper, nickel, lead, iron
and zinc. Calcium picrate is formed by the reaction of picric acid with concrete. In the
last several years, CANUTEC has assisted many individuals in dealing with incidents
involving picric acid. The scenario is usually the same, involving bottles of product that
have been left on a laboratory shelf over a period of years. The dangers of this kind of
situation are twofold. First, the acid, which usually exists as a wetted paste, may dry out
causing the formation of the shock sensitive acid crystals mentioned above. The second
hazard possibility arises from the introduction of impurities into bottles that have been
previously opened and are no longer airtight. These could bring about the formation of
picrate salts inside the bottle or within the threads of the lid. Either of these situations
should be considered extremely serious and handled accordingly.

Picric Acid (2,4,6-Trinitrophenol) Laboratory Synthesis (industrial and laboratory methods):

Picronitric acid, Carbazotic acid, nitroxantic acid. C6H3N3O7; Molar Weight; 229.11. Percentage composition; C:
31.46%, H: 1.32%, N: 18.34%, O: 48.88%. Picric Acid is used in electric batteries, leather industry, dies,
pigments, inks, paints, manufacture of colored glass, textile mordants, as a laboratory reagent, in matches and
explosives. It consists in pale yellow, odorless, intensely bitter crystals of density 1,763 and melting point 122 -
123C. It explodes at 300C. One gram dissolves in 78mL water, 15mL boiling water, 12ml alcohol, 10ml benzene,
35ml chloroform, 65ml ether. It is incompatible with all oxidising substances, albumin, alkaloids and gelatin. It
should be kept in a cool place and remote from fire. (Source: Merck Index 12th edition).
Picric Acid was one of my first Organic Synthesis ever, and was performed at High school, under supervision of
my Higher Level I.B. chemistry teacher when I was 16 years old. It was part of an assignment and I was rather
surprised that our textbook would carry the instructions for the synthesis of a potentially explosive compound, and
more surprised still that we would be given this particular synthesis in class as an assignment. Since we were, I
don't see any problem in replicating it here for the general information of the POWERLABS public. However, the
usual warnings apply:
As with any other nitration, this procedure is hazardous and involves
the use of highly corrosive acids. The final product is toxic and
dangerous. This should only be attempted by experienced chemists!

Reactants: Glassware:
98% Concentrated Sulfuric Acid (H2SO4(l)) 250mL Glass beaker.
68% Concentrated Nitric Acid (HNO3(aq)) Pipette
Phenol (C6H5OH(s)) Stirring Rod
Ethanol (C2H6O(l)) Funnel/filter paper
Distilled Water (H2O(l)) Ice bath

Here all the chemicals used in the synthesis are seen, from left to right, back to front: Absolute Ethanol, Phenol,
Sulphuric Acid (98%), Nitric Acid (68%), Distilled water.

A note on proportions: 0.8grams of phenol are reacted for every 1.5ml of Nitric acid and 1ml of sulfuric acid.

C6H5OH(s) + H2SO4(l) => (HO.C6H4.SO3H + H2O) + HNO3(aq) => C6H3N3O7

25grams of powdered phenol are weighted and added to a 250ml
beaker containing 31.25ml (57.81g) of concentrated sulfuric acid. The
mixture is stirred and than heated on a hotplate at 100C for 30 minutes
until it becomes dark colored, indicating the formation of phenol-4-
sulphonic acid. This is than chilled to -5C on a water bath with salt
added, becoming a cold viscous syrup, to which 47ml of chilled (-5C)
nitric acid are added inside a fume cupboard, making sure that the
mixture is not allowed to warm up prior to the addition of the acid.
Within a few minutes a vigorous reaction will occur which will produce
large amounts of nitrogen dioxide, a red colored (poisonous!) gas. One
must be very careful with sputtering during this reaction.

The reaction is allowed to subside and than the mixture (which has now become a thin, orange/yellow liquid) is
heated on a water bath for one and a half hours, with occasional shaking.

When the heating is complete the mixture is allowed to cool down and 313ml of cold water are added, causing the
Picric Acid to crystallize out of the mixture. The mixture is cooled to 5C so as to precipitate most of the remaining
Picric acid, and than is quickly filtered and washed with 1200mL of cold distilled water so as to remove any traces
of the nitration acids.

The filtrate appears as the fine yellowish mass of crystals seen to the
left. Yield is approximately 40grams for the 25 grams of phenol that
was started out with. These crystals are high purity and have all of the
properties attributed to reagent grade Picric Acid. However, they can
be purified:
Making use of Phenol's high water solubility, and the higher solubility of
dinitro and mononitroPhenol, the Picric Acid can be purified to near
analytical grade by re-crystallization from a solvent mixture of 1 volume
ethanol and 2 volumes water, roughly 9ml of solvent being required
per gram of Picric Acid.

The crystals are than removed by vacuum filtering, are vacuum dried in a dissector, and form into a nearly yellow
mass of mp 123C.
It is advisable to store Picric Acid wet with at least 30% water and in rubber stoppered flasks.

This acid may be used for other synthesis, such as Ammonium Picrate (C6H2.ONH4.(NO2)3) Ammonium picrate,
also called ammonium piconitrate, Explosive D, or carbazoate is a commonly used safety explosive which is
insensitive enough to be used in shells that penetrate armor and detonate inside it. It requires a substantial shock
to cause it to detonate, slightly less than that required to detonate ammonium nitrate. In many ways it is much
safer than picric acid, since it does not have the tendency to form hazardous unstable salts when placed in metal
containers. Vdet 7100M/s. It is made by dissolving picric acid crystals in 15 parts hot, steaming distilled water and
adding clear ammonia in excess, allowing the excess ammonia to evaporate (excess ammonia should not be
used as it will form a red precipitate that is more sensitive than pure Ammonium Picrate. Yellow ammonium
picrate can be obtained from red picrate by recrystallizing it several times from water. It also eventually changes
into the yellow form if stored as a concentrated solution. Keep this material as dry as possible). The powder
remaining should be ammonium picrate. The water should not be heated, as ammonium picrate is sensitive to
heat. Vacuum distillation and open evaporation are relatively safe ways to extract the picrate. Ammonium picrate
most commonly appears as bright yellow crystals, and is soluble in water. These crystals should be treated with
the care due to all shock sensitive materials. Some illegal salutes have been found to contain ammonium picrate,
which makes them much more hazardous. Equation goes as follows:
NH3·H2O + C6H2(NO2)3OH ---> C6H2·(NO2)3·O·NH4 + H2O
Melts at 271°C, impact sensitivity is 20% less impact than TNT, and relative strength is 93 - 100% TNT in the
trauzl test.
Picric Acid can also be produced from Phenol derivatives such as Salicylic and Acetylsalicylic acids. The
procedure is exactly the same as the one outlined above, except a smaller amount of Salicyclic (0,6grams per
1mL H2SO4 and 1,5mL HNO3) our Acetylsalicylic (0,5g per 1mL H2SO4 and 1,5mL HNO3) acids are used. This is
important because Acetylsalicylic acid is the active ingredient in aspirin and can be obtained by dissolving them in
hot ethanol (20 500mG pills per 100mL), filtering out the buffers, and allowing the pure acid to crystallize out. The
reaction than goes:
C9H8O4 -------> C2H4O2 + C7H4O2
(The sulfuric acid breaks down the acetylsalicylic acid to acetic and salicylic acid)

Or if Salicylic acid is used,

C7H4O2 + H2O ---> C6H6O + CO2
(Salicylic acid with heat source converts to carbolic acid (phenol) and carbon dioxide; (in presence of water from
98% H2SO4)
Or the formed phenol just sulfonates rapidly. From Phenol-4-sulfonic acid onwards the reaction proceeds as
outlined above.
The Nitric Acid can also be substituted by adding 15 grams Sodium Nitrate per 80mL H2SO4.
With the NaNO3/H2SO4 nitrating system (H2SO4 already present) without any external cooling; the phenolsulfonic
compound readily nitrates to a polynitro compound (2,4,6-trinitrophenol).

Yet another way of preparing picric acid is by the conversion of benzene directly into picric acid in one step. This
was patented by Mueller Teeters in 1948 (US pat. 2,455,322): 1g of mercuric nitrate is added to 60mL of 70%
nitric acid which is than stirred and added to 23 mL of benzene. The mixture is than heated for several hours and
distilled. Benzene will distill over first, then nitrobenzene, and finally a mixture of dinitrobenzene and dinitrophenol
will come over slowly. The distillation is continued until these volatile organics are removed. The remaining
residue is filtered while hot to remove any impurities and allowed to crystallize. the picric acid that should have
crystallized can be purified by recrystallizing from hot water.

Picric Acid can be used alone or in the synthesis of picrate salts such as, for example:
Potassium Picrate.
Lead Picrate.