High explosives are detonating explosives.

  The chemical reaction

propagates with such rapidity that by the rate of reaction zone into
the material exceeds velocity of sound.  High explosives have again
been sub-divided in to two groups according to their function in the
explosive train i.e. Primary explosives and Secondary explosives.

Primary Explosives:
These are the explosives which are used to start or initiate
the explosion.  These compounds are highly sensitive to
mechanical shock, friction and heat and readily ignited by
direct contact with flame or electrical sparks. The main
function of Primary explosives is to initiate a secondary
explosive by shock wave. Because of their sensitivity they
are used in small quantities. Initiators are mainly used in
military detonators, industrial blasting caps and stab, and
shock primers.
 Figure of insensitivity should not normally
exceed 40.
 quickly develops into detonating wave
 it should not cause any premature detonation
 should be stable in storage and safe to handle
during transportation
 should not react with container
 ease of safe manufacture of explosive
Mercury fulminate:
• Mercury fulminate is a heavy non hygroscopic crystalline solid.
• It is thermally unstable and very sensitive to impact, friction, spark, flame and shock
when dry.
• It reacts with metals such as aluminium, magnesium, zinc, brass and bronze in moist
atmosphere.
• Being a mercury derivative, it is a toxic compound.
• Practically insoluble in water
•Colourless crystals
•Empirical formula: C2N2O2Hg
•Molecular weight:  284.6
•Deflagration point: 1650C
•Impact sensitivity:  0.1-0.2 kp m

SYNTHESIS
• Mercury(II) fulminate is prepared by
dissolving mercury in nitric acid after which the solution
is poured into 95% ethanol. Vigorous gas evolution
takes place and crystals are formed which are filtered
and washed until they become neutral.
• It was first prepared by Edward Charles Howard in
1800.
• The crystal structure of this compound was only
determined in 2007.
Lead azide: (Pb(N3 ) 2)
• Lead azide has a high temperature of ignition and less sensitive to shock and friction than mercury
fulminate.  
• It has good stability to heat and storage. 
• Due to its high temperature of ignition it is generally used in primary mixtures with lead styphnate
which is very easy to ignite. 
• Its contact with copper must be avoided because it leads to the formation of copper azide. 
• Since it is a non conductor it may be mixed with flaked graphite to form a conductive mixture for use
in low energy electrical detonator.
•Insoluble in water
•Colourless crystals
•Molecular weight:  291.3
•Deflagration point: 320 - 3600C
•Impact sensitivity:  0.25 – 0.4 kp m

SYNTHESIS
1.Lead azide is prepared by metathesis between sodium azide and lead nitrate. 
Dextrin can be added to the solution to stabilize the precipitated product. The
solid is not very hygroscopic, and water does not reduce its impact sensitivity.
2. An alternative method involves dissolving lead acetate in a sodium azide
solution.
Lead Styphnate: (Lead trinitroresorcinate)
• It is thermally stable, non-corrosive and non-hygroscopic. It is sensitive to flame and
electrostatic discharge. It is therefore used to sensitize lead azide and initiate burning in
primer compositions.
•Practically insoluble in water and is sparingly soluble in acetone and ethanol. 
•Insoluble in ether, chloroform, benzene and toluene.
•Orange yellow to dark brown crystals
•Empirical formula: C6H3N3O9Pb
•Molecular weight:  468.3
•Deflagration point: 275-2800C
•Impact sensitivity:  0.25 – 0.5 kpm

SYNTHESIS
1.It is prepared by precipitation with a solution of lead nitrate from a solution of magnesium
trinitroresorcinate, maintaining 70 to 75C. After 15minutes of completion of reaction,
temperature is reduced to 35C. It is washed three times in alcohol and then dried in absence
of CO2. It is then sealed and weighed.
2.Since Styphnic acid is very similar to Picric Acid, the procedure used was the same as the
one successfully employed in the synthesis of Lead Picrate.
A saturated solution of Styphnic acid in methanol was formed and to it Lead
Monoxide was added. Heating was continued whilst stirring until a solid mass remained;
C6H3N3O8(s) + PbO(s) => PbC6H2N3O8(s)
• The final product is a yellow/brown colored mass of crystals.
Tetrazene:
• It is slightly hygroscopic and explodes readily from flame, producing a large amount of
smoke. It decomposes in boiling water.
• It ignites readily and is slightly more sensitive to impact than mercury fulminate. Its main
use is for the sensitization of priming composition.
•Practically insoluble in water, alcohol, ether, benzene and carbon tetra chlorides.
•Feathery, colorless to Pale yellow crystals
•Empirical formula: C2H8N10O
•Molecular weight:  188.2
•Deflagration point: 1400C
•Impact sensitivity:  0.1 kp m

SYNTHESIS
1.It is prepared by the action of sodium nitrate with amino guanidine salt.
2.Functionalized tetrazolyl - tetrazenes as energetic compounds have been
synthesized by the oxidation of hydrazines.
In all cases the product obtained was a colorless solid. The tetrazenes
synthesized via this method show no melting points, but extremely
sharp decomposition points.
 Secondary Explosives
• Secondary explosives are generally used as the main charge. 
• These explosives can also be classified according to their chemical structure. 
• The most important class includes the organic compound which contains the
nitro group. 
Picric acid (2,4,6-trinitrophenol ):
• It was used in large caliber shells in World War I.
• In World War II a mixture of ammonium picrate and TNT was widely used in the press loading of
armour piercing shell.
• Soluble in hot water and readily soluble in alcohol, ether, benzene and acetone.
•Yellow crystals
•Empirical formula: C6H3N3O7
•Molecular weight:  229.1
•Deflagration point: 3000C
•Impact sensitivity:  0.75 kp m
•Solidification point: 122.50C
SYNTHESIS:
• The aromatic ring of phenol is highly 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 p-hydroxyphenylsulfonic 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.
TNT (2,4,6-trinitrotoluene) :
• It is the most widely used military explosives.
• Its main features include low melting point, stability, low sensitivity to impact, friction and high temperature and its
relative safe methods of manufacture.
•Almost insoluble in water, sparingly soluble in alcohol and soluble in benzene, toluene and acetone.
•Pale yellow crystals; if granulated; flakes.
•Empirical formula: C7H5N3O6
•Molecular weight:  227.1
•Deflagration point: 3000C
•Impact sensitivity:  1.5 kp m
•Solidification point: 80.80C
SYNTHESIS
• In industry, TNT is produced in a three-step process.
• First, toluene is nitrated with a mixture
of sulfuric and nitric acid to produce mononitrotoluene
(MNT).
• The MNT is separated and then renitrated
to dinitrotoluene or DNT.
• In the final step, the DNT is nitrated to trinitrotoluene or
TNT using an anhydrous mixture of nitric acid and oleum.
• Nitric acid is consumed by the manufacturing process,
but the diluted sulfuric acid can be reconcentrated and
reused.
• Subsequent to nitration, TNT is stabilized by a process
called sulfitation, where the crude TNT is treated with
aqueous sodium sulfite solution in order to remove less
stable isomers of TNT and other undesired reaction
products.
•The rinse water from sulphitation is known as red
water and is a significant pollutant and waste product of
Tetryl (2,4,6-trinitrophenylmethylnitramine):
• It is used in military boosters. (Ref 2, Page 4)
•Practically insoluble in water, sparingly soluble in alcohol, ether and benzene and is more readily
soluble in acetone.
•Pale yellow crystals.
•Empirical formula: C7H5N5O8
•Molecular weight:  287.1
•Deflagration point: 1850C
•Impact sensitivity:  0.3 kp m

SYNTHESIS
Tetryl is produced by simply slowly mixing dimethylaniline with concentrated nitric acid in
the presence of sulfuric acid with cooling arrangement.
PETN (pentaerythritol tetranitrate):
• It is used as a base charge in blasting caps and detonators as the core explosives in detonating cord, in booster
charges, in plastic explosives, and as an ingredient in other explosives.
• The chemical stability of PETN is very high and is considered to be more stable than all other nitrate esters.
• Insoluble in water, sparingly soluble in alcohol, ether and benzene and soluble in acetone and methyl acetate.
•Colourless crystals.
•Empirical formula: C5H8N4O12
•Molecular weight:  316.1
•Deflagration point: 2020C
•Impact sensitivity:  0.3 kp m
•Melting point: 141.30C

SYNTHESIS:
Production is by the reaction of pentaerythritol with concentrated nitric acid to form a
precipitate which can be recrystallized from acetone to give processable crystals.[
RDX (cyclotrimethylene trinitramine):
• It is also known as cyclonite and hexogen.
• It is one of the most important military explosives used today.
• It has high chemical stability lower than that of TNT and an explosive power much greater than TNT.
• RDX is considerably more susceptible than TNT to shock detonation.
• RDX is used as a component in mixtures with other explosives such as TNT and as a plastic explosives.
• A well-known plastic explosive, Semtex is based on RDX and PETN. Mixtures of RDX and wax are used for booster
charges in much military ammunition especially in artillery shells.
• Soluble in acetone, insoluble in water and sparingly soluble in ether and ethanol.  Cyclohexanone, nitrobenzene and
glycol are solvents at elevated temperatures. 
•Colourless crystals.
•Empirical formula: C3H6N6O6
•Molecular weight:  222.1
•Impact sensitivity:  0.75 kp m
•Melting point: 2040C

MANUFACTURE OF RDX

RDX is manufactured by three important processes known as:

1.Classical method of production by Henning

2.Woolwich or direct nitrolysis method
3.Bachmann process
 SYNTHESIS
1.CLASSICAL METHOD:
The manufacture of RDX is done by nitrating hexamethylenetetramine to
hexogen using concentrated nitric acid. The concentrated reaction mixture is then
poured into ice water and RDX is precipitated out.

2. WOOLWICH METHOD:
In woolwich method or direct nitrolysis, essentially of oxidation of methyl
alcohol to formaldehyde, its conversion to hexamethylene tetramine. The
hexamine is reacted with nitric acid to produce RDX. The yield in this process is
70-75%. RDX thus obtained will have traces of HMX.

3. Bachmann process:
Large scale production of RDX is done by using Bachmann process. This
is an American - Canadian process. In this process hexamine is reacted at 75C
with ammonium nitrate and nitric acid mixture in the presence of acetic acid and
acetic anhydride. The yield of RDX is about 79% + 6% HMX and other
intermediates. The waste acetic acid is concentrated, recycled and the
regenerated acetic anhydride is reused.
HMX (Cyclotetramethylenetetranitramine):
• It is known as octogen.
• It is used in military application as booster charges for artillery shells and as a component of solid fuel
rocket propellants.
• HMX exists as a (orthorhombic), b (monoclinic), g (monoclinic) and d (hexagonal) forms of which, ‘b’
form is the least sensitive to impact and the most stable. It is therefore the form required for military
use.
•Practically insoluble in water and sparingly soluble in ether and ethanol. 
Cyclohexanone, nitrobenzene and glycol are solvents at elevated
temperatures.
•Colourless crystals.
•Empirical formula: C4H8N8O8
•Molecular weight:  296.2
•Deflagration point: 2870C
•Impact sensitivity:  0.75 kp m
•Melting point: 2750C
•Exists in four different isomeric forms.  They are α-, β-, γ-, δ- HMX.

SYNTHESIS:
By Bachmann process, by varying the parameters and temperature acid
concentration, ammonium nitrate and acetic anhydride rate of HMX/RDX
can be altered upto 73% yield of HMX.
TATP:
Triacetone triperoxide (TATP) is organic peroxide containing neither metallic elements nor nitro
group. Therefore the presence of peroxide group cannot be detected by standard security procedure
like transmission and vapor detector.
Nitroglycerine (NG):
•It is widely used industrial explosives. It has been the main component in dynamites and is
an ingredient in multi based propellant. It is very sensitive to shock, impact and friction
and used only when desensitized with other liquids or absorbent solids or when mixed with
nitrocellulose. Almost insoluble in water, but soluble in most organic solvents; it is   
sparingly soluble in carbon disulphide. 
•Empirical formula: C3H5N3O9
•Molecular weight:  227.1
•Impact sensitivity:  0.02 kp m
•Solidification point: +13.20C

SYNTHESIS
•The industrial manufacturing process often uses a nearly 1:1 mixture of
concentrated sulfuric acid and concentrated nitric acid.
• The sulfuric acid produces protonated nitric acid species, which are attacked by
glycerin's nucleophilic oxygen atoms.
• The nitro group is thus added as an ester C-O-NO2 and water is produced.
• This is different from an electrophilic aromatic substitution reaction in which nitronium
ions are the electrophile.
NITROCELLULOSE
Nitrocellulose (also: cellulose nitrate, flash
paper, flash cotton, guncotton, flash string) is a
highly flammable compound formed
by nitrating cellulose through exposure to nitric acid or
another powerful nitrating agent. When used as
a propellant or low-order explosive, it was originally
known as guncotton.
 It had been an ingredient in explosive
AMMONIUM NITRATE: since the earliest days primarily as an
• The chemical compound ammonium nitrate, oxidizer in NG dynamite mixtures.
the nitrate salt of ammonia, has the chemical •Readily soluble in water.
•Colourless crystals
formula NH4NO3. •Molecular weight:  80.0
• It is a white crystalline solid which is highly soluble in •Impact sensitivity:  Up to 5 kp m
•Melting point: 169.60C
water. It is predominantly used in agriculture as a high-
•Deflagration point: 169.6-2100C
nitrogen fertilizer. 
• The compound is used as explosives in mining, but
also improvised explosive devices.
• It is the main component of ANFO, a popular
explosive, which accounts for 80% explosives used in
North America.

SYNTHESIS:
The industrial production of ammonium nitrate entails
the acid-base reaction of ammonia with nitric acid:
HNO3 + NH3 → NH4NO3
Dynamite:
• Over the years, formulas for dynamite have been developed to hit every type of rock
blasting.
• Varieties have been developed for severe water conditions utilizing nitro cotton to gel the
NG (the gelatins are one branch of the dynamite family) for cohesiveness to enable loading
into up holes in mines, for safe usage in under- ground coal mines (the permissible having
salts of various types to cool the explosive reaction as part of formula) and for economics by
making formulas with very high ammonium nitrate percentages (and thus no cohesiveness
or water resistance) where severe field conditions do not exists.
• Literally thousands of different formulas might be found, but for years all had the
commonality of having nitroglycerine as a component.
• Dynamites are manufactured under different names.
1.Straight Dynamite:
It contains 10-20% NG-EGDN and are powdery and may deteriorate when exposed
to water.
It was the original dynamite. Presently the composition is: NG-20-57%, Sodium
Nitrate – 59-23%, Carbonaceous fuel-15.4-18.2%, Sulphur-2.95% and Antacid – 1.3-1.2%
2. Ammonia Dynamite:
commonly used today. Normal composition is NG – 12-22%, SN 57-15%,
Ammonium nitrate 12-15%, NC 10.2-8.6%, S-6.7-1.6%, Carbonaceous fuel – 6.7-1.6% and
antacid 1.2-1.15%
3. Gelatine dynamite:
invented by alfred nobel in 1875 by incorporating 92% liquid NG with 8% of colloids
NC.
4. Semigelatine:
contains NC, NG, Ammonium nitrate and carbonaceous ingredients.
5. Military dynamite:
do not use NG explosive. TNT-15%, RDX-75%,Corn Starch – 5%
Liquid oxygen explosives (LOX):
Dynamite faced some minor competition when LOX was introduced into
the surface coal mines. It is a simple material--a cloth cartridge containing
carbon black is soaked in a vat of liquid oxygen until the material in the
cartridge is totally saturated. The cartridges are immediately lowered into
the bore hole stemmed and shot. A drawback is that only a very limited
number of holes can be loaded since the evaporation of the oxygen is
rapid. 
Ammonium nitrate- Fuel oil (ANFO):
These mixtures are made of porous prills of ammonium nitrate
(94%) soaked in fuel oil. In some cases aluminium is added to
increase the explosive strength. These explosives are
inexpensive and safe to handle but low in explosive strength and
detonation velocity. They cannot be used in presence of water.
ANFO is becoming popular for
underground mine operation.
Velocity of detonation = 2000-3000m/s
Slurry explosive water gels:
These explosives are made of aqueous solutions of ammonium nitrate and sodium or
calcium nitrate, gelled by the addition of guar gum or cross linking agents. They are
sensitized by nitro explosives or organic amine nitrates. Combustible materials such as
Aluminium, urea, sugar or glycol are mixed with these solutions. Slurry is a thickened
(usually by a guar gum a polysaccharide) but not a cross linked product. Water gel which
contain a cross linking agent for polysaccharide thickeners. The cross linking agents form a
chemical bond.

Typical slurry explosives contain

Ammonium nitrate (30 – 70%)
Sodium nitrate (10-15%)
Calcium nitrate (15-20%)
Aliphatic amine nitrate up to 40%
Al (10-15%)
TNT or other explosive sensitizers (5-15%)
Gellants (1-2%)
Stabilizers (0.1- 2%),
Ethylene glycol (3-15%)
Water (10-20%)
Explosive emulsions:
Emulsions are sensitized by air bubbles introduced by means of hollow glass of plastic bubble. Because
the emulsions are neither gelled nor cross linked, their storage time is limited. Their relative high
detonation velocity compensate for low explosive strength of the constituents. The common ingredients
are ammonium nitrate, sodium nitrate, fuel oil, wax and emulsifiers sensitized with plastic micro
spheres and other micro-ingredient, (monomethyl amine nitrate, sodium perchlorate)
 Low Explosives:
Low explosives or propellants burn at relatively low rates (cm/sec) whereas high explosives detonate at
velocities of km/sec. The main applications of propellants are in launching projectiles from guns,
rockets and missile systems. Propellants are mixtures of one or more energetic materials, plasticizers,
stabilizers to improve processing characteristics, stabilizers increase storage life and inorganic
additives facilitate safe handling, improve ignitability and decrease muzzle flash.

Propellants:
Black powder (gun powder):
Black powder possibly the oldest explosive used today mainly as an igniter for NC gun
propellants and to some extent in safety blasting fuses, delay fuse, signal and distress
rockets and in fire crackers. It is also used for mining when a lower power explosive is
used.
The composition of black powder:
Potassium nitrate + charcoal + sulphur in the ratio 75:15:10.
Sodium nitrate + charcoal + sulphur
Sulphur less powder: Potassium nitrate + charcoal
Ammonium powder: Potassium nitrate + Ammonium nitrate +charcoal
Smokeless powder:
It is the most widely used propellant based on NC. Propellants containing only
plasticized NC as energy source are called single based propellants. (NC + Stabilizer)
e.g. Diphenylamine (DPA)
Double based propellants contain NC + nitroglycerine and a stabilizer (DPA) such as
NC, NG & Stabilizer as DPA.
Triple base propellants incorporate also a crystalline explosive such as nitro
guanidine. (Propellants also contain stabilizers, plasticizers and coatings and
sometimes a burning modifier. Triple base propellants contain along with NC, ONG
another, crystalline explosive (nitro guanidine) plus plasticizer, coatings and