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History, Nature and

Classification of High
Explosives

Classification of Explosives based on


Chemical Groups
1.

Peroxides / Ozonides

-O O-O O O-

2.

Chlorates / Perchlorates

-OClO2
-OClO3

3.

Nitro

CNO2, -ONO2
NNO2

4.

Azides

5.

Fulminates

ON

N-N
C

Classification of Explosives based on


Chemical Groups (Contd.)
6.

Acetylides

-C

7.

Halides of Nitrogen

NX3 (e.g. NI3)

8.

Organometalics

RMgX

Most of the military explosives belongs to nitro class of


compounds.

Nature of High Explosives

Primary (Initiatory
Explosives)

Secondary (Military or
Civil Explosives)

Very sensitive (less stability)

Less sensitive (high stability)

Undergo very rapid transition


from burning to detonation

Very powerful than primary


explosives

Ability to transmit detonation to


less sensitive explosives

Can be only detonated with heat


or shock from primary explosives

Detonate with heat or shock.

Ex. Picric acid, TNT, RDX, HMX,


TATB, etc.

Ex. Mercury fulminate, Lead


azide, Silver azide, etc.

Primary Explosives

Mercury Fulminate (C2N2O2Hg)

Composition
Mercuric nitrate + Alcohol (in Nitric acid)

C NO)2Hg

(Liebig, 1823; Wieland & Solonina, 1909 & 1910 resp.)

Used in early electrical blasting caps and primers for small arms. Has poor
storage characteristics and corrosiveness.

Salient Features
After initiation it easily detonates and on detonation, it decomposes to stable

products
C NO)2Hg

2CO + N2 + Hg

It is sensitive to impact & friction, and is easily detonated by sparks & flames.
It is also very sensitive to sunlight and decomposes with the evolution of gas but
Other Ex.: AgONC
can be desensitized by the addition of water.

Lead Azide (PbN6)

Composition
Lead acetate + Sodium azide

N N N
Pb
N N N

(Curtius, 1891)

A major initiating explosive used in all blasting caps and other hot-wire
detonators due to excellent storage characteristics.

Salient Features

It has a good shelf life in dry conditions, but is unstable in the presence of
moisture and oxidising agents.

It is less sensitive to impact than mercury fulminate.


It has high capacity for initiating other secondary explosives to detonation.

Lead Styphnate (C6H3N3O9Pb)

Composition
O
O2N

NO2
Pb

Lead nitrate + Magnesium styphnate

O
NO2

Salient Features

Lead 2,4,6-trinitroresorcinate

It is insoluble in water and most organic solvents. It is non-hygroscopic.


It is very sensitive to the discharge of static electricity and can easily be
ignited by a flame or electric spark.
It is very dangerous to handle and is used in ignition caps.

2+

Silver Azide (AgN3)

Composition
Silver nitrate + Sodium azide

AgN N N

Salient Features
It is slightly hygroscopic and is very vigorous initiator. It decomposes under the

influence of ultra-violet irradiation.


If the intensity of radiation is sufficiently high the crystals may explode by
photochemical decomposition.

Tetrazene (C2H8N10O)

Composition
Sodium nitrite + Aminoguanidine

NH2
C N N N C NH2 . H2O

N N
NH
H
Tetrazolyl guanyltetrazene hydrate

(Hoffmann & Roth, 1910)

Salient Features
It is slightly hygroscopic and stable at ambient temperatures. It hydrolyses in

boiling water evolving nitrogen gas.


The detonation properties of tetrazene depend on the density of the material.
On compaction it will not detonate. So it is unsuitable for filling detonators.

Secondary Explosives

Blackpowder (Gunpowder)

Composition

Fuel (Charcoal + Sulfur) + Oxidizer (Potassium Nitrate)

Blackpowder

Characteristics

- The first explosive composition prepared in 220 BC, accidentally.


- Earlier used to breach the walls of castles and cities (1320).
- Blasting aid for recovering ore and mines (1627).
- A superior quality was produced by griniding & pressing the fuels & oxidizer into solid mass.

Nitroglycerine

Composition
H
H C OH

Nitration

H C OH

H C O NO2

H C OH
H

H C O NO2
H

Glycerol

H
H C O NO2

(Ascanio Sobrero, 1846 &


Immanuel Nobel, 1863)

Nitroglycerine

Characteristics

Nitroglycerine has advantage over blackpowder as it contains both fuel and oxidizer
elements in the same molecule which gives intimate contact for both components.
Used for difficult mining & tunnelling operations.

Nitrocellulose (Guncotton)

Composition

(Schonbein & Bottger, 1847)

CH2OH
H CH
O

CH2ONO2
O

OH
C

H
C

OH

C
H

Nitration
O
n

Cellulose

H CH
C

ONO2 H
C
C
H

C
H

ONO2

Nitrocellulose

Characteristics

Due to the polymeric nature it is an essential feature of gun propellant, rocket


propellants and gelatine blasting explosives.
In military and commercial explosives nitrocellulose could be detonated using a
mercury fulminate detonator.

Dynamite

Composition
Alfred Nobel (1875) discovered that on mixing nitrocellulose with
nitroglycerine a gel was formed, named as Dynamite.

Characteristics
This gel was developed to produce blasting gelatine, gelatine dynamite and

later ballisitite a smokeless powder.

The explosive properties of dynamites were enhanced by the addition of


ammonium nitrate.

Ammonium Nitrate

Composition
NH3 + HNO3
Ammonia

(NH4NO3)

Nitric acid
(Glauber, 1654)

Characteristics

The most common inorganic explosive which is extremely difficult to initiate.

When mixed with other explosives or with fuels in the form of powder, slurry, or
gel mixtures, it becomes an effective an inexpensive commercial explosive for use
in blasting.

Picric acid (2,4,6-trinitrophenol)

Composition
OH

OH
Nitration

O2 N

Phenol

Characteristics

NO2

NO2

(Glauber, 1742 &


Turpin, 1885)

Initially it was used as a dye for silk and wool.


It attacks common metals (Zn, Cu, Fe) and produces very explosive salts.
Its explosive power is superior than TNT.
Picric acid was used in grenade and mine fillings.

Tetryl
(2,4,6-trinitrophenylmethylnitramine)

Composition
H3C

H3C

CH3
Nitration

NO2

O2 N

Dimethylaniline

NO2

NO2

(Mertens, 1877)

Characteristics
It is pale, yellow, crystalline solid with melting temp. 129 OC
It is moderately sensitive to initiation by friction.
It was extensively used during World War II.
Tetryl is quite toxic to handle and is therefore replaced by RDX.

TNT (2,4,6-trinitrotoluene)

Composition
CH3

CH3
Nitration

O2N

NO2

3 step process

Toluene

NO2

(Wilbrand, 1863)

Characteristics
It is pale, yellow, crystalline solid with melting temp. 80.8 OC.
It has good chemical and thermal stability and has good compatibility with
other explosives.
It has low manufacturing cost and is safe in handling with low sensitivity to
impact and friction.

Nitroguanidine (Picrite)

Composition
NH2
HN C

NH2

Nitration

NH2
HN C

N NO2
H

Guanidine

(Jousselin, 1877)

Characteristics
It is stable below its melting point (232 OC) but decomposes very fast on
melting to form ammonia, water vapor and solid products.
It is also used as propellants as it possesses a low heat and temperature of
explosion.

PETN (Pentaerythritol tetranitrate)

Composition
H2 H2
HO C C OH
C
HO C H2C OH
H2

Nitration

H2 H2
O2N O C C O NO2
C
O2N O C H2C O NO2
H2

Pentaerythritol

Characteristics
It is most stable and least reactive nitric ester explosive.
A powerful secondary explosive and has a great shattering effect therefore,
used in commercial blasting caps, detonation cords and boosters.
It is sensitive to friction and impact and hence mixed with polymer bonded
explosives (PBX).

RDX
(Hexogen/Cyclonite/Cyclotrimethylenetrinitramine)

Composition
N
N

N
N

Hexamethylenetetramine

Nitration

NO2
N
CH2
CH2
O2 N N

C
H2

N NO2

(Henning, 1899 &


Herz, 1920)

Characteristics
RDX is white crystalline solid with melting temp. 204 OC.
It is chemically and thermally more stable than PETN.
Insensitive explosive compositions containing RDX can be achieved by
embedding the RDX crystals in a polymeric matrix as PBX.

HMX
(Octogen / Cyclotetramethylenetetranitramine)

Composition

NO2

N
N

N
N

Hexamethylenetetramine

Nitration
(acetic anhydride,
paraformaldehyde &
ammonium nitrate)

H2C
O2 N N
H2C

CH2
N NO2
CH2

N
NO2

Characteristics
It is also formed as a by product in the manufacturing of RDX.
It appears in 4 different crystalline forms in which the -form is least
sensitive to impact and hence employed in secondary explosives.
The ignition temp. of HMX (335 OC) is higher than RDX (260 OC) .
It is more resistant to attack by alkali than RDX however, its explosive
power is slightly lesser than RDX.

TATB (triaminotrinitrobenzene)

Composition
Nitration

Cl

Cl

O 2N

NO2

Cl

Cl
NO2

NH2

Cl

Cl

Characteristics

Amination

O 2N

NO2

H2N

NH2

NO2
(Jackson and Wing, 1888)

It is a yellow-brown coloured.

It is known as heat-resistant explosive as it has very high melting and


decomposition temp. (350 OC).

HNS (Hexanitrostilbene)

Composition
CH3

O2N

NO2
NaOCl

Oxidation

NO2

O2 N

NO2 O2N
H
C C
H
NO2 O2N

Characteristics
It is insensitive to electric spark.

It is resistant to heat as well as radiation. Therefore used in heat-resistant


booster explosives.

NO2

NTO (5-nitro-1,2,4-triazole-3-one)

Composition
O
HCl
H2N C
HN NH2

HCOOH

Semicarbazide
hydrochloride

H
N

HN
TO

Nitration
CH

HN

H
N

C NO2

NTO

Characteristics
It is a new energetic material having stability greater than RDX. It is
also less sensitive.
NTO is a substitute for ammonium perchlorate or ammonium nitrate in
solid rocket propellants (since it does not liberate undesirable products
such as HCl).

TNAZ (1,3,3-trinitroazetidine)

Composition
O

Cl

(Epichlorohydrin)

Multi-step
Synthesis
Fluorochem Process

NO2
N
H2C CH2
C
NO2
O2N

Characteristics
It is a white crystalline solid having melting temp. 101 OC.

It has relatively high vapor pressure compared to other explosives.


It forms eutectic mixtures with TNT, Tetryl and HMX.