Explosives:-

Explosives are compounds or mixture of compounds which under the influence of mechanical or thermal shock
decomposes spontaneously and rapidly producing large amount of heat energy along with release of gases, light, sound
and shockwaves. Explosive reaction is exothermic. So, the products get heated to a high temperature and high pressure is
exerted on the surrounding.

During explosion oxygen combines with hydrogen and carbon to form water, carbon dioxide and carbon monoxide. Some
of the explosives contain sufficient percentage of oxygen to oxide whole of the hydrogen and carbon contents whereas the
other may lack sufficient oxygen required for the complete oxidation of hydrogen and [Link] such cases oxygen rich
compound is added for the complete combustion. A variety of organic and inorganic compounds can act as explosives.

Characteristics of explosives:
An explosive compounds should have the following characteristics in order to produce the desired products.

1. It should have at least one chemical bond with low bond dissociation energy so that can be easily broken.
2. It should be stable under normal conditions [Link] must not be volatile and hygroscopic
3. It must be decomposes at a fast rate so that tremendous amount of energy within the limited time to cause an
effective explosion.
4. It should have a positive oxygen balance.
5. It should possess high scattering power.
6. It should be cheap, non-toxic and chemically inert under normal conditions.
7. In case of primary explosives, it should explode rapidly by the application of heat/friction/mechanical impact.

Oxygen Balance:-
The oxygen balance is a measure of the oxygen contained in the molecule which is used to oxidize C and H to CO2
& H2O respectively. Generally, it is expressed as a percentage surplus or deficiency of oxygen by weight.
Let us consider the oxidation molecule CxHyOz
𝑦 𝑦
CxHyOz xCO2 + H2O+ z−(x+ ) O2
From this equation, we can conclude that x atoms of oxygen are required to oxidize x atoms of C & atoms of oxygen are
required to oxidize y atoms of hydrogen. Thus,
𝑦
Surplus oxygen = z−(x+ )
O2
𝑦
z−(x+ ) ×16×100
Oxygen balance = O2
[Link]. CX Hy Oz

List of some compounds to their oxygen balance:

Compounds [Link] {z-(x+ )} Oxygen balance
NH4NO3(AN) 80 3-(0+ ) =1 =20
Pb(N3)2 (lead Azide) 290 0 0
C7H5N3O6 (TNT) 227 6-(7+ ) = - = -24.7
C6H4N4O5(DDNP)Diazodinitrophenol 212 5-(6+ ) =-3 = -22.64
C3H6N6O6(RDX)(Cyclonite or
222 0 0
Cyclomethylene trinitrotoluene)
C5H8N4O12(PETN)(Pentaerythrital
316 12-(5+ ) =3 =15.2
tetranitrate)
Classification of explosives
They are usually classified into three groups.

1. Primary explosives (initiating explosives or detonators): -

Primary explosives are highly sensitive to heat, friction or any impact. Therefore, they should be handled very
carefully. But these explosive generally have less energy and they are mainly used in small quantities to initiate the
explosion of main explosives and hence are called initiating explosives or detonators. For example, Lead
Azide{Pb(N3)2}, silver Azide(AgN3), mercury fulminate {(Hg(CNO)2}, diazodinitrophenol(DDNP) etc.
These explosives are used in blasting caps and cartridges.

2. Low explosives (or propellant):

Low explosives are less sensitive to heat, friction or any impact than primary explosives but are more sensitive than
high explosives. They are simply burn but do not explode suddenly. The chemical reactions takes places in such
explosives are comparatively slower and their burning proceeds from the surface towards the inside layers at
approximate rates of 20 cm per second. These can be easily controlled since they evolved gases disperse readily
without building high pressure. They are used as propellant and in fireworks. For example:-Gun powder and nitro
cellulose (smokeless powder) etc.

3. High explosives:
High explosives are higher energy contents than the primary explosives. However, they are quite stable and less
sensitive to fire and mechanical shock. Generally, small amount of primary explosive (detonator) is placed in contact
with high explosives. Primary explosive starts the rapid chemical reaction in the body of high explosive which then
proceeds at a high rate of 1500 to 10000 m/s. The volume of gases evolved especially under the influence of high
temperatures which have a shattering effect. For example; single compound like Ammoinium nitrate, RDX, picric
acid and binary explosive mixture of TNT and other explosives) like amatol Amatol (mixture of TNT with
ammonium nitrate), Pentolite (mixture of TNT and PETN (penta Erythritol Tetranitrate) 50% each), Tetrytol
(mixture of 70% tetryl and 30% TNT), Tropex (mixture of 40% RDX 40% TNT and 20% Al powder), Titronal (
mixture of 80% TNT and 20% Al flakes)etc.

Precautions during storage of explosives:

Following precautions should be taken while storing the explosives.

i) The different explosives should be stored in separate boxes.

ii) The detonators and explosive should be stored separately.
iii) The flame lantern should not be used in any case. When power failure takes place, use of only torches should
be made for lighting purposes.
iv) All the electric fittings and wirings should be properly insulated and frequently checked.
v) Only authorized persons should be allowed to enter the explosive store.
vi) Smoking/ fire should be strictly prohibited within a radius of 50 m from the explosive store.
vii) The magazine should not be constructed within 500m from any working furnace.
viii) The boundary of the explosive store should be protected by high barbed-wire fencing and proper “Caution
Boards” should be installed around it.
ix) Lightning conductors should be provided to safeguard the magazine.
Preparation and application of some important explosives:-

A. 2,4,6 trinitrotoluene(TNT):-
Preparation:-It is prepared by treating toluene with nitrating mixture of Conc.HNO3 and conc.H2SO4.
CH3

CH3Cl/FeCl3

Thus obtained liquid product of TNT is washed with ammonical solution of sodium sulphite (Na2SO3) and then
with cold water. When TNT is crystallized out, this is filtered, purified and dried.
Decomposition reaction:-

TNT 3.5CO+3.5C+2.5H2O+1.5N2+190 KCal

Uses:-

i) It is used as a chemical intermediate in the manufacture of dyestuffs and photographic chemicals.

ii) It has been widely used for filling shells and airborne demolition bombs.
iii) It is mostly used for military purpose as it is safe to manufacture, transport and store.
iv) It is used in extraction of oil and gas from shale formations.
v) It has been used in manufacture of binary explosives like amatex, amatol, ammonal( etc.

B. Triniroglycerine (TNG) or Nitroglycerine(NG) or Glycerol trinirate(GTN):-

Preparation:-
It is prepared by treating glycerol to a cooled mixture of 60% conc.H2SO4 and 40% [Link] 10oC
with constant stirring.

CH2−OH CH2−ONO2

H2SO4
CH−OH +3HNO3 CH−ONO2 +3H2O

CH2−OH CH2−ONO2

Glycerol GTN
 Thus obtained mixture of nitroglycerine is run into container when NG rises to top while excess acids form lower
layer. The NG layer is separated by separating funnel and washed first with water then with dilute 2% sodium
carbonate solution to remove traces of acids completely.

Decomposition reaction:

4C3H5(NO3)3 12CO2+6N2+10H2O+O2

Uses:-

i) It is used in production of dynamite and other explosives.

ii) It is also used as an ingredient in military propellants for use in firearms.
iii) It has been used in conjunction with hydraulic fracturing, a process used to recover oil and gas from shale
formations.
iv) It is employed in medicine as treatment for angina pector’s for congestive heart failure and hypertension.
v) It has high shattering effect and is used in firing bullet.

C. Gun cotton or (Nitrocellulose) or cellulose nitrate:-

Preparation:-
It is prepared by treating cellulose with the nitrating mixture of conc. nitric acid and sulphuric acid.
.

Cellulose OR Nitrocellulose

OR

3H2SO4
[C6H7O2(OH)3]n+3HNO3 [C6H7O2(ONO2)3]n+3H2O
12CO2+6N2+10H2O+O2
Nitrocellulose

Thus formed nitrocellulose is dissolved in a mixture of ether and alcohol. when the solvent is evaporated, a jelly like solid
is left behind. The product is treated with traces of acid and diphenylamine as a stabilizers, it is pressed into cylindrical
rods. It is also called smokeless powder because it produces CO2, CO, N2 water vapor and almost no smoke.
Uses :-

i) Used to make smokeless powder which serves as a propellant in rifles and artillery shells.
ii) Used in torpedoes and submarine.
iii) Used in the manufacture of plastic celluloid.
iv) Solution of nitrocellulose is used in wound dressings.

D. Plastic explosives:
Plastic explosives are the combination of high explosive and wax or oil. These are in plastic state and can be
moulded into various shapes without any serious risk. They are available as flexible sheet which can be cut into
require shapes into sheets. Special caps are used to start explosion. They are mainly used for industrial application
and military uses. Eg: RDX or cyclonite (Royal Demolition Explosive), HMX (High Melting Explosive),
PETN (pentaerythritol tetranitrate).

RDX

Uses:-

i) It is used in the demolition of barriers and fortifications by engineers, combat engineers and illicit actors
ii) It is used in warheads during military operations
iii) It is used as armor in tanks
iv) It is used for shock-hardening high manganese-percentage steel commonly found in train rail components and
earth digging implements