1

Explosives
Theory:
Chemistry and
Physics of
Explosives
Prof. Dr. M. Zubair Abu Bakar
Chemistry and Physics of Explosives 2

Explosive:
• An explosive is a chemical compound or mixture of compounds that undergoes a very rapid
decomposition when initiated by energy in the form of heat, impact, friction or shock.
• This decomposition produces more stable substances, mostly gases, and a large amount of
heat. The very hot gases produce extremely high pressures within the borehole, and it is these
pressures that cause rock to be fragmented.
Detonation:
• If the speed of the reaction of the explosive is faster than the speed of sound in the explosive, the
product is called a high explosive.
Deflagration:
• If the reaction of the explosive is slower than the speed of sound in the explosive, the product is
called a low explosive.
Principal Ingredients of 3

an Explosive
• The principal reacting ingredients in an explosive are fuels
and oxidizers.
• Common fuels in commercial products are fuel oil,
carbon, aluminum, TNT (Trinitrotoluene; C7H5N3O6),
smokeless powder, monomethylamine nitrate and
monoethanol amine nitrate.
• Fuels often perform a sensitizing function. Common
explosive sensitizers are nitroglycerin, nitro starch,
aluminum, TNT, smokeless powder, monomethylamine
nitrate, and monoethanol amine nitrate.
• Microballoons and aerating agents are sometimes added
to enhance sensitivity.
• The most common oxidizer is ammonium nitrate,
although sodium nitrate and calcium nitrate may also be
used.
• Other ingredients of explosives include water, gums, thickeners and cross-linking agents 4
used in slurries, gelatinizers, densifiers, antacids, stabilizers, absorbents, and flame
retardants.
• In molecular explosives such as nitroglycerin, TNT, and PETN (pentaerythritol
tetranitrate), the fuel and oxidizer are combined in the same compound.
• Most ingredients of explosives are composed of elements oxygen, nitrogen, hydrogen,
and carbon. In addition, elements such as aluminum are sometimes used.
Zero Oxygen Balance
• Zero oxygen balance is defined as the point at which a mixture has sufficient oxygen to
completely oxidize all the fuels it contains but there is no excess oxygen to react with the
nitrogen in the mixture to form nitrogen oxides.
• Theoretically, at zero oxygen balance the gaseous products of detonation are H2O, CO2,
N2, although in reality small amounts of NO, CO, NH2, CH4, and other gases are
generated.
 Zero Oxygen Balance 5

• From fig 1, it can be seen that partial oxidation

of carbon to carbon monoxide, which results
from an oxygen deficiency, releases less heat
than complete oxidation to carbon dioxide.
• The oxides of nitrogen, which are produced
when there is excess oxygen, are heat robbers;
that is they absorb heat when generated.
• Free nitrogen, being an element, neither
absorbs nor releases heat upon liberation.
• Gases resulting from improper oxygen balance
are not only inefficient in terms of heat energy
released but are also poisonous.
• Al2O3 and MgO, are although solid (products of oxidation of Al and Mg), but the amount of heat
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generated adds significantly to the explosive’s energy.
• Magnesium is too sensitive to be used in commercial explosives.
• Some inert solids like CaO and Na2O are also produced, but they do not take any part in the
explosion, and their excess is not desired, since they cause hindrance in the passage of the
gases, resulting in decreased energy.
 Compounding of Chemical Explosives 7

• The principle of oxygen balance is best illustrated by the reaction of NH4NO3 and
fuel oil (CH2)n, commonly called as ANFO (blasting agent).
• These equations assume an ideal detonation reaction, which assumes thorough
mixing of ingredients, proper particle sizing, adequate confinement, charge
diameter and priming and protection from water.
• Eq.1 represents the reaction of an oxygen-balanced mixture containing 94.5% AN and 5.5%
FO (none of the gases produced are poisonous; heat of 0.93 kcal/g of ANFO is released). 8
• Eq. 2 represents 92.0% of AN and 8.0% of FO, the excess fuel creates an oxygen deficiency
(CO which is poisonous is produced instead of CO2). Lower heat (0.81 kcal/g) is produced
because of lower heat of formation of CO.
• Eq. 3 shows a fuel deficient (only 3.4% FO and 96.6% AN) reaction, which creates an excess
oxygen condition.
• Some of the nitrogen from the ammonium nitrate combines with this excess oxygen to form
NO, which will react with oxygen in the atmosphere to form extremely toxic NO2.
• The CO produced by an overfuled mixture is less toxic than NO and NO2. For these reasons, a
slight oxygen deficiency is preferable and the common ANFO mixture for field is 94% AN and
6% FO.
 Compounding of Chemical Explosives 9
Formula Molecular Weight Amount of Heat Generated (Qe)
Kcal/mole
AlO 43.0 +10.7
Al2O 70.0 -31.7
Al2O3 102.0 -399.1
CaO 56.1 -151.9
CaO2 72.1 -158.3
CH2 14.0 -7.0
CO 28.0 -26.4
CO2 44.0 -94.1
H2O 18.0 -57.8
HNO3 63.0 -49.4
NH4NO3 80.1 -87.3
Al 27.0 0
N2 28.0 0
NH3 17.0 -11.0
NO 30.0 +21.6
NO2 46.0 +8.1
O2 16.0 +59.2
 3𝑁𝐻4 𝑁𝑂3 + 𝐶𝐻2 → 7𝐻2 𝑂 + 𝐶𝑂2 + 3𝑁2 (1)
10
• Calculate net heat released or absorbed by this reaction using different Qe values for different
substances:
3 −87.3 + 1 −7 → 7 −57.8 + 1 −94.1 + 3 0
−268.9 → −498.7
Net heat released = -498.7- (-268.9)= -229.8 kcal (Exothermic reaction)
• Calculate grams of reactants used:
3 80.1 + 1 14.0 → 254.3 𝑔𝑚𝑠
−229.8 𝑘𝑐𝑎𝑙
𝑄𝑒 = = −0.904
254.3 𝑔𝑚
• Calculate percentages of reactants used:
Weight of NH4NO3 used = 3 (80.1) = 240.3 g
Weight of Fuel Oil used = 1(14) = 14 g
240.3
% age of NH4NO3 = × 100 = 94.5%
254.3
14
% age of NH4NO3 = × 100 = 5.5%
254.3
 2𝑁𝐻4 𝑁𝑂3 + 𝐶𝐻2 → 5𝐻2 𝑂 + 𝐶𝑂 + 2𝑁2 (2)
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• Calculate net heat released or absorbed by this reaction using different Qe values for different
substances:
2 −87.3 + 1 −7 → 5 −57.8 + 1(−26.4) + 2 0
−181.6 → −315.4
Net heat released = -315.4 - (-181.6)= -133.8 kcal (Exothermic reaction)
• Calculate grams of reactants used:
2 80.1 + 1 14.0 → 174.2 𝑔𝑚𝑠
−133.8 𝑘𝑐𝑎𝑙
𝑄𝑒 = = −0.768
174.2 𝑔𝑚
• Calculate percentages of reactants used:
Weight of NH4NO3 used = 2(80.1) = 160.2 g
Weight of Fuel Oil used = 1(14) = 14 g
160.2
% age of NH4NO3 = × 100 = 92 %
174.2
14
% age of NH4NO3 = × 100 = 8 %
174.2
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4𝑁𝐻4 𝑁𝑂3 + 𝐶𝐻2 → 9𝐻2 𝑂 + 𝐶𝑂2 + 𝑁𝑂 + 3 𝑁2 (3)
2 12

• Calculate net heat released or absorbed by this reaction using different Qe values for different
substances:
1
4 −87.3 + 1 −7 → 9 −57.8 + 1 −94.1 + (+21.6) + 3 0
2
−349.2 → −592.7
Net heat released = -592.7 - (-349.2)= -243.5 kcal (Exothermic reaction)
• Calculate grams of reactants used:
4 80.1 + 1 14.0 → 334.4 𝑔𝑚𝑠
−243.5 𝑘𝑐𝑎𝑙
𝑄𝑒 = = −0.728
334.4 𝑔𝑚
• Calculate percentages of reactants used:
Weight of NH4NO3 used = 4(80.1) = 320.4 g
Weight of Fuel Oil used = 1(14) = 14 g
320.4
% age of NH4NO3 = × 100 = 95.81 %
334.4
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% age of NH4NO3 = × 100 = 4.2 %
334.4
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Detonation Pressure and Borehole Pressure

• The chemical reaction of an explosive creates extremely high
pressures. It is these pressures which cause rock to be broken
and displaced.
• Fig.2 (adopted from Dr. Richard Ash of UMR/MST) shows a
column of explosive or blasting agent that has been initiated.
• Detonation has proceeded to the center of the column. The
primary reaction occurs between a shock front at the leading
edge and a rear boundary known as Chapman-Jouget (C-J)
plane.
• Part of the reaction may occur behind the C-J plane,
particularly if some if some of the explosive’s ingredients are
coarse.
• The length of the reaction zone depends on explosive’s
ingredients, particle size, density, confinement and critical
diameter (minimum diameter at which the explosive will
function dependably; critical diameter for ANFO is 1 inch ).
• High explosives, which have short reaction zones, have smaller
critical diameters than blasting agents.
• The pressure profiles in fig. 2 (bottom) show the explosive 14
forces (by explosive and blasting agent) applied to the rock
being blasted.
• Each explosive or blasting agent has its own particular
pressure profile depending on its ingredients, particle size,
density and confinement.
• The initial pressure, called the detonation pressure (Pd) is
created by the supersonic shock front moving out from the
detonation zone. It gives the explosive its shattering action in
the vicinity of the borehole.
• If the explosive reacts slower than the speed of sound
(deflagration), which is normally the case with black powder,
there is no detonation pressure.
• The detonation pressure is followed by a sustained pressure
called explosion pressure (Pe) or borehole pressure.
• Borehole pressure is created by the rapid expansion of the hot
gases within the borehole.
• The detonation pressure of the high explosives is often several
times that of blasting agents, but the borehole pressure of the
two types of products are of the same general magnitude.
 Velocity of Detonation (VOD)
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• The velocity with which the detonating wave is moving through an explosive is known as velocity
of detonation.
• The greater is the VOD of an explosive, the greater will be its detonation pressure (Pd) and hence
its brisance or shattering effect.
• Explosives with low VOD will tend to release the gas pressure over a longer period of time.
• Borehole pressure (Pe) is usually one half of the detonation pressure.
Reasons For Not Having Ideal Theoretical Values of VOD
• Any explosive should have a certain VOD, but when an explosive is used in the field conditions,
we do not get ideal results. The following may be the reasons.
1. Improper Priming
Because of improper priming most of the explosive is consumed in the following stages of the reaction:
i. Slow acting combustion → ii. Rapid deflagration → iii. Low order detonation → iv. Fully developed
detonation.
Therefore, most of the time is spent in first three stages and fully developed detonation is attained at the
end. To avoid this situation a primer of high VOD and high detonation pressure should be used.
2. Proper Confinement
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Without proper confinement, we can not get ideal VOD; hence proper confinement is a key to get
ideal VOD.
3. Poor Mixing
Poor mixing of the ingredients of an explosive directly affects the VOD e.g., in case of ANFO it might
be possible that ammonium nitrate and fuel oil are not properly mixed.
4. Water Desensitization
If water/moisture is present in the borehole and we are using an explosive which is not water
resistant, then in that case ideal VOD will not be achieved e.g., ANFO in case of bulk loading
condition will be in contact with the borehole walls, which will affect its VOD. Moreover, presence of
water creates an excess of oxygen, which results in the production of toxic oxides of nitrogen. The
fumes of oxides of nitrogen may also be produced due to improper priming.
5. Diameter of Explosive (cartridge)/ Blasthole (Coupling Ratio)
Diameter of the explosive is a key to have good VOD and Pd. The greater is the size of borehole, the
greater will be the VOD and also the fragments size. For ANFO maximum VOD is attained at 15
inches. Providing a high coupling ratio, increases VOD (Coupling ratio is the %age of the hole
diameter filled with explosive).
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References

• Richard A Dick, Larry R. Fletcher, and Dennis V. D’Andrea. Information Circular

8925; Explosives and Blasting Procedures Manual, United States Department of
Interior and Bureau of Mines.