A WRITE UP ON

THE CHEMISTRY OF EXPLOSIVES

BY
POWERFUL GROUP (GROUP B)
DEPARTMENT OF CHEMISTRY
FACULTY OF PHYSICAL SCIENCE
UNIVERSITY OF ILORIN, ILORIN, KWARA
STATE.
COURSE: INDUSTRIAL CHEMICAL PROCESS II
(CHM 441)
LECTURER IN CHARGE: DR. A.O RAJEE
DATE OF PRESENTATION: 12/02/2024
 ACKNOWLEDGMENT
All thanks to God Almighty for this privilege and to the lecturer in charge; Dr A.O Rajee, for the
opportunity given to us to do a research work and presentation on the caption “CHEMISTRY OF
EXPLOSIVES” ,may Almighty God increase your wisdom and bless you abundantly.

To all the group members, thank you for your support, understanding, patience, cooperation and
encouragement, may we all reach the topmost top

And to all our fellow colleagues,we really appreciate you all, Thanks.
 NAMES AND MATRIC NUMBERS OF THE GROUP MEMBERS
S/N NAMES MATRIC NUMBERS
1. ABODERIN OLUWASEUN ADEKUNLE 19/56EE012
2. ABUBAKAR ABDULBASIT OLANREWAJU 19/56EE013
3. ADEKUNLE MAROOF OLAWALE 19/56EE026
4. ALABI SHAKIRAT AWUJOOLA 19/56EE063
5. OLAWUYI MATTEW OLAJIDE 19/56EE165
6. ZUBAIR HALYMAN OPEYEMI 19/56EE225
7. ADERIBIGBE ABDULWASI AKANI 19/56EE036
8. ADEOLA OLAOLUWA DAVID 19/56EE031
9. LAWAL FARUQ TIMILEYIN 19/56EE129
10. SALIU LATEEFAH DAMILOLA 19/56EE200
11. KOMOLAFE JOSEPH IMISIOLUWA 19/56EE128
12. OGUNDEKO ADEDOLAPO S. 19/56EE146
13. OYINLOYE OKIKIJESU DORCAS 19/56EE187
14. OLAYANJU FOLAKE FEYIKEMI 19/56EE166
15. AYINLA BALIQIS FOLASADE 19/56EE078
16. AMOO EMMANUEL OLUWASEYI 19/56EE068
17. ADELANWA MISTURA OLAYINKA 19/56EE029
18. IDAKWOJI SUMAYYAH IDRIS 19/56EE113
19. ABDULWAHEED SOFIYAT TAIWO 19/56EE007
20. SUHAIB ARAFAT OLUWADAMILOLA 19/56EE205
21. FASOLA PRECIOUS EMILAYO 19/56EE105
22. AKINBUSUYI JOSEPH OLAOLUWA 19/56EE059
23. ADETUNJI OLUWAFEMI OLUMIDE 20/56EE172
24. OLOYEDE JOY KIKELOMO 20/56EE186
25. SHOKUNBI OLUWAMAYOWA FAVOUR 20/56EE192
 TABLE OF CONTENTS

 Introduction
 Definitions of explosives
 Constituents of explosives
 Characteristics of explosives
 List of explosives
 Classification of explosives
 Based on the velocity of detonation
High energy explosives
Low energy explosives
Military explosives
Commercial explosives
Homemade explosives
 Based on the chemical composition
Organic explosives
Peroxide explosives
Nitro-explosives
Organic azides
Inorganic explosives
Nonmetal explosives
 Blasting mechanics
 Energy release, explosive output, and critical diameter
 Detonation velocity
 Detonation and borehole pressure
 Blasting agents and ammonium nitrate
 Detonation and deflagration
 The application of explosives to metal cutting, rock drilling and controlled
earth shifting
 Consequences of explosives to the human heart
 References
 INTRODUCTION
EXPLOSIVES were originally developed for military applications and most of the advances in
explosive technology have been stimulated by military requirements particularly during the two
World Wars. Civil applications of explosives have been largely in the fields of demolition work,
quarrying and fragmentation of rock for construction work, ore extraction, etc. The destructive
power of explosives is so well known that their suitability for constructive applications under the
right conditions is often overlooked. It is only fairly recently that interest has developed in the
use of explosives for metal processing including welding, hardening and high energy rate
forming. Many other constructive uses are possible. It is hoped that this article will draw
attention to some of these uses by surveying the applications of explosives in the diverse fields of
metal cutting, ultra-high speed machining, rock drilling and controlled earth shifting.

DEFINITIONS

An explosive substance is a solid or liquid substance (or mixture of substances) which is in itself
capable by chemical reaction of producing gas at such a temperature and pressure and at such a
speed as to cause damage to the surroundings. Pyrotechnic substances are included even when
they do not evolve gases.

A pyrotechnic substance is a substance or mixture of substances designed to produce an effect by

heat, light, sound, gas or smoke or a combination of these as the result of non-detonative self-
sustaining exothermic chemical reactions.

An explosive is a solid or liquid substance or mixture of substances which is liable, on the

application of heat or a blow to a small portion of the mass, to be converted in a very short
interval of time into other more stable substances largely or entirely gaseous. A considerable
amount of heat is also invariably evolved, and consequently there is a flame.

CONSTITUENTS OF EXPLOSIVES

Nearly all commercial explosives are composed partly of combustible elements, of which carbon
and hydrogen are the most important, and partly of oxygen combined, but not directly with the
hydrogen and carbon. On explosion the oxygen combines with the hydrogen to form water, and
with the carbon to form carbon monoxide or dioxide, or a mixture of the two. It is the heat set
free in this combustion that is the main or entire cause of the rise of temperature. The formation
of these two oxides of carbon liberates very different quantities of heat; 12 grams of carbon unite
with 16 grams of oxygen to form 28 grams of carbon monoxide with the liberation of 29 large
Calories, and the quantity of carbon unites with 32 grams of oxygen with the liberation of 97
large Calories.
Consequently an explosive is considerably more efficient if it contains sufficient oxygen to
oxidize the carbon entirely to dioxide, but the effect is reduced to some extent by the relatively
high specific heat of carbon dioxide. In some classes of explosives, however, a very high
temperature is objectionable; this is the case with smokeless powders and explosives for use in
coal mines. Smokeless powders, therefore, are generally made of such a composition that the
greater part of the carbon is oxidized only to monoxide. But there is always some carbon dioxide
formed, for it takes up some of the oxygen from the water vapor and liberates hydrogen, or if the
total quantity of oxygen be very small there may even be free carbon produced. In the case of
safety explosives for coal mines, the temperature of explosion is also sometimes kept low by
restricting the proportion of oxygen, hut this means is not free from objection because carbon
monoxide is poisonous. Other methods are therefore adopted in some safety explosives to reduce
the temperature.

CHARACTERISTICS OF EXPLOSIVES
In general, an explosive has four basic characteristics:
(1) It is a chemical compound or mixture ignited by heat, shock, impact, friction, or a
combination of these conditions;
(2) Upon ignition, it decomposes rapidly in a detonation;
(3) There is a rapid release of heat and large quantities of high-pressure gases that expand rapidly
with sufficient force to overcome confining forces; and
(4) The energy released by the detonation of explosives produces four basic effects; (a) rock
fragmentation; (b) rock displacement; (c) ground vibration; and (d) air blast
A general theory of explosives is that the detonation of the explosives charge causes a high-
velocity shock wave and a tremendous release of gas. The shock wave cracks and crushes the
rock near the explosives and creates thousands of cracks in the rock. These cracks are then filled
with the expanding gases. The gases continue to fill and expand the cracks until the gas pressure
is too weak to expand the cracks any further, or are vented from the rock.

The ingredients in explosives manufactured are classified as:

Explosive bases: An explosive base is a solid or a liquid which, upon application or heat or
shock, breaks down very rapidly into gaseous products, with an accompanying release of heat
energy. Nitroglycerine is an example.

Combustibles: A combustible combines with excess oxygen in an explosive to achieve oxygen

balance, to prevent the formation of nitrous oxides (toxic fumes), and to lower the heat of the
explosion.

Oxygen carriers: Oxygen carriers assure complete oxidation of the carbon in the explosive
mixture, which inhibits the formation of carbon monoxide. The oxygen carriers assist in
preventing a lowering of the exploding temperature. A lower heat of explosion means a lower
energy output and thereby less efficient blasting.

Antacid: Antacids are added to an explosive compound to increase its long term storage life, and
to reduce the acidic value of the explosive base, particularly nitroglycerin (NG).

Absorbents: Absorbents are used in dynamite to hold the explosive base from exudation,
seepage, and settlement to the bottom of the cartridge or container. Sawdust, rice hulls, nut
shells, and wood meal are often used as absorbents.

Antifreeze: Antifreeze is used to lower the freezing point of the explosive.

Air gap sensitivity: Air gap sensitivity is a measure of an explosive’s cartridge-to-cartridge

sensitivity to detonation, under test conditions, expressed as the distance through air at which a
primed half-cartridge (donor) will reliably detonate an unprimed half-cartridge (receptor).

Cap Sensitivity: Cap sensitivity is a measure of the minimum energy, pressure, or power
required for initiation of a detonation; i.e., “cannot be detonated by means of a No. 8 test blasting
cap when unconfined.

” Strength Two strength ratings are used for commercial dynamites. Weight strength compares
products on an equal-weight basis, and cartridge strength or bulk strength compares products on
an equal-volume basis. Both are expressed in percent, using straight nitroglycerin dynamite as a
standard. Complicating this picture is the variety of ingredient mixes among manufacturers, so
that 40 percent gelatin dynamite and 40 percent ammonia dynamite do their work differently;
similarly, 40 percent ammonia dynamite from two different manufacturers will give somewhat
different results. Thus, a blaster who had always used one manufacturer's product could change
suppliers and suddenly start complaining about “bad powder.” To further confuse the issue, some
manufacturers continue to use the terms “weight strength” and “bulk strength” as a comparative
numerical rating against ANFO at 100. With the advent of new explosives, particularly the
ANFOs and the slurries, the dynamite method of judging strength failed to give relevant data. It
became necessary to account not only for a product's relative stored energy, but also its rate of
energy release, its gas volume potential, and its heat of detonation. A number of factors are
currently used to judge an explosive's ability to do the work desired, and today's blaster must
consider at least the following:

 Detonation Pressure is a measure of the product's shock wave energy, influenced by the
product's density (latent energy) and detonation velocity (rate of energy release).

 Pressure Magnitude or Gas Pressure is a measure of the potential expanding-gas energy,

influenced by the product's density (latent gas volume) and the heat and velocity of
detonation (rate of gas production and expansion). Though oversimplified, one way to
think of “strength” is to compare an explosive to a mechanical means of breaking and
moving rock. We can break rock with a sledgehammer, and a detonation pressure is our
explosive hammer. As density increases, the “weight of the hammer” increases; as
velocity increases, we “swing the hammer” faster and harder. We can move rock with a
bulldozer,and gas pressure is our explosive dozer. As density increases, the dozer gets
bigger; as velocity increases, the dozer runs faster sometimes so fast that it outruns the
rock it is trying to move.
CLASSIFICATION OF EXPLOSIVES

Chemical explosives are usually classified in literature according to either the velocity of
detonation (high energy/low energy explosives) or the source/application
(military/commercial/homemade explosives)

Classification based on the velocity of detonation

High energy explosives

High energy explosives detonate creating a supersonic shock wave that propagates usually
exceeding 4000 m/s. Three classes are typically subdivided for high explosives according to their
sensitivity to explode: primary, secondary and tertiary explosives.

– Primary explosives are extremely sensitive to different weak stimuli (such as heat, spark or
friction) by which detonation initiates. In general, primary explosives are not particularly
powerful. Because of these properties, they are usually used in little amounts as detonators of
secondary high explosives. Some typical primary explosives are mercury fulminate, silver
fulminate, lead azide, cuprous acetylide, lead picrate, lead styphnate, diazodinitrophenol,
tetrazoles, NG, TATP and HMTD.

– Secondary explosives are practically insensitive to weak stimuli and they usually require the
input of a strong shock to detonate. Most secondary explosives are exceptionally powerful (with
velocities of detonation that exceed 6000 m/s). Secondary explosives include the most common
explosives used in the military field such as RDX, PETN, HMX, TNT, 1,3,5-triamino2,4,6-
trinitrobenzene (TATB), tetryl, picric acid, CL20 and NC.

– Tertiary explosives is an extra group, sometimes added in the classification, to include and
separate those insensitive explosives widely used for mining and demolition purposes, which
have lower velocities of detonation than military secondary explosives. ANFO, ANAl and
dynamite compositions are common examples of tertiary explosives.

Low energy explosives

Unlike high energy explosives, low energy explosives deflagrate creating a subsonic wave front
that does not reach the speed of sound. The explosion that low explosives may produce is a
consequence of the overpressure generated inside a container by the accumulation of gas
products from deflagration. Because of the progressive production of these gas products during
their deflagration, low explosives are mostly used as propellants, either in pyrotechnics, space
rockets or ammunition for firearms. Smokeless powder, black powder and flash powder are
typical examples of low explosives.

Military explosives Military explosives are high explosives meeting strict requirements in
terms of performance, functionality and safe handle, storage and transport. They have to be
powerful while insensitive to weak/medium intense stimuli, requiring the use of detonators to
detonate. [1–4] Military explosives are generally organic molecules containing only carbon,
hydrogen, oxygen and nitrogen atoms. Particularly, oxygen and nitrogen atoms are typically
found as nitro-groups (-NO2) in these molecules. The explosive nature of these molecules is due
to those nitro-groups, thus military explosives are usually referred as nitro-explosives. Common
military explosives are RDX, PETN, HMX and TNT.

Commercial explosives

Commercial explosives include those explosives that are legally used for nonmilitary purposes
including the explosives used in mining industry, demolitions, and firearms/rocket/ pyrotechnic
propellants.[3–8] Dynamite and ANFO compositions are the most common commercial
explosives used today for mining and demolition purposes. They are high explosives with
relatively small velocities of detonation (in comparison with military explosives), which enable a
more precise control about the required power to move and fragment rocks and buildings.

Homemade explosives

Homemade explosives include all “do-it-yourself” explosives. With the arrival of Internet last
century, it is no longer necessary to be a chemist to produce or synthetize explosives. Freely
accessible recipes guiding step by step about how to obtain, produce and synthetize different
explosives are available online. These recipes typically include oxidizer-fuel explosive mixtures
such asANFO.

Figure 1 Classification of explosives proposed by Akhavan in 2004

Classification Based on the chemical composition
Organic explosives

Pure individual organic molecular explosives include those explosive molecules that contain at
least one atom of carbon and no atoms of an element different to C, H, O, N or halogen in their
structure. This includes, for example, TNT (C7H5N3O6), TATP (C9H18O6) or even
nitroguanidine (CH4N4O2), which only has one atom of carbon. Because of the large number of
organic explosives that exist today, organic explosives are usually sub-divided into several
different classes (peroxide explosives, nitro-explosives, organic azides, halogen amino
compounds, and azo/diazo compounds (including diazomethane)). In addition, a sixth class
named “other organic explosives” is also presented in which including those organic explosives
that are not included in previous classes.

Peroxide explosives Peroxide explosives are organic explosives characterized by having in their
structure one or more peroxide groups (-OO-). The most popular peroxide explosives are TATP
and HMTD.[6,19]

Nitro-explosives

Nitro-explosives are organic explosives characterized by having in their structure one or more
nitro-groups (-NO2). Nitro-explosives are also sub-divided into four different classes depending
on the atom to which nitro-group is chemically bonded.

Nitro-aromatic. Nitro-group is bonded to an aromatic carbon (C(Ar)-NO 2). E.g. TNT, tetryl,
picric acid and TATB.

Nitro-aliphatic. Nitro-group is bonded to an aliphatic carbon (C-NO 2). E.g. nitromethane, nitro-
ethane, and FOX-7 (1,1-diamino-2,2-dinitroethene).

Nitramine. Nitro-group is bonded to a nitrogen atom (N-NO2). E.g. RDX, HMX, and CL-20.

Nitrate ester. Nitro-group is bonded to an oxygen atom (O-NO2). E.g. PETN, NG and NC

Organic azides

Organic explosive azides are characterized by having in their structure at least one carbon atom
and one azide group (-N3). Cyanuric triazide (C3N12) or ammonium azidotetrazolate (NH4CN7)
are common examples of organic triazides with explosive properties.

Organic halogen amino compounds Halogen amino explosive compounds are organic explosives
characterized by having in their structure at least one carbon atom and one halogen-amino group
(-NX2), such as methyldichloramine (CH3NCl2).
Azo/diazo explosive compounds Azo/diazo explosive compounds are organic explosives
characterized by having in their structure at least one carbon atom and one or more azo/diazo
groups (-N¼N-/-NN). Diazomethane (CH2N2) and diazodinitrophenol (which combines nitro
and diazo groups) are common examples of azo/diazo explosives.

Other organic explosives. As previously introduced, most organic molecular explosives contain
either peroxide, nitro, azide, halogen-amino or azo/diazo groups in their structure. In fact, the
explosive character of organic explosives is usually due to those groups. Nevertheless, there are
some exceptions. Thus, an extra group is created to include every organic explosive that does not
contain neither peroxide, nitro, azide, halogen-amino nor azo/diazo groups in its structure. For
this reason, a wide variety of chemically different compounds has a place in this group such as
tetracene (C18H12) or fulminic acid (HCNO).

Inorganic explosives

Pure individual inorganic explosives include those explosive compounds that either 1) do not
contain carbon atoms in their structure or 2) contain at least one atom different to carbon,
hydrogen, oxygen, nitrogen or halogen in their structure. This includes, for example, lead azide
(Pb(N3)2), nitrogen trichloride (NCl3) or ammonium nitrate (NH4NO3), which do not contain
carbon atoms; but also, silver fulminate (AgCNO), cuprous acetylide (CU 2C2), lead styphnate
(PbC6HN3O8) or lead picrate (PbC12H4N6O14), which, despite containing carbon atoms,
contain at least one atom different to C, H, O, N or halogen (generally a metal element).[3,19] In
fact, inorganic explosives are usually subclassified in two classes depending on this issue: those
explosives containing metal elements and those explosives only composed of nonmetal elements.

Nonmetal inorganic explosives

Nonmetal inorganic explosives are those explosive substances that do not contain neither carbon
nor metal atoms in their structure. Concretely, most explosives included in this group are
exclusively composed of nitrogen, hydrogen, oxygen and halogen (mainly chlorine). These
explosives might be further sub-classified into:

Ammonium nitrate (NH4NO3). Ammonium nitrate is an inorganic ionic salt composed of nitrate
anion (i.e. a nitrogen atom equally bonded to three oxygen atoms (NO 3), and ammonium cation
(i.e. a nitrogen atom equally bonded to four hydrogen atoms (NH4)

Ammonium dinitramide (NH4N(NO2)2). Ammonium dinitramide is an inorganic ionic salt

composed of dinitramide anion (i.e. a nitrogen atom equally bonded to two nitro groups
(N(NO2)2 - )), and ammonium cation.

Ammonium chlorate/perchlorate (NH4ClO3/NH4ClO4). Ammonium chlorate and ammonium

perchlorate are inorganic ionic salts composed of chlorate/perchlorate anion (i.e. a chlorine atom
equally bonded to three/four oxygen atoms (ClO3 - /ClO4 - )), and ammonium cation.
Nitrogen halides. The nitrogen halides contain three atoms of one of the halogens bound together
with one atom of nitrogen, such as nitrogen triiodide (NI3) or nitrogen trichloride (NCl3).

Hydrazine and derivatives (N2H4). Hydrazine is an inorganic molecule composed of two

nitrogen atoms, bonded to two hydrogen atoms each (H2N-NH2)

ENERGY RELEASE, EXPLOSIVE OUTPUT, AND CRITICAL DIAMETER

For most explosives, where a small volume of a solid is converted into a large volume of gas, a
good approximation of the energy release DG is dominated by the enthalpy change DH: DG =
DH–TDS, where DH is given by the heat of formation of the products minus the heat of
formation of the reactants [see Eqs. (1) and (2)]. Hence, it is desirable that chemical explosives
have as positive a heat of formation as possible.

To maximize the working fluid (i.e., gas) generated in an explosion, chemical explosives are
designed to be dense and to have high oxygen and/or nitrogen content. It is this requirement for
gas formation that favours explosives having C, H, N, and O atoms. To react with sufficient
rapidity, an explosive must contain its own source of oxygen.

BLASTING MECHANICS

Upon detonation, explosives affect rock by various interrelated means. While the following
discussion simplifies a complex and (in some aspects) largely theoretical subject, it should
provide a basic grasp of blast mechanics. The same mechanisms apply to whatever material is
being blasted (wood, concrete, steel, soil, ice, etc.); however, results are highly dependent on
material integrity. As a result, this discussion will consider only monolithic bedrock in order to
avoid confusion.

1. Detonation Shock Wave: Upon initiation, the detonation (explosive oxidation) zone proceeds
down the column of explosive at the product's detonation velocity. At the front of this detonation
zone, an energy pulse or “shock wave” is generated and transmitted to the adjacent rock; any air
space between the explosive and the rock absorbs wave energy and reduces its effect on the rock.
The shock wave travels outward as a compression wave in all directions from the borehole,
moving at or near detonation velocity. The rock immediately surrounding the borehole is crushed
to some extent, dependent on how much the force of the wave exceeds the compression strength
of the rock. The force of the wave overcomes the elastic limits of the rock, causing it to bend
outward and crack. These are radial cracks in that they radiate out from the borehole and they are
generated at speeds related to the sonic velocity of the rock itself (+/–8,000 fps in hard rock, +/–
1,500 fps in soft rock). If the rock mass is too large to permit bending, such as behind the
borehole, no radial fracture occurs; the wave energy is simply absorbed by the rock.

2. Shock Wave Reflection: At this point, the result of the blast will only be very large wedge-
shaped blocks, still interlocked. However, when the shock wave reaches a free face, the outward-
bending compressive force releases, and the wave is reflected back into the rock as a tension
wave. The speed of the shock wave has been slowed somewhat, and its energy lowered, but if the
distance from the borehole to the free face is not too great, it still carries enough force to
overcome the tensile strength of the rock. Rock, like concrete, has far greater strength in
compression than in tension (for instance, granite with compression strength of 30,000 psi has a
tensile strength of only 1200 psi). The reflected tension wave causes lateral cracking in the rock
between the radial cracks, creating “fragmentation.” Obviously, the greater the distance between
the borehole and the free face, the more the wave energy is used along the way, and the larger
those “fragments” will be. If there is no free face, such as behind the borehole, there will be no
wave reflection and no lateral cracking. A point to remember is that any break in rock continuity
will act as a free face; a crack or weather seam is as good as a quarry face in this regard.

3. Gas Pressure and Rock Movement: Upon detonation along with the shock wave, the solid
explosive is instantly converted to superheated gas that is trying to occupy a space 10,000 to
20,000 times its original solid volume, and exerting a pressure that can exceed 1.5 million psi.
Without this gas pressure, the fractured rock would not move and would remain interlocked. The
fractured rock mass has a certain inertia (consider this a desire to stay where it is), which the gas
pressure must initially overcome to start rock movement. Thus, there is “hesitation” between
detonation and the start of rock movement, lasting roughly one millisecond per foot of distance
between the borehole and the free face (i.e., if the distance is 10 feet, movement will start
roughly 10 milliseconds after detonation). Once inertia is overcome, the rock moves outward
away from the borehole at around one foot each 10 milliseconds, or between 40 and 70 mph,
although smaller fragments can move faster and be shot out as flyrock. As with the detonation
shock wave, nice even results in rock movement require rock continuity; cracks and weather
seams will allow gas venting, and result in uneven and sometimes surprising directions and
distances of rock throw.
Fig. 2 The mechanics of blasting

DETONATION VELOCITY

Detonation velocity is an important property to consider when rating an explosive. It may be

expressed as a confined or unconfined value and is normally given in feet per second (fps). The
confined detonation velocity measures the speed at which the detonation wave travels through a
column of explosive within a borehole or other confined space. The unconfined velocity
indicates this rate when the explosive is detonated in the open. Because explosives generally are
used under some degree of confinement, the confined value is more significant. Most
manufacturers, however, measure detonation velocity in an unconfined column of explosive 1
1/4 inches in diameter, although some measurements are made within the confinement of an iron
pipe or using a different diameter.

The confined detonation velocity of commercial explosives varies from 5000 to 25,000 fps
(Tables 2-1 through 2-6). With cartridge explosives, the confined velocity is seldom attained
because complete confinement is usually impossible. For blasting in hard rock, a high-velocity
explosive is preferable. In a softer or highly jointed rock, a low-velocity explosive , for example,
(ANFO) with a heaving action may give satisfactory results at a lower cost. Some explosives,
and particularly blasting agents, are more sensitive to diameter changes than others. In charges
with larger diameters, say six inches or more, the velocity may be medium to high. But as
diameters get smaller, the velocity is reduced until, at the blasting agent’s critical diameter,
( approximately three inches for ANFO, propagation is no longer assured and misfires are
likely).
Table 2. Properties of high-density ammonia dynamite

Table 3. Properties of a low-density ammonia dynamite, low-velocity series.

DETONATION AND BOREHOLE PRESSURE

Detonation pressure is a function of the detonation velocity and density of an explosive. The
nomograph (Figure 2-2) can be used to approximate the detonation pressure of an explosive
when the detonation velocity and specific gravity are known. As can be seen, the detonation
pressure is more dependent on detonation velocity than specific gravity. A high detonation
pressure is necessary when blasting hard, dense rock. In softer rock, a lower pressure is
sufficient. Detonation pressures of explosives range from 10 to over 140 Kilobars (l Kilobar =
14,504 psi).

WATER RESISTANCE: An explosive's water resistance is a measure of its ability to withstand

exposure to water without deteriorating or losing sensitivity. Sensitivity is the ease with which an
explosive detonates. In dry work, water resistance is of no consequence. If water is standing in
the borehole, and the time between loading and firing is fairly short, an explosive with a water-
resistance rating of “good” is sufficient. If the exposure is prolonged, or if the water is
percolating through the borehole, “very good” to excellent” water resistance is required. In
general, gelatins and emulsions offer the best water resistance. Higher-density explosives have
fair to excellent water resistance, whereas low-density explosives and blasting agents have little
or none. Brown nitrogen oxide fumes from a blast often mean the explosive has deteriorated
from exposure to water.

FUME CLASS: Ideally, detonation of a commercial explosive produces water vapor, carbon
dioxide, and nitrogen. In addition, undesirable poisonous gases such as carbon monoxide and
nitrogen oxides are usually formed. These gases are known as fumes, and the fume class of an
explosive indicates the nature and quantity of the undesirable gases formed during detonation.
Better ratings are given to explosives producing smaller amounts of fumes. For open work,
fumes are not usually an important factor, In confined spaces, however, the fume rating of an
explosive is important. In any case, the blaster should ensure that everyone stays away from
fumes generated in a shot. Carbon monoxide gradually destroys the brain and central nervous
system, and nitrogen oxides immediately form nitric acid in the lungs. Fume classes can be from
poor to good and are rated Class A or B by the Bureau of Mines and class 1, 2, 3, by IME. Class
A and Class 1 typically emit less noxious fumes per gram of explosive than Class B or Classes 2
or 3.

SHELF LIFE: Shelf lives of various products described are listed in their respective tables. For
most explosives products, a shelf life of one year is recommended, although satisfactory
performance can be expected from most products two, three, and even four years later. Consult
the appropriate manufacturer to determine shelf life ratings beyond one year. NPS-65 mandates a
maximum shelf-storage of two years.

PERMISSIBLES OR PERMITTED EXPLOSIVES: A permissible explosive is one which has

been approved by the U.S. Bureau of Mines or the British Ministry of Fuel and Power for the use
in gas or dust-filled mines. When detonated or exploded, all explosives produce a flame that
varies in volume, duration, and temperature. Black powder produces the longest lasting flame,
while dynamites typically produce a shorter lasting, but more intense flame. Permissible
explosives are especially designed to produce a flame of low volume, short duration, and low
temperature. This is accomplished by adding certain salts to the explosives formula in order to
cool or quench the flame to prevent the ignition of gas or dust within the confined space of a
mine. Permissible explosives are generally modified types of emulsions, water-gels, or ammonia
dynamites, all in cartridge or chub form.

BLASTING AGENTS AND AMMONIUM NITRATE

A blasting agent is any material or mixture consisting of a fuel and oxidizer that is intended for
blasting and that is not otherwise classified as an explosive.

A blasting agent consists primarily of inorganic nitrates (ammonium and sodium nitrates) and
carbonaceous fuels. The addition of an explosive ingredient, such as TNT, in sufficient quantity,
changes the classification of the mixture from a blasting agent to an explosive. When
unconfined, blasting agents cannot be detonated by means of a No. 8 test blasting cap unless an
explosive ingredient or sensitizer is added. No. 8 test caps contain the equivalent of two grams of
a mixture of 80 percent mercury fulminate and 20 percent potassium chlorate.

Nitrocarbonitrate is synonymous with a blasting agent, including ANFO, and is an official

classification for interstate transportation. Blasting agents may be classified as (1) dry blasting
agents, (2) emulsions, (3) water gel or (4) slurry blasting agents. Bulk Mixed Compounds: This
includes the majority of the ammonium nitrate-fuel oil mixtures and bulk slurries which are often
mixed on the job by the supplier in the delivery truck. The detonation velocities range between
9000 and 15,000 feet per second. This product has no water resistance and fair to good fumes, if
properly mixed and detonated. Pre-mixed Nitrocarbonitrates (NCN): Another term for
ammonium nitrate mixes. These include products prepared by a commercial manufacturer and
purchased by the consumer in the ready-to-use package form. The densities of these products are
variable. Velocity ranges from 12,000 to 15,000 feet per second. Cycling of Ammonium Nitrate:
Ammonium nitrate, for its weight, supplies more gas upon detonation than any other explosive.
In pure form, ammonium nitrate is almost inert (powerless) and is composed of 60 percent
oxygen by weight, 33 percent nitrogen, and seven percent hydrogen. Two characteristics make
this compound both unpredictable and dangerous. Ammonium nitrate is water soluble and if
uncoated, can attract water from the atmosphere and slowly dissolve itself.

For this reason, most prills have a protective coating of wax or clay which acts as a moisture
retardant. The second and most important characteristic is a phenomenon called “cycling.” This
is the ability of a material to change its crystal form with temperature. Ammonium nitrate will
have one of five crystal forms depending on the temperature. The cycling phenomenon can
seriously affect both the storage and performance of any explosive which contains ammonium
nitrate. Most dynamites, both regular nitroglycerin or permissibles, contain some percentages of
ammonium nitrate, while blasting agents are almost totally comprised of this compound. The
cycling effect in dynamite is not due to other ingredients mixed with the ammonium nitrate. For
this reason, cycling does not greatly affect dynamite the way it does ANFO. The two
temperatures at which cycling will occur under normal conditions are 0 and 90°F. This is to say
that products which are stored over the winter, or for a period of time during the summer, most
likely will undergo some amount of cycling. During the summer, in poorly ventilated powder
magazines, the cycling temperature may be reached daily. The effect of cycling of ammonium
nitrate when isolated from the humidity in the air is that the prills break down into finer and finer
particles, or enlarge to the point at which they are virtually inert. When the temperature exceeds
90°F, the prills break down into smaller crystals. This causes the density to increase from 0.8 to
1.2 gm/ cc. A density increase will also increase the detonation velocity of the compound. The
detonation velocity of ammonium nitrate with a density near 0.8 is around 10,000 feet per
second. Ammonium nitrate with a density near 1.2 may have a velocity of 15,000 feet per
second. To further complicate the situation, some blasting agents are not sealed well enough to
exclude humidity. After 31 the ammonium nitrate has undergone one cycle, the waterproof
protective coating is broken and the water vapor in the air condenses on the particles. As cycling
continues and more water collects, the mass starts to dissolve and upon dissolving, starts to
recrystallize into large crystals. Therefore, it is evident that a volume of ANFO after cycling may
have very dense areas and areas of large crystals which are not as dense. The performance of this
product may range from that of a very powerful explosive to one that just burns, or one that will
not shoot at all.

DETONATION AND DEFLAGRATION

With proper initiation, chemical explosives (as opposed to mechanical or atomic explosives)
undergo violent decomposition to produce heat, gas, and rapid expansion of matter. The practical
effect will depend on the speed at which the decomposition takes place as well as on the amount
of gas and heat released. We can distinguish two important cases, as follows:

1. Chemical reaction proceeds through the material at a rate less than or equal to the speed of
sound in the unreacted material. This is known as a ‘‘deflagration’’.

2. Chemical reaction proceeds through the material at a rate greater than the speed of sound in
the unreacted material. This is known as a ‘‘detonation’’.

Both deflagrations and detonations can produce what a lay observer might describe as an
‘‘explosion’’.

Nonetheless, a detonation is a special type of explosion with specific physical characteristics. It

is initiated by the heat accompanying shock compression; it liberates sufficient energy, before
any expansion occurs, to sustain the shock wave. The shock wave propagates into the unreacted
material at supersonic speed, typically 1500–9000 m/s.

THE APPLICATION OF EXPLOSIVES TO METAL CUTTING, ROCK DRILLING

AND CONTROLLED EARTH SHIFTING

METAL CUTTING AND FRACTURING

Explosive operations on metals can be divided into two principal groups, stand-off operations
and contact operations. Most forming processes are of the stand-off type where the explosive
charge is separated from the workpiece by an intermediate medium, usually a liquid, so that the
forming is generated by shock waves within the medium. In contact operations the charge is
placed directly on the workpiece or an adjacent buffer of solid material causing very high
pressures to be developed at the contact interface. These pressures, of the order of several million
pounds/in~, are very much higher than those developed in stand-off operations and can readily
produce extreme plastic deformation, fracturing and disintegration. The local peak pressure
depends on the explosive and the type of material in contact with it, while the mass of explosive
and inertia of the workpiece only affect the rate of decay of this peak pressure.

EXPLOSIVE DRILLING

The use of explosives for drilling deep holes in the earth has been quite extensively investigated
in the U.S.S.R. and a very complete summary of the subject has been given by Ostrovskii. is The
chief use of such bores is for oil exploration and recovery where bore holes of 10,000 ft and
more are often required. These are normally drilled with a rotary bit about which drilling mud is
circulated to remove loose material, cool the drill and provide a pressure greater than that
expected in any oil-bearing strata. Suspended solids in this mud help to seal the bore initially.
The power source is normally at the top of the hole with the torque carried through the drill pipe,
but recently some holes have been drilled with a bottom power source provided by a turbine or a
submerged motor. In either case the entire drilling string has to be raised to charge the bit and as
the life of a bit is short a very large proportion of the time is spent in raising and lowering this
extremely long pipe. This operation becomes increasingly difficult and time-consuming as the
depth of the hole increases and the position is aggravated by a drop in drilling efficiency due to
the high temperatures and pressures which reduce the life of the bit at these lower levels.

Figure 2 Diagram of explosive drilling equipment

EARTH SHIFTING BY EXPLOSIVES

The primary use of explosives in earth-moving operations is to break up rock and other hard
material down to a size which can be handled by mechanical earth-moving equipment. It is
extensively used in this way in open-cast mining, road building and most forms of civil
engineering works. In many quarrying operations the explosive not only breaks up the quarry
face, but, in addition, causes the rock to fall to the floor of the quarry where it fragments further
and can conveniently be handled. Comprehensive information on these uses of explosives has
been collected by Langefors and KihlstromJ ~ The present availability of high-powered nuclear
explosives has aroused interest in the possibility of using explosives to move quantities of earth
purely by explosions with little or no assistance from mechanical equipment. Basically this is
done by burying an explosive some distance underground and detonating it to form a crater. A
large proportion of the ejected material will rise vertically, or nearly so, tending to fall back into
the newly formed crater so that the efficiency of the process is low. One can distinguish between
the true crater which includes all the ruptured material, and the apparent crater after fall back ;
the apparent crater in many cases is only a small fraction of the size of the true crater.

CONSEQUENCES OF EXPLOSIVES TO HUMAN HEALTH

Human exposure to explosives can occur from various sources, including occupational exposure
during its production and in the environment owing to the contamination of soil and groundwater
reservoirs in old areas of production and military training. Explosions, the result of the potential
for propagation of detonation in soils, lead to a contamination of > 10 % and throw shrapnel
throughout the region. These pieces can have a size of 100 cm 3 or more, although the most
common are in the order of 1 cm3. Shrapnel can be hazardous to unprotected workers,
particularly those using the weapons, within which the pieces of metal can be allocated and thus
becoming endogenous sources of contamination. The DNTs are absorbed through the skin,
respiratory tract and gastrointestinal tract, and excreted in urine. In the urine of workers
occupationally exposed, acid dinitrobenzoic 2, 4(2, 4-DNBA) was identified as the main
metabolite of DNT. Furthermore, methemoglobin can be formed depending on the dose in the
blood after short-term exposure. Nonspecific general symptoms (headaches, irritation of mucous
membranes, nausea, vomiting) can occur following exposure to DNT, as well as a discoloration
of the skin and hair. Both DNT, 2, 4-DNT and 2, 6-DNT, show acute toxicity with a low level of
carcinogenicity. The DNTs are carcinogenic in animal experiments. An increased risk of
hepatobiliary carcinoma was reported in workers exposed to DNTs during the production of
ammunition. Urothelial cancer has been reported in persons highly exposed to DNT in Germany.
In addition, the increased occurrence of cardiovascular changes after exposure to DNTs for a
long period remains a topic of discussion. Although the mishandling during the manufacture of
TNT can seem a thing of the past in developed countries, environmental deposition of TNT and
other explosives in those countries, unfortunately, are still present in areas of military testing,
resulting in thousands of unexploded ordnance or owing to the storage of explosives. Similar to
DNT, TNT is readily absorbed by the skin, respiratory tract and gastrointestinal tract, and mainly
excreted through urine. Nitro reductases in the liver metabolize TNT, forming 2-amino-4,6-
dinitrotoluene (2-ADNT) and 4-amino-2,6-dinitrotoluene (4-ADNT) as its major metabolites.
The nitrous and hydroxylamine groups responsible for the toxicity of TNT react with biological
molecules, causing carcinogenic and mutagenic effects. The complete reduction of the nitro
group to an amino group decreases the mutagenic effect of the compound. Dihydroxylamine-
dinitrotoluene, a TNT metabolite, can cause hemotoxic symptoms in workers exposed to TNT.
Occupational exposure to TNT, depending on the dose, can cause irritation of the skin and
mucous membranes, impaired liver function, red blood cell disorders, aplastic anemia, and
peeling skin and hair. Hemolytic anemia has been reported in individuals with glucose-6-
phosphatedehydrogenase deficiency following exposure to TNT. Moreover, in single studies, an
increased incidence of cataracts and changes in sperm were reported after exposure to TNT.
Human populations have been inadequately studied with regard to TNT carcinogenicity.
Information is limited on the toxicity of RDX in humans.

REFRENCES

1. Zapata, F., & García-Ruiz, C. (2020). Chemical Classification of Explosives. Critical

Reviews in Analytical Chemistry, 1–18.
2. Jehuda Yinon & John C. Hoffsommer (1977) Analysis of Explosives, C R C Critical
Reviews in Analytical Chemistry, 7:1, 1-35.
3. Lima, D. R. S., Bezerra, M. L. S., Neves, E. B., & Moreira, F. R. (2011). Impact of
ammunition and military explosives on human health and the environment. Reviews on
Environmental Health, 26(2).
4. Marshall, M., & Oxley, J. C. (2009). Explosives. Aspects of Explosives Detection, 11–26.
5. McLeish, R. D. (1966). The application of explosives to metal cutting, rock drilling and
controlled earth shifting. International Journal of Mechanical Sciences, 8(5), 397–409.