English
Noun
explosives
- Plural of explosive
An explosive material is a material that either
is
chemically or
otherwise
energetically
unstable or produces a sudden expansion of the material usually
accompanied by the production of
heat and large changes in pressure
(and typically also a flash and/or loud noise) upon initiation;
this is called the
explosion.
Chemical explosives
Explosives are classified as low or high
explosives according to their rates of
decomposition: low
explosives burn rapidly (or deflagrate), while high explosives
undergo detonations. No sharp distinction exists between low and
high explosives, because of the difficulties inherent in precisely
observing and measuring rapid decomposition.
The
chemical
decomposition of an explosive may take years, days, hours, or a
fraction of a second. The slower processes of decomposition take
place in storage and are of interest only from a stability
standpoint. Of more interest are the two rapid forms of
decomposition,
deflagration and
detonation.
The term "detonation" is used to describe an
explosive phenomenon whereby the decomposition is
propagated by the explosive
shockwave
traversing the explosive material. The shockwave front is capable
of passing through the high explosive material at great speeds,
typically thousands of meters per second.
Explosives usually have less potential energy
than petroleum fuels, but their high rate of energy release
produces the great blast pressure.
TNT has a detonation
velocity of 6,940 m/s compared to 1,680 m/s for the detonation of a
pentane-air mixture, and the 0.34-m/s
stoichiometric flame
speed of gasoline combustion in air.
Explosive force is released in a direction
perpendicular to the surface of the explosive. If the surface is
cut or shaped, the explosive forces can be focused to produce a
greater local effect; this is known as a
shaped
charge.
In a low explosive, the decomposition is
propagated by a flame front which travels much more slowly through
the explosive material.
The properties of the explosive indicate the
class into which it falls. In some cases explosives can be made to
fall into either class by the conditions under which they are
initiated. In sufficiently large quantities, almost all low
explosives can undergo a Deflagration to Detonation Transition
(DDT). For convenience, low and high explosives may be
differentiated by the
shipping and storage classes.
Explosive compatibility groupings
Shipping labels and tags
will include
UN
and national, e.g.
USDOT,
hazardous
material Class with Compatibility Letter, as follows:
- 1.1 Mass Explosion Hazard
- 1.2 Non-mass explosion, fragment-producing
- 1.3 Mass fire, minor blast or fragment hazard
- 1.4 Moderate fire, no blast or fragment: a consumer firework is 1.4G or 1.4S
- 1.5 Explosive substance, very insensitive (with a mass
explosion hazard)
- 1.6 Explosive article, extremely insensitive
A Primary explosive substance (1.1A)
B An article containing a primary explosive
substance and not containing two or more effective protective
features. Some articles, such as detonator assemblies for blasting
and primers, cap-type, are included. (1.1B, 1.2B, 1.4B)
C Propellant explosive substance or other
deflagrating explosive substance or article containing such
explosive substance (1.1C, 1.2C, 1.3C, 1.4C)
D Secondary detonating explosive substance or
black powder or article containing a secondary detonating explosive
substance, in each case without means of initiation and without a
propelling charge, or article containing a primary explosive
substance and containing two or more effective protective features.
(1.1D, 1.2D, 1.4D, 1.5D)
E Article containing a secondary detonating
explosive substance without means of initiation, with a propelling
charge (other than one containing flammable liquid, gel or
hypergolic liquid) (1.1E,
1.2E, 1.4E)
F containing a secondary detonating explosive
substance with its means of initiation, with a propelling charge
(other than one containing flammable liquid, gel or hypergolic
liquid) or without a propelling charge (1.1F, 1.2F, 1.3F,
1.4F)
G Pyrotechnic substance or article containing a
pyrotechnic substance, or article containing both an explosive
substance and an illuminating, incendiary, tear-producing or
smoke-producing substance (other than a water-activated article or
one containing white phosphorus, phosphide or flammable liquid or
gel or hypergolic liquid) (1.1G, 1.2G, 1.3G, 1.4G)
H Article containing both an explosive substance
and white phosphorus (1.2H, 1.3H)
J Article containing both an explosive substance
and flammable liquid or gel (1.1J, 1.2J, 1.3J)
K Article containing both an explosive substance
and a toxic chemical agent (1.2K, 1.3K)
L Explosive substance or article containing an
explosive substance and presenting a special risk (e.g., due to
water-activation or presence of hypergolic liquids, phosphides or
pyrophoric substances) needing isolation of each type (1.1L, 1.2L,
1.3L)
N Articles containing only extremely insensitive
detonating substances (1.6N)
S Substance or article so packed or designed that
any hazardous effects arising from accidental functioning are
limited to the extent that they do not significantly hinder or
prohibit fire fighting or other emergency response efforts in the
immediate vicinity of the package (1.4S)
Exotic explosives
In addition to chemical explosives, there
exists varieties of more exotic explosive material, and theoretical
methods of causing explosions. Examples include
nuclear
explosives,
antimatter and abruptly
heating a substance with a high-intensity
laser or
electric
arc.
Low explosives
A low explosive is usually a mixture of a
combustible
substance and an
oxidant
that decomposes rapidly (
deflagration); unlike most
high explosives, which are compounds.
Under normal conditions, low explosives undergo
deflagration at rates that
vary from a few
centimeters per second to
approximately 400
metres
per second. It is possible for them to deflagrate very quickly,
producing an effect similar to a detonation. This usually occurs
when ignited in a confined space.
Low explosives are normally employed as
propellants. Included in
this group are
gun powders,
pyrotechnics and
illumination devices such as
flares.
High explosives
High explosives are normally employed in
mining, demolition, and military warheads. They undergo detonation
at rates of 1,000 to 9,000 meters per second. High explosives are
conventionally subdivided into two classes differentiated by
sensitivity:
- Primary
explosives are extremely sensitive to mechanical shock,
friction, and heat, to which they will respond by burning rapidly
or detonating.
- Secondary
explosives, also called base explosives, are relatively
insensitive to shock, friction, and heat. They may burn when
exposed to heat or flame in small, unconfined quantities, but
detonation can occur. These are sometimes added in small amounts to
blasting
caps to boost their power. Dynamite, TNT,
RDX, PETN, HMX, and others are
secondary explosives. PETN is often considered a benchmark
compound, with materials that are more sensitive than PETN being
classified as primary explosives.
Some definitions add a third category:
- Tertiary
explosives, also called blasting agents, are so insensitive to
shock that they cannot be reliably detonated by practical
quantities of primary explosive, and instead require an
intermediate explosive
booster of secondary explosive. Examples include an ammonium
nitrate/fuel oil mixture (ANFO) and slurry or
"wet bag" explosives. These are primarily used in large-scale
mining and construction operations.
Note that many if not most explosive chemical
compounds may usefully
deflagrate as well as
detonate, and are used in high as well as low explosive
compositions. This also means that under extreme conditions, a
propellant can detonate. For example,
nitrocellulose
deflagrates if ignited, but detonates if initiated by a
detonator.
Detonation of an explosive charge
The explosive train, also
called an initiation sequence or firing train, is the sequence of
charges that progresses from relatively low levels of energy to
initiate the final explosive material or main charge. There are
low- and high-explosive trains. Low-explosive trains are as simple
as a rifle cartridge, including a primer and a propellant charge.
High-explosives trains can be more complex, either two-step (e.g.,
detonator and
dynamite) or three-step (e.g.,
detonator,
booster
of primary explosive, and main charge of secondary explosive).
Detonators are often made from
tetryl and
fulminates.
Composition of the material
An explosive may consist of
either a chemically pure compound, such as
nitroglycerin, or a
mixture of an
oxidizer
and a
fuel, such as
black
powder.
Mixtures of an oxidizer and a fuel
An
oxidizer is a pure substance
(
molecule) that in a
chemical reaction can contribute some atoms of one or more
oxidizing elements, in which the
fuel component of the explosive
burns. On the simplest level, the oxidizer may itself be an
oxidizing
element, such
as
gaseous or
liquid oxygen.
Chemically pure compounds
Some chemical compounds are
unstable in that, when shocked, they react, possibly to the point
of detonation. Each molecule of the compound dissociates into two
or more new molecules (generally gases) with the release of
energy.
- Nitroglycerin:
A highly unstable and sensitive liquid.
- Acetone
peroxide: A very unstable white organic
peroxide
- TNT: Yellow
insensitive crystals that can be melted and cast without
detonation.
- Nitrocellulose:
A nitrated polymer which can be a high or low explosive depending
on nitration level and conditions.
- RDX,
PETN, HMX: Very powerful
explosives which can be used pure or in plastic explosives.
The above compositions may describe the majority
of the explosive material, but a practical explosive will often
include small percentages of other materials. For example,
dynamite is a mixture of highly
sensitive nitroglycerin with
sawdust, powdered
silica, or most commonly
diatomaceous
earth, which act as stabilizers. Plastics and polymers may be
added to bind powders of explosive compounds; waxes may be
incorporated to make them safer to handle;
aluminium powder may be
introduced to increase total energy and blast effects. Explosive
compounds are also often "alloyed": HMX or RDX powders may be mixed
(typically by melt-casting) with TNT to form
Octol or
Cyclotol.
Chemical explosive reaction
A chemical explosive is a
compound or mixture which, upon the application of heat or shock,
decomposes or
rearranges with extreme rapidity, yielding much
gas and heat. Many substances not
ordinarily classed as explosives may do one, or even two, of these
things. For example, at high temperatures (> 2000°C) a mixture
of
nitrogen and
oxygen can be made to
react with great rapidity and yield the gaseous product
nitric
oxide; yet the mixture is not an explosive since it does not
evolve heat, but rather absorbs heat.
- N2 + O2 → 2NO - 43,200 calories (or 180 kJ) per mole of
N2
For a chemical to be an explosive, it must
exhibit all of the following:
- Rapid expansion (i.e.,. rapid production of gases or rapid
heating of surroundings)
- Evolution of heat
- Rapidity of reaction
- Initiation of reaction
Evolution of heat
The generation of heat in large
quantities accompanies every explosive chemical reaction. It is
this rapid liberation of heat that causes the gaseous products of
reaction to expand and generate high
pressures. This rapid
generation of high pressures of the released gas constitutes the
explosion. It should be noted that the liberation of heat with
insufficient rapidity will not cause an explosion. For example,
although a pound of coal yields five times as much heat as a pound
of
nitroglycerin,
the coal cannot be used as an explosive because the rate at which
it yields this heat is quite slow.
Rapidity of reaction
Rapidity of reaction distinguishes the
explosive reaction from an ordinary combustion reaction by the
great speed with which it takes place. Unless the reaction occurs
rapidly, the thermally expanded gases will be dissipated in the
medium, and there will be no explosion. Again, consider a wood or
coal fire. As the fire burns, there is the evolution of heat and
the formation of gases, but neither is liberated rapidly enough to
cause an explosion. This can be likened to the difference between
the energy discharge of a
battery,
which is slow, and that of a flash
capacitor like that in a
camera flash, which
releases its energy all at once.
Initiation of reaction
A reaction must be capable of being
initiated by the application of shock or heat to a small portion of
the mass of the explosive material. A material in which the first
three factors exist cannot be accepted as an explosive unless the
reaction can be made to occur when desired.
Sensitiser
A sensitiser is a powdered or fine particulate
material that is sometimes used to create voids that aid in the
initiation or propagation of the detonation wave. It may be as
high-tech as glass beads or as simple as seeds.
Military explosives
To determine the suitability of an explosive
substance for
military
use, its
physical properties must first be
investigated. The usefulness of a military explosive can only be
appreciated when these properties and the factors affecting them
are fully understood. Many explosives have been studied in past
years to determine their suitability for
military use and most have been
found wanting. Several of those found acceptable have displayed
certain characteristics that are considered undesirable and,
therefore, limit their usefulness in military applications. The
requirements of a military explosive are stringent, and very few
explosives display all of the
characteristics necessary
to make them acceptable for military
standardization. Some of
the more important characteristics are discussed below:
Availability and cost
In view of the enormous quantity demands of
modern warfare, explosives must be produced from cheap raw
materials that are nonstrategic and available in great quantity. In
addition, manufacturing operations must be reasonably simple,
cheap, and safe.
Sensitivity
Regarding an explosive, this refers to the ease
with which it can be ignited or detonated—i.e., the
amount and intensity of
shock,
friction, or
heat that is required. When the
term
sensitivity is
used, care must be taken to clarify what kind of sensitivity is
under discussion. The relative sensitivity of a given explosive to
impact may vary greatly from its sensitivity to friction or heat.
Some of the test methods used to determine sensitivity are as
follows:
- Impact
Sensitivity is expressed in terms of the distance through which a
standard weight must be dropped to cause the material to explode.
- Friction
Sensitivity is expressed in terms of what occurs when a weighted
pendulum scrapes across the material (snaps, crackles, ignites,
and/or explodes).
- Heat
Sensitivity is expressed in terms of the temperature at which
flashing or explosion of the material occurs.
Sensitivity is an important consideration in
selecting an explosive for a particular purpose. The explosive in
an armor-piercing projectile must be relatively insensitive, or the
shock of impact would cause it to detonate before it penetrated to
the point desired. The explosive lenses around nuclear charges are
also designed to be highly insensitive, to minimize the risk of
accidental detonation.
Stability
Stability is the
ability of an explosive to be stored without
deterioration.
The following factors affect the stability of an
explosive:
- Chemical
constitution. The very fact that some common chemical compounds
can undergo explosion when heated indicates that there is something
unstable in their structures. While no precise explanation has been
developed for this, it is generally recognized that certain radical
groups, nitrite (–NO2), nitrate (–NO3), and azide (–N3), are
intrinsically in a condition of internal strain. Increasing the
strain by heating can cause a sudden disruption of the molecule and consequent
explosion. In some cases, this condition of molecular instability
is so great that decomposition takes place at ordinary
temperatures.
- Temperature of
storage. The rate of decomposition of explosives increases at
higher temperatures. All of the standard military explosives may be
considered to have a high degree of stability at temperatures of
-10 to +35 °C, but each has a high temperature at which the rate of
decomposition
rapidly accelerates and stability is reduced.As a rule of thumb,
most explosives become dangerously unstable at temperatures
exceeding 70 °C.
- Exposure to the sun. If
exposed to the ultraviolet rays of the sun,
many explosive compounds that contain nitrogen groups will rapidly
decompose, affecting their stability.
- Electrical
discharge. Electrostatic
or spark sensitivity to
initiation is common to a number of explosives. Static or other
electrical discharge may be sufficient to inspire detonation under
some circumstances. As a result, the safe handling of explosives
and pyrotechnics
almost always requires electrical
grounding of the operator.
Power
The term "power" (or more properly,
performance) as applied to
an explosive refers to its ability to do work. In practice it is
defined as the explosive's ability to accomplish what is intended
in the way of energy delivery (i.e., fragment projection, air
blast, high-velocity jets, underwater shock and bubble energy,
etc.). Explosive power or performance is evaluated by a tailored
series of tests to assess the material for its intended use. Of the
tests listed below, cylinder expansion and air-blast tests are
common to most testing programs, and the others support specific
applications.
- Cylinder expansion test. A standard amount of explosive is
loaded into a long hollow cylinder,
usually of copper, and detonated at one end. Data is collected
concerning the rate of radial expansion of the cylinder and maximum
cylinder wall velocity. This also establishes the Gurney
energy or 2E.
- Cylinder fragmentation. A standard steel cylinder is loaded
with explosive and detonated in a sawdust pit. The fragments
are collected and the size distribution analyzed.
- Detonation pressure (Chapman-Jouguet
condition). Detonation
pressure data derived from measurements of shock waves transmitted
into water by the detonation of cylindrical explosive charges of a
standard size.
- Determination of critical diameter. This test establishes the
minimum physical size a charge of a specific explosive must be to
sustain its own detonation wave. The procedure involves the
detonation of a series of charges of different diameters until
difficulty in detonation wave propagation is observed.
- Infinite-diameter detonation velocity. Detonation velocity is
dependent on loading density (c), charge diameter, and grain size.
The hydrodynamic theory of detonation used in predicting explosive
phenomena does not include diameter of the charge, and therefore a
detonation velocity, for an imaginary charge of Infinite diameter.
This procedure requires a series of charges of the same density and
physical structure, but different diameters, to be fired and the
resulting detonation velocities extrapolated to predict the
detonation velocity of a charge of infinite diameter.
- Pressure versus scaled distance. A charge of specific size is
detonated and its pressure effects measured at a standard distance.
The values obtained are compared with that for TNT.
- Impulse versus scaled distance. A charge of specific size is
detonated and its impulse (the area under the pressure-time curve)
measured versus distance. The results are tabulated and expressed
in TNT equivalent.
- Relative bubble energy (RBE). A 5- to 50-kg charge is detonated
in water and piezoelectric gauges measure peak pressure, time
constant, impulse, and energy.
-
- The RBE may be defined as Kx 3
- RBE = Ks
- where K = bubble expansion period for experimental (x) or
standard (s) charge.
Brisance
In addition to strength, explosives display a
second characteristic, which is their shattering effect or brisance
(from the French meaning to "break"), which is distinguished from
their total work capacity. An exploding propane tank may release
more chemical energy than an ounce of nitroglycerin, but the tank
would probably fragment into large pieces of twisted metal, while a
metal casing around the nitroglycerin would be pulverized. This
characteristic is of practical importance in determining the
effectiveness of an explosion in fragmenting shells, bomb casings,
grenades, and the like.
The rapidity with which an explosive reaches its peak pressure is a
measure of its brisance. Brisance values are primarily employed in
France and Russia.
The sand crush test is commonly employed to
determine the relative brisance in comparison to TNT. No test is
capable of directly comparing the explosive properties of two or
more compounds; it is important to examine the data from several
such tests (sand crush,
trauzl,
and so forth) in order to gauge relative brisance. True values for
comparison will require field experiments.
Density
Density of loading
refers to the mass of an explosive per unit volume. Several methods
of loading are available, including pellet loading, cast loading,
and press loading; the one used is determined by the
characteristics of the explosive. Dependent upon the method
employed, an average density of the loaded charge can be obtained
that is within 80-99% of the theoretical maximum density of the
explosive. High load density can reduce
sensitivity by making the
mass more resistant to
internal friction. However, if density
is increased to the extent that individual
crystals are crushed, the
explosive may become more sensitive. Increased load density also
permits the use of more explosive, thereby increasing the power of
the
warhead. It is
possible to compress an explosive beyond a point of sensitivity,
known also as "dead-pressing," in which the material is no longer
capable of being reliably initiated, if at all.
Volatility
Volatility,
or the readiness with which a substance
vaporizes, is an undesirable
characteristic in military explosives. Explosives must be no more
than slightly volatile at the temperature at which they are loaded
or at their highest storage temperature. Excessive volatility often
results in the development of pressure within rounds of ammunition
and separation of mixtures into their constituents. Stability, as
mentioned before, is the ability of an explosive to stand up under
storage conditions without deteriorating. Volatility affects the
chemical composition of the explosive such that a marked reduction
in stability may occur, which results in an increase in the danger
of handling. Maximum allowable volatility is 2 ml of gas evolved in
48 hours.
Hygroscopicity
The introduction of
water into an explosive is highly
undesirable since it reduces the sensitivity, strength, and
velocity of detonation of the explosive.
Hygroscopicity
is used as a measure of a material's moisture-absorbing tendencies.
Moisture affects explosives adversely by acting as an inert
material that absorbs heat when vaporized, and by acting as a
solvent medium that can cause undesired chemical reactions.
Sensitivity, strength, and velocity of detonation are reduced by
inert materials that reduce the continuity of the explosive mass.
When the moisture content evaporates during detonation, cooling
occurs, which reduces the temperature of reaction. Stability is
also affected by the presence of moisture since moisture promotes
decomposition of the explosive and, in addition, causes corrosion
of the explosive's metal container. For all of these reasons,
hygroscopicity must be negligible in military explosives.
Toxicity
Due to their chemical structure, most explosives
are toxic to some extent. Since the toxic effect may vary from a
mild headache to serious damage of internal organs, care must be
taken to limit toxicity in military explosives to a minimum. Any
explosive of high toxicity is unacceptable for military use.
Explosive product gases can also be toxic.
Measurement of chemical explosive reaction
The development of new and improved types of
ammunition requires a continuous program of research and
development. Adoption of an explosive for a particular use is based
upon both proving ground and service tests. Before these tests,
however, preliminary estimates of the characteristics of the
explosive are made. The principles of
thermochemistry are
applied for this process.
Thermochemistry is concerned with the changes in
internal energy, principally as heat, in chemical reactions. An
explosion consists of a series of reactions, highly exothermic,
involving decomposition of the ingredients and recombination to
form the products of explosion. Energy changes in explosive
reactions are calculated either from known chemical laws or by
analysis of the products.
For most common reactions, tables based on
previous investigations permit rapid calculation of energy changes.
Products of an explosive remaining in a closed
calorimetric
bomb (a constant-volume explosion) after cooling the bomb back
to room temperature and pressure are rarely those present at the
instant of maximum temperature and pressure. Since only the final
products may be analyzed conveniently, indirect or theoretical
methods are often used to determine the maximum temperature and
pressure values.
Some of the important characteristics of an
explosive that can be determined by such theoretical computations
are:
- Oxygen balance
- Heat of explosion or reaction
- Volume of products of explosion
- Potential of the explosive
Oxygen balance (OB%)
Oxygen
balance is an expression that is used to indicate the degree to
which an explosive can be oxidized. If an explosive molecule
contains just enough oxygen to convert all of its carbon to carbon
dioxide, all of its hydrogen to water, and all of its metal to
metal oxide with no excess, the molecule is said to have a zero
oxygen balance. The molecule is said to have a positive oxygen
balance if it contains more oxygen than is needed and a negative
oxygen balance if it contains less oxygen than is needed. The
sensitivity,
strength,
and
brisance of an
explosive are all somewhat dependent upon oxygen balance and tend
to approach their maximums as oxygen balance approaches zero.
Heat of explosion
When a chemical compound is formed from
its constituents, heat may either be absorbed or released. The
quantity of heat absorbed or given off during transformation is
called the
heat of
formation. Heats of formations for solids and gases found in
explosive reactions have been determined for a temperature of 15 °C
and atmospheric pressure, and are normally given in units of
kilocalories per gram-molecule. (See table 12-1). A negative value
indicates that heat is absorbed during the formation of the
compound from its elements; such a reaction is called an
endothermic reaction.
The arbitrary convention usually employed in
simple thermochemical calculations is to take heat contents of all
elements as zero in their
standard
states at all temperatures (standard state being defined as
natural or ambient conditions). Since the heat of formation of a
compound is the net difference between the heat content of the
compound and that of its elements, and since the latter are taken
as zero by convention, it follows that the heat content of a
compound is equal to its heat of formation in such non-rigorous
calculations. This leads to the principle of initial and final
state, which may be expressed as follows: "The net quantity of heat
liberated or absorbed in any chemical modification of a system
depends solely upon the initial and final states of the system,
provided the transformation takes place at constant volume or at
constant pressure. It is completely independent of the intermediate
transformations and of the time required for the reactions." From
this it follows that the heat liberated in any transformation
accomplished through successive reactions is the algebraic sum of
the heats liberated or absorbed in the several reactions. Consider
the formation of the original explosive from its elements as an
intermediate reaction in the formation of the products of
explosion. The net amount of heat liberated during an explosion is
the sum of the heats of formation of the products of explosion,
minus the heat of formation of the original explosive. The net
difference between heats of formations of the reactants and
products in a chemical reaction is termed the heat of reaction. For
oxidation this heat of reaction may be termed
heat of
combustion.
In explosive technology only materials that are
exothermic—that have
a heat of reaction that causes net liberation of heat—are of
interest. Hence, in this context, virtually all heats of reaction
are positive. Reaction heat is measured under conditions either of
constant pressure or constant volume. It is this heat of reaction
that may be properly expressed as the "heat of explosion."
Balancing chemical explosion equations
In order to assist in balancing chemical
equations, an order of priorities is presented in table 12-1.
Explosives containing C, H, O, and N and/or a metal will form the
products of reaction in the priority sequence shown. Some
observation you might want to make as you balance an
equation:
- The progression is from top to bottom; you may skip steps that
are not applicable, but you never back up.
- At each separate step there are never more than two
compositions and two products.
- At the conclusion of the balancing, elemental nitrogen, oxygen,
and hydrogen are always found in diatomic form.
- C6H2(NO2)3CH3; constituents: 7C + 5H + 3N + 6O
Using the order of priorities in table 12-1,
priority 4 gives the first reaction products:
- 7C + 6O → 6CO with one mol of carbon remaining
Next, since all the oxygen has been combined with
the carbon to form CO, priority 7 results in:
Finally, priority 9 results in: 5H → 2.5H2
The balanced equation, showing the products of
reaction resulting from the detonation of TNT is:
- C6H2(NO2)3CH3 → 6CO + 2.5H2 + 1.5N2 + C
Notice that partial moles are permitted in these
calculations. The number of moles of gas formed is 10. The product
carbon is a solid.
Volume of products of explosion
Avogadro's
law states that equal volumes of all gases under the same
conditions of temperature and pressure contain the same number of
molecules, that is, the
molar volume
of one gas is equal to the molar volume of any other gas. The molar
volume of any gas at 0°C and under normal atmospheric pressure is
very nearly 22.4 liters. Thus, considering the nitroglycerin
reaction,
- C3H5(NO3)3 → 3CO2 + 2.5H2O + 1.5N2 + 0.25O2
the explosion of one mole of nitroglycerin
produces 3 moles of CO2, 2.5 moles of H2O, 1.5 moles of N2, and
0.25 mole of O2, all in the gaseous state. Since a molar volume is
the volume of one mole of gas, one mole of nitroglycerin produces 3
+ 2.5 + 1.5 + 0.25 = 7.25 molar volumes of gas; and these molar
volumes at 0°C and atmospheric pressure form an actual volume of
7.25 × 22.4 = 162.4 liters of gas.
Based upon this simple beginning, it can be seen
that the volume of the products of explosion can be predicted for
any quantity of the explosive. Further, by employing
Charles' Law
for perfect gases, the volume of the products of explosion may also
be calculated for any given temperature. This law states that at a
constant pressure a perfect gas expands 1/273.15 of its volume at 0
°C, for each degree Celsius of rise in temperature.
Therefore, at 15 °C (288.15
kelvin) the molar volume of an
ideal gas is
- V15 = 22.414 (288.15/273.15) = 23.64 liters per mole
Thus, at 15 °C the volume of gas produced by the
explosive decomposition of one mole of nitroglycerin becomes
- V = (23.64 l/mol)(7.25 mol) = 171.4 l
Explosive strength
The potential of an explosive is the
total work that can be performed by the gas resulting from its
explosion, when expanded adiabatically from its original volume,
until its pressure is reduced to atmospheric pressure and its
temperature to 15 °C. The potential is therefore the total quantity
of heat given off at constant volume when expressed in equivalent
work units and is a measure of the strength of the explosive.
Example of thermochemical calculations
The PETN reaction will be examined as an example
of thermo-chemical calculations.
- PETN: C(CH2ONO2)4
- Molecular weight = 316.15 g/mol
- Heat of formation = 119.4 kcal/mol
(1) Balance the chemical reaction equation. Using
table 12-1, priority 4 gives the first reaction products:
Next, the hydrogen combines with remaining
oxygen:
Then the remaining oxygen will combine with the
CO to form CO and CO2.
Finally the remaining nitrogen forms in its
natural state (N2).
The balanced reaction equation is:
- C(CH2ONO2)4 → 2CO + 4H2O + 3CO2 + 2N2
(2) Determine the number of molar volumes of gas
per mole. Since the molar volume of one gas is equal to the molar
volume of any other gas, and since all the products of the PETN
reaction are gaseous, the resulting number of molar volumes of gas
(Nm) is:
- Nm = 2 + 4 + 3 + 2 = 11 Vmolar/mol
(3) Determine the potential (capacity for doing
work). If the total heat liberated by an explosive under constant
volume conditions (Qm) is converted to the equivalent work units,
the result is the potential of that explosive.
The heat liberated at constant volume (Qmv) is
equivalent to the liberated at constant pressure (Qmp) plus that
heat converted to work in expanding the surrounding medium. Hence,
Qmv = Qmp + work (converted).
- a. Qmp = Qfi (products) - Qfk (reactants)
-
- where: Qf = heat of formation (see table 12-1)
-
-
- Qmp = 2(26.343) + 4(57.81) + 3(94.39) - (119.4) = 447.87
kcal/mol
-
- (If the compound produced a metallic oxide, that heat of
formation would be included in Qmp.)
- b. Work = 0.572Nm = 0.572(11) = 6.292 kcal/mol
- As previously stated, Qmv converted to equivalent work units is
taken as the potential of the explosive.
- c. Potential J = Qmv (4.185 × 106 kg)(MW) = 454.16 (4.185 ×
106) 316.15 = 6.01 × 106 J kg
- This product may then be used to find the relative strength
(RS) of PETN, which is
- d. RS = Pot (PETN) = 6.01 × 106 = 2.21 Pot (TNT) 2.72 ×
106
References
- Army Research Office. Elements of Armament Engineering (Part
One). Washington, D.C.:
U.S. Army Materiel Command, 1964.
- Commander, Naval Ordnance Systems Command. Safety and
Performance Tests for Qualification of Explosives. NAVORD OD 44811.
Washington, D.C.: GPO, 1972.
- Commander, Naval Ordnance Systems Command. Weapons Systems
Fundamentals. NAVORD OP 3000, vol. 2, 1st rev. Washington, D.C.:
GPO, 1971.
- Departments of the Army and Air Force. Military Explosives.
Washington, D.C.: 1967.
- USDOT Hazardous Materials Transportation Placards
- Swiss Agency for the Environment, Forests, and Landscap.
'Occurrence and relevance of organic pollutants in compost,
digestate and organic residues', Research for Agriculture and
Nature. 8
November 2004. p 52, 91,
182.
explosives in Arabic: متفجرات
explosives in Bulgarian: Взривни вещества
explosives in Catalan: Explosiu
explosives in Czech: Výbušnina
explosives in Danish: Sprængstof
explosives in German: Sprengstoff
explosives in Modern Greek (1453-): Εκρηκτικές
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explosives in Spanish: Explosivo
explosives in Esperanto: Eksplodaĵo
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explosives in Polish: Materiał wybuchowy
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explosives in Russian: Взрывчатые вещества
explosives in Simple English: Explosive
material
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explosives in Chinese: 炸藥