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Introduction to Naval Weapons Engineering

Chemical Explosives

The main purpose of any warhead is to inflict damage on the target. The way the damage is caused may vary with different types of
warheads, but in the most general sense, damage is caused by the transfer of energy from the warhead to the target. The energy is typically
mechanical in nature and takes the form of a shock wave or the kinetic energy of fragments. In either case, a large amount of energy must be
released. For many warheads that energy is stored in the form of chemical explosives.

Explosive Reactions

There are many chemical reactions that will release energy. These are known as exothermic reactions. If the reaction proceeds slowly, the
released energy will be dissipated and there will be few noticeable effects other than an increase in temperature. On the other hand, if the
reaction proceeds very rapidly, then the energy will not be dissipated. Thus, a great quantity of energy can be deposited into a relatively small
volume, then manifest itself by a rapid expansion of hot gases, which in turn can create a shock wave or propel fragments outwards at high
speed. Chemical explosions may be distinguished from other exothermic reactions by the extreme rapidity of their reactions. In addition to
the violent release of energy, chemical explosions must provide a means to transfer the energy into mechanical work. This is accomplished by
expanding product gases from the reaction. If no gases are produced, then the energy will remain in the products as heat.

Most chemical explosions involve a limited set of simple reactions, all of which involve oxidation (reaction with oxygen). A relatively easy
way to balance chemical explosive equations is to assume that the following partial reactions take place to their maximum extent (meaning
one of the reactants is totally consumed) and in order of precedence:

Table
1. Priorities of explosive reactions.

Reaction (to completion)

Priority

Metal + O Metallic Oxide (ex: ZnO or PbO)

1

C + O CO (gas)
2

2H + O H2O (gas)
3

CO + O CO2 (gas) (The CO comes from reaction (2))

4

Excess O,H & N O2, N2, & H2 (gases)

5

Example- balance the combustion of TNT: C7H5N3O6.

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No metals, so start with priority 2:

6C + 60 6CO, leaving 1C, 5H, 3N;

No oxygen left, skip priorities 3 and 4.

Lastly, the gases combine:

3N 3/2 N2

5H 5/2 H2, leaving 1 C not consumed.

Overall:
C7H5N3O6 6CO + 5/2 H2 + 3/2 N2 + C.

The total amount of energy released in the reaction is called the heat of explosion. It can be calculated by comparing the heats of formation
before and after the reaction DE = DEf(reactants) - DEf (products). The heats of formation for the products and many common explosives
(reactants) are given in Table 2. The heat of explosion is defined so that it will be positive for an exothermic reaction.

Table 2. Heats of formation.

Formula DEf (kJ/mol)

Name MW (g/mol)

28
CO -111.8

CO2 -393.5
44

H2O -240.6
18

C3H5N3O9 -333.66
Nitroglycerin 227

C3H6N6O6 +83.82
RDX 222

C4H8N8O8 +104.77
HMX 296

C5H8N4O12 -514.63
PETN 316

C7H5N3O6 -54.39
TNT 227

C7H5N5O8 +38.91
TETRYL 287

Notes:
1) CO,CO2 and H2O are assumed to be in gaseous form.
2) DEf for N2,H2,O2 and all other elements are all zero.

Example: find the heat of explosion for TNT.

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Before: DEf = -54.4 kJ/mol

After: DEf = 6(-111.8) + 5/2(0) + 3/2(0) + 1(0) = -670.8 kJ/mol

DE = (-54.4) + 670.8 - = 616.4 kJ/mol,

Since DE > 0, the reaction is exothermic, and the heat of explosion is +616.4 kJ/mol.

Expressed on a mass basis, TNT releases

kJ/mol)(1000 J/1 kJ)(1 mol/227 g) = 2175 J/g.

1 kg of TNT releases 2.175 x 106 J of energy.

Since most of the energy release comes from oxidation reactions, the amount of oxygen available is a critical factor. If there is insufficient
oxygen to react with the available carbon and hydrogen, the explosive is considered to be oxygen deficient. The converse is considered
oxygen rich. A quantitative measure of this is called the oxygen balance, defined as:

OB = -(100 %)MW(O)/MW(explosive) [ 2C + H/2 + M - O]

where:

C,H,M&O are the number of moles of carbon, hydrogen, metal and oxygen in the balanced reaction and MW is the molecular weight of
oxygen (= 16 g/mol) or the explosive.

Example- find the oxygen balance for TNT.

OB = -(100 %)(16/227)[2(7) + 5/2 - 6] = -72%

As a general rule, the oxygen balance should be near zero to get the maximum amount of energy release. Other concerns like stability or
volatility often limit the oxygen balance for chemical compounds. TNT is an example of a relatively powerful explosive that is oxygen
deficient.

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Some explosives are mixtures of chemicals that do not react and are known as composites. A common example is composite B-3 which is
made up of a 64/36 mixture of RDX (C3H6N6O6) and TNT. If written in the same notation, it would be C6.851H8.750N7.650O9.300 and would
have an oxygen balance, OB = -40.5%. ANFO which is a 94/6 mixture of ammonium nitrate and fuel oil has a -0.6% oxygen balance.
Composite explosives generally have oxygen balances that are closer to the ideal case of zero. Here are the mixtures used for some common
composite explosives:

Table 3. Composite explosives.

Composition
Name Formula

80/20 Ammonium nitrate/TNT C0.62H4.44N2.26O3.53

AMATOL

94/6 Ammonium nitrate/#2 Diesel oil C0.365H4.713N2.000O3.000

ANFO

91/9 RDX/WAX C1.87H3.74N2.46O2.46

COMP A-3

64/36 RDX/TNT C6.851H8.750 N7.650O9.300

COMP B-3

91/5.3/2.1/1.6 RDX/Di(2-ethyhexyl)
C1.82H3.54N2.46O2.51
COMP C-4 sebacate/Polyisobutylene/Motor Oil

75/15/10 RDX/TNT/Plasticizers
DYNAMITE -

Strength of Explosives

The determining factor in the conversion of the heat of explosion into mechanical work is the amount of product gases available for
expansion. In the case of TNT, 10 moles of gas are produced for each mole of explosive. We can exploit this fact to make predictions about
the actual explosive strength of other chemicals. This is known as the Berthelot approximation, which states that the relative explosive
strength of a material (as compared to TNT on a mass basis) may be calculated on the basis of two factors:

the change in internal energy (DE) and

the amount of gas produced. If we combine these factors and put in values for our reference, TNT, we obtain:

Relative Strength (%) = 840 Dn DE /MW2

where:
Dn = the number of moles of gas per mole of explosive
DE = the heat of explosion in kJ/mol
MW = molecular weight of explosive in g/mol

The factor of 840 accounts for the units and values of DE and Dn for TNT.

Example- calculate the Berthelot relative strength for RDX

RDX: C3H6N6O6 3CO + 3H2O + 3N2

MW = 222 g/mol
Dn = 9 mol

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DEf (before)= 83.82 kJ/mol

DEf (after) = 3(-111.8) + 3(-240.6) = -1057.2 kJ/mol

Therefore:
RS = 840 (9) (83.82 + 1057.2)/2222
RS = 175 %

The relative explosive strength calculated in this manner is of limited use. What is really important is the actual strength which can only be
measured by experiment. There are a variety of standard tests, most of which involve a direct measurement of the work performed. Here are
some example measurements for RDX:

Ballistic mortar test: 140 %

Trauzl block test: 186 %
Sand crush test: 136 %

all of which compare favorably with our Berthelot approximation.

Categories of Explosives

Not only must explosive materials be highly energetic, as characterized by the relative strength, but they must also react violently. The speed
of the reaction is vital to the build up of a large amount of energy into a small volume. Reactions that proceed slowly allow the energy that is
released to be dissipated (this is a consideration involving the interaction of the shock wave with targets). An explosion will create either a
shock wave, throw fragments outward our both. If the energy release is slow, the shock wave will be gradual and extended and the fragment
velocity low. On the other hand, a violent reaction will be characterized by a very sharp (short duration, high pressure) shock wave and large
fragment velocities. This rapidity of reaction is called the brisance, or shattering potential of the explosion. It is a property of the material and
the degree of confinement. If an explosion is restrained initially, it can build up a large pressure and achieve the same effect. The rapidity of
the reaction is used as a method of classification of explosive materials.

Explosive materials which react very violently (are brisant) are known as high explosives. They are used solely for their destructive power. In
contrast, there are some materials that react more slowly. These are known as low explosives. They release a large amount of energy, but due
to the relatively slow rate of reaction the energy is more useful as a propellant where the expansion of the gases is used to move projectiles.
An example would be gunpowder, which although quite energetic, is classified as a low explosive and used primarily as a propellant. It is
true that confinement will increase the brisance of gunpowder but there is a wide variety of materials that react much more quickly and
violently than gunpowder.

Initiation of the Explosive Reaction

Although the oxidation reactions that release energy in explosive reactions are energetically possible, they do not occur spontaneously. There
is usually some small barrier that must be overcome by the input of energy that will start the reaction, which then will continue by itself until
completion. The input of energy to overcome the barrier is known as initiation (or detonation). Sometimes only mechanical force is required
like in the case of nitroglycerin. In other situations, it requires heat like from a match or electricity. The ease of which an explosive may be
detonated is its sensitivity. For safety considerations, explosive materials are separated into three categories: those which will detonate easily,
called sensitive or primary explosives; those which require slightly more energy to detonate, called intermediate explosives; and those which
require relatively more energy to detonate, called insensitive or secondary explosives. The terms refer to how the different materials will be
physically configured in a working explosive device.

Table 4. Common explosives and their uses.

Primary H.E. Intermediate H.E. Secondary H.E.

(detonators) (boosters) (main charges)

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Tetrytol
Mercury fulminate RDX

PETN
Lead azide Comp-A,B,C

Tetryl
Lead styphnate Cyclotol

TNT
Tetracene HBX-1,3

DDNP H-6
MINOL 2

Ammonium Picrate

Primary explosive materials are used to detonate the entire explosive device. That is, they are usually connected to some external device
which starts the detonation. In this capacity, the primary explosive is called the fuse. The energy from the explosive detonation of the primary
material is used to set off the booster which in turn sets off the main charge which is made up of secondary (insensitive material). This
combination of a small quantity of sensitive material used to set off a large amount of secondary material is known as the explosive train. It is
called a train, because the events occur in sequence. The main charge must be made up of insensitive material for the safety of those handling
the device. In practice, the fuse is rarely stored with the device until it is required for use. In this manner, the device remains relatively safe,
since it is only made up of secondary (insensitive) material and cannot be detonated.

Figure 1. High explosive

train.

Once the fuse is installed, the entire device requires great care in handling to prevent inadvertent detonation. Often, the device is configured
so that the explosive train must pass through a small physical port that connects the fuse to the main charge. This port can be blocked until the
device will be used. As an example, the port may consist of two rotating plates with off-center holes. When the plates are aligned, the two
holes will line up and permit operation. This is called arming the device. Otherwise, the holes will not be aligned and the device will be safe.
The mechanism with plates is called the safing and arming device. Other configurations exist, but they all accomplish the same function: to
prevent inadvertent detonation and permit detonation when authorized.

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