The vast majority of explosives are chemical explosives. Explosives usually have less potential energy than fuels, but their high rate of energy release produces a 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.

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.

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

Gas

Gas is one of the three classical states of matter . Near absolute zero, a substance exists as a solid. As heat is added to this substance it melts into a liquid at its melting point , boils into a gas at its boiling point, and if heated high enough would enter a plasma state in which the electrons...

 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

Nitrogen

Nitrogen is a chemical element that has the symbol N, atomic number of 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless, and mostly inert diatomic gas at standard conditions, constituting 78.08% by volume of Earth's atmosphere...

 and oxygen

Oxygen

Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

 can be made to react with great rapidity and yield the gaseous product nitric oxide

Nitric oxide

Nitric oxide, also known as nitrogen monoxide, is a diatomic molecule with chemical formula NO. It is a free radical and is an important intermediate in the chemical industry...

; yet the mixture is not an explosive since it does not evolve heat, but rather absorbs heat.

N₂ + O₂ → 2 NO − 43,200 calorie

Calorie

The calorie is a pre-SI metric unit of energy. It was first defined by Nicolas Clément in 1824 as a unit of heat, entering French and English dictionaries between 1841 and 1867. In most fields its use is archaic, having been replaced by the SI unit of energy, the joule...

s (or 180 kJ

Joule

The joule ; symbol J) is a derived unit of energy or work in the International System of Units. It is equal to the energy expended in applying a force of one newton through a distance of one metre , or in passing an electric current of one ampere through a resistance of one ohm for one second...

) per mole

Mole (unit)

The mole is a unit of measurement used in chemistry to express amounts of a chemical substance, defined as an amount of a substance that contains as many elementary entities as there are atoms in 12 grams of pure carbon-12 , the isotope of carbon with atomic weight 12. This corresponds to a value...

 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

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.

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

Thermochemistry

Thermochemistry is the study of the energy and heat associated with chemical reactions and/or physical transformations. A reaction may release or absorb energy, and a phase change may do the same, such as in melting and boiling. Thermochemistry focuses on these energy changes, particularly on the...

 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

Calorimeter

A calorimeter is a device used for calorimetry, the science of measuring the heat of chemical reactions or physical changes as well as heat capacity. Differential scanning calorimeters, isothermal microcalorimeters, titration calorimeters and accelerated rate calorimeters are among the most common...

 (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

Balancing chemical explosion equations

In order to assist in balancing chemical equations, an order of priorities is presented in table 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.

Table 1. Order of Priorities

Priority	Composition of explosive	Products of decomposition	Phase of products
1	A metal and chlorine	Metallic chloride	Solid
2	Hydrogen and chlorine	HCl	Gas
3	A metal and oxygen	Metallic oxide	Solid
4	Carbon and oxygen	CO	Gas
5	Hydrogen and oxygen	H2O	Gas
6	Carbon monoxide and oxygen	CO2	Gas
7	Nitrogen	N2	Gas
8	Excess oxygen	O2	Gas
9	Excess hydrogen	H2	Gas
10	Excess carbon	C	Solid

Example, TNT:

C₆H₂(NO₂)₃CH₃; → : 7C + 5H + 3N + 6O

Using the order of priorities in table 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:

3N → 1.5N₂

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.

Example of thermochemical calculations

The PETN

PETN

Pentaerythritol tetranitrate , also known as PENT, PENTA, TEN, corpent, penthrite , is the nitrate ester of pentaerythritol. Penta refers to the five carbon atoms of the neopentane skeleton.PETN is most well known as an explosive...

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 1, priority 4 gives the first reaction products:

5C + 12O → 5CO + 7O

Next, the hydrogen combines with remaining oxygen:

8H + 7O → 4H₂O + 3O

Then the remaining oxygen will combine with the CO to form CO and CO₂.

5CO + 3O → 2CO + 3CO₂

Finally the remaining nitrogen forms in its natural state (N₂).

4N → 2N₂

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 (N_m) is:

N_m = 2 + 4 + 3 + 2 = 11 V_molar/mol

(3) Determine the potential (capacity for doing work). If the total heat liberated by an explosive under constant volume conditions (Q_m) is converted to the equivalent work units, the result is the potential of that explosive.

The heat liberated at constant volume (Q_mv) is equivalent to the heat liberated at constant pressure (Q_mp) plus that heat converted to work in expanding the surrounding medium. Hence, Q_mv = Q_mp + work (converted).

a. Q_mp = Q_fi (products) − Q_fk (reactants)

where: Q_f = heat of formation (see table 1)

For the PETN reaction:

Q_mp = 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 Q_mp.)

b. Work = 0.572N_m = 0.572(11) = 6.292 kcal/mol

As previously stated, Q_mv converted to equivalent work units is taken as the potential of the explosive.

c. Potential J = Q_mv (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