Evolution of Heat

The generation of heat in large quantities accompanies most explosive chemical reaction. The exceptions are called entropic explosives and include organic peroxides such as acetone peroxide. It is the rapid liberation of heat that causes the gaseous products of most explosive reactions to expand and generate high pressures. This rapid generation of high pressures of the released gas constitutes the explosion. 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. In fact, a substance which burns less rapidly (i.e. slow combustion) may actually evolve more total heat than an explosive which detonates rapidly (i.e. fast combustion). In the former, slow combustion converts more of the internal energy (i.e. chemical potential) of the burning substance into heat released to the surroundings, while in the latter, fast combustion (i.e. detonation) instead converts more internal energy into work on the surroundings (i.e. less internal energy converted into heat); c.f. heat and work (thermodynamics) are equivalent forms of energy. See Heat of Combustion for a more thorough treatment of this topic.
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. 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. In explosive technology only materials that are exothermic—that have a net liberation of heat—are of interest. 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."E