Appendices: Chemistry of Pyrotechnics

Appendices (?) “Chemistry of Pyrotechnics”
John A. Conkling

Overview: This section exists to fill in a gap in knowledge. While I am aware of the dangers of becoming helplessly lost in out-of-scope research, I believe that at least a skin-deep understanding of the Chemistry of Pyrotechnics is required for two reasons. Firstly so that I am able to draw a relationship between thermodynamic properties and the chemical constituents of a “firework”. Secondly, and just as importantly, to facilitate communication between myself and individuals working in this field. That said, this section is no more than a summary of select parts of a basic piece of literature relating to the manufacture of pyrotechnics. As such it may seem somewhat scattered, as the flow of the book is broken up in a way which highlights parts which I felt were meaningful to the problem of presented by my dissertation. It is assumed the reader has a basic understanding of some simple chemical properties and terms.

Thermodynamics
Pyrotechnic explosions involve an oxidation-reduction reaction. In basic terms, the fuel in a firework will be the an electron “donor” (thus it is “reduced”), and some other compound will be an electron “acceptor” (thus is it “oxidized”). Of great importance are the following questions: • Is the reaction spontaneous? Will it actually occur if the oxidizer and fuel are mixed together? • What is the rate at which this reaction occurs? For a reaction to be spontaneous, it is said that the products of the reaction must be of a lower free energy state than the reactants. Free Energy is the amount of work this thermodynamic system can perform. This “free energy” G, has 2 constituent parts. Enthalpy (H), which may be considered the “internal energy” of the system, and Entropy, which can be considered the “randomness” of the system, or better still, how evenly this “internal energy” is distributed within the system. Therefore, for our reaction to be spontaneous ΔH must be a negative. As expected, the unit of Enthalpy, are calorie/mole, where 1 calorie = 4.184 Joule. Heat of Reaction It is possible to approximate the heat of a reaction by knowing what reactive products will be and using known values of “heats of formation.” A common Potassium Perchlorate mixture will produce 2.24 Calories/gram, about 9.37 Joule/gram. Rates of Chemical Reactions It was previously stated that for a reaction to be “spontaneous” ΔH must be a negative figure. However, even with large values of ΔH it will often be the case that reactions will not activate until an input of energy aptly named the “activation energy” is made.

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if 0. An immensely high figure.0024 moles of gas at a temperature of nearly 2000k. the temperature of the system rises.2 moles of permanent gas are produced per 100 grams of black powder. the lower the melting point of the oxidizer. However. For example. Pyrotechnic reactions will often produce solid residual material and. in K P = pressure.Appendices: Chemistry of Pyrotechnics As expected. R = some constant. V = volume occupied by gas. more importantly. This is no doubt critical in understanding the pressure effects that will be experienced by a structure. once this activation barrier is broken. Explosive effects in pyrotechnics will not occur if the material is not confined! 2 .0821 T = temperature.6 liters at atmospheric pressure! The volume occupied by gases can be approximated using the “ideal gas equation” V = nRTP-1 Where.1ml. the more reactive it will be. one Mole of water (18. we know that black powder burns to produce 50% hot gas products.2grams will produce 0. 0. one mole of water vapor occupies approximately 30.0g) occupies approximately 18ml. and 50% solid residue. continues to rise.2g of black powder where to be confined in a volume of 0. n = number of moles of gas. 1. the transition phases of the oxidizers is very important in the creation of a self propagating reaction. Carbon Dioxide and Carbon Monoxide. a volume of hot gaseous vapor. one can find the expected pressure within the containment vessel. It is further known that. Generally speaking. Note that the degree of confinement is massively important in the build up pressures. Gases and Expansion Products It is common knowledge that a gas will occupy more volume than a solid. Having a good understanding of these transition phases is critical to the research being carried out. Giving an example. States of Matter & Transitions In pyrotechnics. in atm The important implication of the above is that. in liters. depending on the containment of the explosive. and thus increases the overall rate of reaction exponentially. and knowing the products of a reaction. especially where expanding gases are concerned. these products being mostly Nitrogen. obviously rupturing the container. This gives an expected pressure of around 3941ATM. So the original 0.

Again. The reaction will provide heat. Function of Oxidizers Oxidizing agents in a pyrotechnic mixture will be oxygen-rich ionic solids which decompose at moderately high temperatures liberating oxygen in a gaseous form. good oxygen content (39.ClO. Since these types of reactions provide their own oxygen. Common Fuels & Oxidizers Common Oxidizers • Potassium Perchlorate: KClO4. further details would be out of the scope of this research. The decomposition of Potassium Nitrate is strongly endothermic.. light and noise. Importantly. Function of Fuels Fuels in pyrotechnic mixtures are good electron donors.. • Potassium Chlorate: KClO3. In fireworks it will often be mixed with fine powders of metals such as aluminum or magnesium to give a “photoflash” effect. Compounds such as this are basically the most intimate high-energy mixes that exist. Curiously about 70% of the solid fuel in a solid fuel rocket is NHClO. Lead Azide. light weight gas with a rapid burning rate. Contains 39. Very controversial. • Strontium Nitrate: [Sr(NO3)2]. Examples of these are Ammonium Nitrate. Pyrotechnic effects will generally “burn” rather than explode. a good fuel should produce a high volume of very hot. smoke. A relatively “recent” oxidizer to appear on the scene. hardly ever the only oxidizer in a mixture. also known as “saltpeter”.. The choice of oxidizer is obviously very important to the pyro-chemist. it should be known that most large accidents in firework manufacturing plants have been because of this material. So reactive that they should be worked only when wet.2% oxygen by weight. not the physical level. a white crystalline material. the desired effects will be produced. however it can be mixed to give a red flame reaction. By preparing mixtures of an oxidizer and a fuel. These compounds are explosive by nature. and this heat allows a chemist to produce any number of effects: colors. It is considered a good oxidizer for colored flame compositions. • Ammonium Perchlorate: NH. an inorganic salt which will readily react with most organic compounds. Trinitrotoluene (TNT) and Nitroglycerine.6%). it is important to note these fires cannot be suffocated. Easily ignitable. 3 .Appendices: Chemistry of Pyrotechnics Components of High-Energy Mixtures In nature it is rare to find compounds which have ready-oxidizable and ready-reducible components within the same molecule. one of the oldest solid oxidizers known. However further understanding is not required for the scope of this research. • Potassium Nitrate: KNO3. This intimacy is on the ionic level. so active metals should be used as fuels.

This produces “grains” which retain the original homogenous nature of the mix. 3.g. Granulation: To prevent segregation of the now homogenous material a binder is added to the mix. The more intimate the mixing. Preparing the Individual Components: Generally the oxidizers and fuels may have to be ground to the correct particle size and screened. the more likely we are to have accidental ignition. and then graded through a mesh. with magnesium (Mg) being a close second. 4. the better the end result. Glossary Pyrotechnic Initiator: Some chemical compound (e. 4 . This is always a high risk part of the process. Loading: The granulated powders are loaded into cardboard tubes or into pellets for later use. The large heat outputs are used to start reactions in less reactive pyrotechnic mixtures. Non-metals may also be used. The mixture is treated with an organic liquid such as alcohol. when the oxidizer and the fuel are brought together and mixed very thoroughly. so protection really is critical. You will find large quantities of the powder here. 2. Relevant Preparation Issues It will be a good exercise to breakdown the manufacturing operation for the purpose of research. Intimate mixing. Preparation of Compositions: A delicate part of the procedure. however. very popular is aluminum (Al). Thermite mixtures) which have reactions which are easy to initiate and are highly exothermic. This mixing should be done remotely.Appendices: Chemistry of Pyrotechnics • Barium Nitrate: [Ba(NO3)2]. generally used as part of a mixture for green flame reactions. 1. Common Fuels Fuels will often be finely graded metal powders. Equipment used to grind an oxidant should never be used to grind a fuel and vice versa.

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