Rocket Engine - Chemistry

Chemistry

Rocket propellants require a high specific energy (energy per unit mass), because ideally all the reaction energy appears as kinetic energy of the exhaust gases, and exhaust velocity is the single most important performance parameter of an engine, on which vehicle performance depends.

Aside from inevitable losses and imperfections in the engine, incomplete combustion, etc., after specific reaction energy, the main theoretical limit reducing the exhaust velocity obtained is that, according to the laws of thermodynamics, a fraction of the chemical energy may go into rotation of the exhaust molecules, where it is unavailable for producing thrust. Monatomic gases like helium have only three degrees of freedom, corresponding to the three dimensions of space, {x,y,z}, and only such spherically symmetric molecules escape this kind of loss. A diatomic molecule like H₂ can rotate about either of the two axes perpendicular to the one joining the two atoms, and as the equipartition law of statistical mechanics demands that the available thermal energy be divided equally among the degrees of freedom, for such a gas in thermal equilibrium 3/5 of the energy can go into unidirectional motion, and 2/5 into rotation. A triatomic molecule like water has six degrees of freedom, so the energy is divided equally among rotational and translational degrees of freedom. For most chemical reactions the latter situation is the case. This issue is traditionally described in terms of the ratio, gamma, of the specific heat of the gas at constant volume to that at constant pressure. The rotational energy loss is largely recovered in practice if the expansion nozzle is large enough to allow the gases to expand and cool sufficiently, the function of the nozzle being to convert the random thermal motions of the molecules in the combustion chamber into the unidirectional translation that produces thrust. As long as the exhaust gas remains in equilibrium as it expands, the initial rotational energy will be largely returned to translation in the nozzle.

Although the specific reaction energy per unit mass of reactants is key, low mean molecular weight in the reaction products is also important in practice in determining exhaust velocity. This is because the high gas temperatures in rocket engines pose serious problems for the engineering of survivable motors. Because temperature is proportional to the mean energy per molecule, a given amount of energy distributed among more molecules of lower mass permits a higher exhaust velocity at a given temperature. This means low atomic mass elements are favoured. Liquid hydrogen (LH2) and oxygen (LOX, or LO2), are the most effective propellants in terms of exhaust velocity that have been widely used to date, though a few exotic combinations involving boron or liquid ozone are potentially somewhat better in theory if various practical problems could be solved.

It is important to note in computing the specific reaction energy, that the entire mass of the propellants, including both fuel and oxidizer, must be included. The fact that air-breathing engines are typically able to obtain oxygen "for free" without having to carry it along, accounts for one factor of why air-breathing engines are very much more propellant-mass efficient, and one reason that rocket engines are far less suitable for most ordinary terrestrial applications. Fuels for automobile or turbojet engines, utilize atmospheric oxygen and so have a much better effective energy output per unit mass of propellant that must be carried, but are similar per unit mass of fuel.

Computer programs that predict the performance of propellants in rocket engines are available.