Static-Bomb Combustion Calorimetry in Oxygen

Static-bomb combustion calorimetry is particularly suited to obtaining enthalpies of combustion and formation of solid and liquid compounds containing only the elements C, H, O, and N. The origins of the method can be traced back to the work of Berthelot in the late nineteenth century [18,19]. 

Most static-bomb calorimeters used are of the isoperibol type, such as the one in figure 7.1. Here, the bomb A is a pressure vessel of 300 cm3 internal volume. Combustion bombs are usually made of stainless steel and frequently have an internal platinum lining to prevent corrosion. In a typical high-precision experiment, the platinum ignition wire B connects the two electrodes C, which are affixed to the bomb head. A cotton thread fuse D (other materials such as polyethene are also used), of known energy of combustion, is weighed to a precision of 10-5 — 10-6 g and tied to the platinum wire. A pellet E of the compound 

In the bomb process, reactants at the initial pressure pi and temperature 7 are converted to products at the final pressure pf and temperature Tf. The primary goal of a combustion calorimetric experiment, however, is to obtain the change of internal energy, Ac//°(7r), associated with the reaction under study, with all reactants and products in their standard states pi = pf = O.IMPa) and under isothermal conditions at a reference temperature 7r (usually 298.15 K). Once AC//°(298.15K) is known, it is possible to derive the standard enthalpy of combustion, AC77°(298.15K), and subsequently calculate the standard enthalpy of formation of the compound of interest from the known standard enthalpies of formation of the products and other reactants. 

Note that in addition to the main reaction, the bomb process includes contributions from ignition and all side reactions. These contributions have to be included in the calculation of the energy change associated with the main reaction. Two side reactions normally considered are the combustion of the cotton fuse and the formation of nitric acid from the oxidation of traces of atmospheric N2 that remain inside the bomb even after purging. 

As mentioned, the addition of a small amount of water to the bomb ensures that the vapor phase remains saturated throughout the experiment, so that liquid water is produced in the combustion reaction. It also ensures that the mixture of nitric oxides formed by the oxidation of the N2 will be converted to NOjT(aq), which is simple to determine. 

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