An approach is presented to accurately design emergency relief systems for even the most complex chemical reactions. Two examples illustrate how large differences in relief requirements can result if small, but important, aspects of the calorimetry data are overlooked. Although both simple and rigorous kinetic models may seem to predict calorimetry data reasonably well, these examples demonstrate the importance of well-designed experiments, optimization algorithms, rigorous kinetic modeling, correct physical properties, and dynamic simulations.

The first example shows how the inclusion of a subtle equilibrium reaction in the kinetic model will allow venting of an intermediate species, decreasing the reactant available for the highly exothermic irreversible reaction. The second example emphasizes the importance of a rigorous model for the decomposition of a large molecule where bond cleavage can occur between repetitive groups.

This example takes advantage of the tempering effect of intermediate decomposition products which are accounted forwith the rigorous model.