Exothermic reaction processing must be concerned with potential consequence
s when heat released by the reaction exceeds that removed by the reactor co
olant,system, a situation known commonly as a runaway reaction. We have inv
estigated a complicated reaction process in which two exotherms can occur -
the process of making the desired product, o-nitroaniline (o-NA), from amm
onia and o-chloronitrobenzene (T Onset around 140 degrees C), and the decom
position of the product, o-NA (T Onset around 225 degreesC. A severe indust
rial loss occurred in 1971 at a plant-producing o-nitroaniline, an incident
that has been the subject of several AlChE loss prevention presentations a
nd papers. In this article, we take a closer look at the chemistry, involve
d, and the ability, to use thermo-kinetic analyses to understand the reacti
ons involved, and how these influenced the accident that occurred. Further,
we present the progress we've made towards predictive models for the kinet
ics and the pressure-time data. Several useful generalizations have evolved
. First, is the need to include experiments that use stoichiometric mixture
s when assessing exothermic reactions. Second, is the need to understand th
e role of reaction intermediates, and how they may influence the operation
of the plant.