CRITICAL-TEMPERATURES FOR THE THERMAL-EXPLOSION OF LIQUIDS

Following the example of Semenov's formulation concerning the critical condition for the thermal explosion of a gas, a relation describing the corresponding conditions for a liquid placed in an arbitrary container is presented. In consequence, it is shown that it is possible to calculate the critical temperature for thermal explosion (hereafter symbolized as T(c)) of a specific quantity of liquid placed in an arbitrary container by measuring experimentally the rate of heat generation of the sample as well as the rate of heat transfer of the container in temperature increments of 1.25 K. The T(c) values of nine liquid organic peroxides are then calculated in accordance with the above approach for the practical situation arising when the liquids are either in a Dewar vessel or in a 5- or a 10-L polyethylene container. For the Dewar vessel, the corresponding measured values were available, and they showed good agreement with the calculated ones. The results of this study suggest that the application of Semenov's self-ignition condition to the calculation of the T(c) value of a liquid is possible without stirring, provided that both the rate of heat generation and the rate of heat transfer are measured during the early stages of the self-heating process.