A detailed investigation of the role of self-heating in the spontaneous ignition of gaseous diethyl peroxide has been made. Special emphasis has been given to quantitative aspects and, in particular, to the direct measurement of the temperature in the reacting gas. Entry times for reactants are accurately controlled by an electromagnetic valve. Temperature-position profiles are mapped from the moment of admission to within milliseconds of explosion. The results establish beyond doubt the thermal character of this explosion and also afford new information about the limitations of the generally accepted standard techniques. In sub-critical conditions around 190°C, a symmetrical (parabolic) temperature distribution is established within 0.2 sec after entry. Within the limits of experimental error, the shape and size of the profiles are in full agreement with the predictions of thermal explosion theory. The profile gradually decays as the peroxide is consumed. In super-critical conditions, accurate temperature profiles are more difficult to obtain, since the temperature increases very swiftly towards the onset of ignition; this necessitates very strict control of the initial conditions. The temperature profiles are again found to be parabolic, even at the very instant of explosion. The effect of inert diluents on the critical conditions for ignition have been examined in terms of the measured thermal conductivities of the mixtures. Qualitatively, there is the expected correlation between critical pressure and thermal conductivity, but the quantitative predictions are not exact. By systematically studying the temperature effects accompanying the entry of a wide variety (twenty) of inert gases, their origins have been identified. They arise from dynamic heating, inescapable on rapid entry to an evacuated vessel, and potentially of considerable size (over 200°C). These effects can be reduced in intensity but not altogether avoided and there can be little doubt that many previous investigations of pressure-temperature limits have suffered from them.
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