Experimental data on the thermal kinetics of organic peroxides

Abstract

The heat effects from the exothermic decomposition of concentrated organic peroxides have been investigated experimentally for three peroxy esters ( tert-butyl peroxy benzoate, tert-butyl peroxy 2-ethyl hexanoate and tert-butyl peroxy pivalate). Four different calorimetric instruments were used: adiabatic and isothermal storage tests, differential thermal analysis and the low pressure autoclave. The heat generation values which could be measured with these instruments vary from 10 −2 to 10 −4 W kg −1 (Watt per kilogram of peroxide). From the experimental data the following thermal kinetic information was obtained: total heat of decomposition, activation energy, heat generation factor, and the occurrence of induced decomposition. The storage/control temperatures and run-away data were calculated with these parameters. The calculated values agree with the experimental data for peroxides directly determined in the industrial 30-1 container. The advantage of the computation by means of parameters is that the thermal conditions of practical situations as met, e.g., in production units can also be calculated. These thermal conditions can hardly be determined by direct experiments.