Decomposition reactions of liquids and solids can be observed by the heat development using microcalorimetric methods. By determination of the released heat flow for heating up a sample, it is possible to get details to answer safety relevant questions. For reactions nth order the overall activation energy and the accompanying frequency factor can be determined, provided that the heat release is determined by the rate of a single reaction step. Researches have been carried out whether these parameters are useable for safety technical specifications. Autocatalytic affected decomposition reactions are connected with special problems. This affects the experimental examination or interpretation of results, and also the precise identification of beginning decomposition reactions in technical reactors. The application of microcalorimetric measurements on decomposition reactions is described and associated problems are pointed out. The conclusions from thermoanalysis data alone are not sufficient in the final consequence for safety technical assessments. (c) 2005 Elsevier B.V. All rights reserved.