Loss of temperature control is one of the major reasons that can lead to runaway reaction. This occurrence is commonly named thermal runway. The aim of this paper is the application of thermal runaway criteria in order to predict the onset of runaway phenomena and define the range of stability related to operating conditions in the reactor, with specific reference to the esterification of acetic anhydride and methanol catalysed by sulphuric acid tested in isoperibolic conditions. The isoperibolic calorimeter has also been used to obtain thermodynamic, kinetic and physical chemistry data necessary to develop a model for the reaction. Some runaway criteria applied in this work require a model for the process, so a model for the analyzed system been developed. Because of the modest reaction enthalpy and low activation energy this reacting system provide a severe test to the runaway criteria. In this work, various runaway criteria have been applied to the experimental and simulated data and the results obtained have been compared. (C) 2011 Elsevier Ltd. All rights reserved.