A systematic approach to determination of the kinetics of the exothermic esterification of methanol and acetic anhydride by reaction calorimetry (RC) was addressed in this study. Arrhenius parameters were obtained from isothermal, adiabatic, and temperature-programmed methods. The activation energy, pre-exponential factor, and heat of reaction were determined to be 72.6 +/- 0.5 kJ mol(-1), (3.6 +/- 0.6) x 10(7) s(-1) mol(-1) dm(3), and 67.3 +/- 3.0 kJ mol(-1) respectively. Here, the adiabatic temperature rise of runaway reaction and the critical heat-transfer parameter were obtained using the Mettler RC1 AP01 reactor. A second-order reaction under the condition of excess acetic anhydride was successfully identified and used to simulate adiabatic runaway situations in scale-up quantity. Results in this study demonstrated that combining different calorimeters’ features with experimental techniques would create an effective technique capable of obtaining reliable results for both the Arrhenius parameters and thermal hazard assessment.