A systematic experimental study has been performed in order to investigate the effect of particle size and temperature on the devolatilization rate of large tyre rubber particles. Cylindrical tyre particles with diameters between 7.5 and 22 mm were devolatilised in a macro-TGA reactor, at temperatures between 490 and 840 degrees C in an inert atmosphere. The effect of particle size and surrounding temperature on the rate of devolatilization was observed to be significant, i.e. larger particle diameters and lower temperatures increased the devolatilization time. A detailed mathematical model for the devolatilization process including internal and external heat transfer, three parallel independent devolatilization reactions and reaction enthalpy effects has been developed and solved using an implicit finite difference method. Comparison of the model predictions with experimental data, reveals that the devolatilization process of large tyre rubber particles at temperatures above 490 degrees C can be considered to be controlled mainly by heat transfer and reaction kinetics. The model analysis further shows that exothermic devolatilization reaction enthalpy effects cannot be neglected in the prediction of the intra particle temperature rise. A sensitivity analysis of the model parameters, demonstrates that the specific heat capacity of the virgin fuel and the activation energies of the devolatilization reactions is the most important model parameters in the prediction of devolatilization times of large tyre rubber particles. (C) 2006 Elsevier Ltd. All rights reserved.