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Thermal decomposition of 25.4mm diameter dry wood spheres is studied both experimentally and theoretically. Wood spheres were pyrolyzed in a vertical tube furnace at temperatures ranging from 638K to 879K. Mass loss and temperatures of the sample were measured during pyrolysis. Center temperature measurements showed two distinct thermal events consisting of sequential endothermic and exothermic reactions. A numerical investigation of these endo/exothermic reactions using various pyrolysis kinetics models was conducted to determine the pyrolysis mechanism and the heats of the pyrolysis reactions. A comparison of the experimental and numerical results showed that (i) Contrary to the suggestions in the literature, the contributions of the secondary tar decomposition and lignin decomposition to the center temperature exothermic peak are small. (ii) Exothermic decomposition of the intermediate solid …