Our earlier study showed significant differences in average particle velocity between simulation and experimental results for devolatilizing biomass particles in an idealised entrained flow reactor [N. Guo et al., Fuel, 2020]. This indicates that the simulations do not accurately describe the physicochemical transformations and fluid dynamic processes during devolatilization. This article investigates the reasons for these discrepancies using time-resolved analyses of the experimental data and complementary modelling work. The experiments were conducted in a downdraft drop-tube furnace with optical access, which uses a fuel-rich flat flame (CH4[sbnd]O2[sbnd]CO2) to heat the particles. Gas flow was characterized using particle image velocimetry, equilibrium calculations and thermocouple measurements. High-speed images of devolatilizing Norway spruce (Picea Abies) particles were captured and analysed using time-resolved particle tracking velocimetry methods. The data were used to estimate the balance of forces and fuel conversion. Thrust and “rocket-like” motions were frequently observed, followed by quick entrainment in the gas flow. Rocketing particles were, on average, smaller, more spherical and converted faster than their non-rocketing counterparts. These differences in conversion behaviour could be captured by a particle-size dependent, 0-D devolatilization model, corrected for non-isothermal effects. The results from this investigation can provide a basis for future modelling and simulation work relevant for pulverized firing technologies. © 2021 The Author(s)