Yallourn brown coal particles were heated at rates in the order of 10(3) K s(-1) and pyrolyzed in two different reactors, a drop-tube reactor (DTR) and a Curie-point reactor (CPR). In DTR the vapor-phase secondary (extra-particle) reactions of volatiles occurred concurrently with the primary reactions within the particle, while in CPR the volatiles were swept out of the heating zone immediately after formed so that their secondary reactions were efficiently suppressed. The char yields for the pyrolyses in these two reactors were described by the same functions of temperature. This enabled to evaluate the decrease or increase in the yield of volatile products due to the secondary reactions that proceeded within the volatiles＇ residence for time shorter than 2 s. The evaluation was done by a parameter, Delta Y(i), defined as Delta Y(i) = Y(i)(DT)Y(i)(CP) where Y(i)(DT) and Y(i)(CP) are the yields of volatile product i for pyrolyses in DTR and CPR, respectively. Delta Y(tar) was found to decrease with increasing pyrolysis temperature and reached -19 mol-C per 100 mol-C in the coal, while it was negligible at temperatures lower than 873 K. Delta Y(tar) at 1173 K was much lower than that expected when Y(tar)(DT) was assumed to decrease only due to dealkylation to form gaseous hydrocarbons and deoxygenation to form carbon monoxide, -10 mol-C. The difference between the above two Delta Y(tar)s was explained well by the reaction of tar with steam (water formed by the primary pyrolysis) occurring above 1073 K and resulting in a considerable decrease in Delta Y(H2O) and the corresponding increase in Delta Y(CO) and Delta Y(H-2). The addition of steam to the carrier nitrogen gas further promoted the reduction of Y(tar)(DT) and Delta Y(tar) to 1 and - 23 mol, respectively. The reduction of Delta Y(tar) for the pyrolysis of acid washed coal was much less significant than that for the original coal. Thus the observed steam reforming of tar was found to be catalyzed by Fe, Ca and/or Mg species that were initially dispersed in the coal matrix as ion-exchanged cations. The addition of steam also increased the total conversion of carbon into volatiles at 1173 K from 44 to 56 mel, indicating the gasification of char by steam within an estimated residence time of coal/char particles. (C) 2000 Elsevier Science Ltd. All rights reserved.