The paper presents experimental data of catalytic steam gasification of brown coal containing aqua-iron species, and the chemical mechanism(s) at a molecular level. Experimental techniques provided weight loss from catalysed reaction of char with steam of 17 wt% at 800 degrees C and 40 wt% at 900 degrees C, over 15 min, on a dry ash free basis (daf). Inorganic and organic oxygen, identified using XPS in the char samples, was derived from reactions with steam. High yields of H-2 resulted from catalysed reactions between char and steam. Semi-empirical (SE) quantum molecular modelling using MOPAC, of reaction routes for high temperature pyrolysis and steam gasification, provided results consistent with experimental data for weight loss, iron species, and the distribution of inorganic and organic oxygen in char samples after reaction with steam. The catalysis mechanism(s) that have been examined are considered to be a hybrid of organometallic and heterogeneous chemistry, involving iron hydride species that precede H-2 formation; oxygen insertion into [Fe-C-] to form [Fe-O-C-] followed by elimination of CO, creating another [Fe-C] site to continue the catalytic cycle. SE modelling indicates concerted reactions were more energetically favoured. Initial results from molecular dynamics (MD) show a higher concentration of H2O molecules about the active site [Fe-C]. (C) 2011 Elsevier Ltd. All rights reserved.