The catalytic steam gasification of coke from Athabasca bitumen was investigated by thermogravimetric analysis using K(2)CO(3) and Na(2)CO(3) as catalysts, both of which reduced the activation energy of the reaction considerably to 1.2 x 10(5) J mol (1) and 1.3 x 10(5) J mol (1), respectively, down from 2.1 x 10(5) J mol (1) for the uncatalyzed reaction. The reaction rates varied with the partial pressure of steam between 60 kPa and 85 kPa consistent with a Langmuir-Hinshelwood model, but a first order equation was also sufficient given the low partial pressures. The initial rate of gasification of the coke particles correlated linearly with the estimated external surface area of the particles, as expected from a surface reaction involving a nonporous solid. The initial reaction rate increased with increasing the catalyst loading up to 2.4 (mol potassium)/kg. A portion of the catalyst penetrated into the coke, as confirmed by secondary ion mass spectroscopy analysis, where it could not promote the reaction with steam. This result was consistent with a small increase observed in the reaction rate at low catalyst loading. The shrinking core model was successful in predicting the rates at higher conversions from the initial rate data, despite increases in BET surface area with conversion. (C) 2011 Elsevier Ltd. All rights reserved.