In this study, a mechanism for mercury chlorination in flue gases resulting from the combustion of pulverised coal has been presented. Arrhenius parameters of the gas-phase elementary reactions in the Hg-Cl sub-mechanism have been updated and are mainly based on recent experimental and quantum mechanical rate determinations. The mechanism is validated by comparison to accurate experimental data that is unbiased by Hg oxidation in the impinger solutions of aqueous chemistry methods. Solid-phase retention of Hg0 has been studied in parallel to char combustion; the heterogeneous model describes condensation of mercury on fly ash particles. The combined homogeneous- heterogeneous model predictions show comparable trends to those of power plant data. This approach aims to provide an improved prediction of mercury speciation from coal-fired power plants and to shed light on the chemical kinetic changes encountered during oxy-coal operation. © 2010 The Combustion Institute.