The heat generated from the reactions of oxygen-containing functional groups in coal has been studied using organic chemistry and quantum chemistry analysis methods. Structural models of the oxygen containing functional groups in coal were established and used to analyze the reactions of these groups during spontaneous combustion. The Gibbs free energy and enthalpy changes associated with these reactions were determined using quantum mechanical analysis, and the results indicated that the dehydration and dehydrogenation reactions of the hydroxyl groups in coal were only mildly exothermic, whereas reactions involving the oxidation of the carbonyl groups were much more exothermic. In contrast, reactions resulting in the generation of carbon monoxide were endothermic. By comparing the heat release characteristics of the reactions of the oxygen-containing functional groups with the levels of oxygen consumption and gas production, as well as temperature profiles of the reactions, it was concluded that the decomposition of oxygen-containing functional groups is critical to the production of heat during the initial stages of the spontaneous combustion of coal and that oxidation does not occur during this period. These results also explain why the temperature of coal rises slowly during the initial stages of its spontaneous combustion. (C) 2017 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.