To further study the mechanism of coal self-heating, the reaction sequences and thermodynamic properties between sulfur-containing groups and oxygen during coal self-heating were analyzed. The benzyl mercaptan and diphenyl sulfide were selected as typical sulfur-containing structures existing in coal. Their structural parameters, frontier orbital characteristics, and thermodynamic parameters were analyzed through quantum chemistry calculation and their detailed reaction sequences with oxygen were proposed. The results indicate that the thiol structure in coal can easily react with oxygen at low temperatures and release large amounts of heat (146.70 kJ/mol) during coal self-heating, providing active free radicals and energy for subsequent chain reactions of coal spontaneous combustion. The oxidation reaction between the thioether structure and oxygen cannot occur at room temperature. With the accumulation of heat, thioether gradually becomes active and reacts with oxygen to form sulfoxide and release an enormous amount of heat (248.09 kJ/mol), which can be further oxidized to sulfone with an increase in temperature. The reaction models of thiol and thioether groups during coal self-heating were proposed, which involves eight main reaction sequences (R1~R8). It indicates that the reactions of thiol and thioether groups play crucial roles during the evolution of coal self-heating, with a slow oxidation stage at low temperatures and an accelerated oxidation stage at high temperatures. Key words: sulfur-containing groups, quantum chemistry calculation, reaction model, coal self-heating. Pour etudier plus en detail le mecanisme de combustion spontanee du charbon, nous avons analyse les sequences de reaction entre les groupes contenant du soufre et l'oxygene durant la combustion spontanee du charbon, ainsi que les proprietes thermodynamiques de ces reactions. Nous avons selectionne le benzylmercaptan et le sulfure de diphenyle comme structures typiques contenant du soufre presentes dans le charbon. Nous avons analyse, par des calculs de chimie quantique, les parametres structuraux et thermodynamiques de ces composes ainsi que les caracteristiques de leurs orbitales frontieres et nous avons propose des sequences detaillees de leur reaction avec l'oxygene. Les resultats indiquent que la structure du thiol dans le charbon peut facilement reagir avec l'oxygene a basse temperature et liberer de grandes quantites de chaleur (146,70 kJ/mol) au cours de la combustion spontanee du charbon, fournissant ainsi des radicaux libres actifs et de l'energie qui permettent a des reactions en chaine de produire ensuite dans le processus de combustion spontanee du charbon. La reaction d'oxydation entre la structure thioether et l'oxygene ne peut pas se produire a temperature ambiante. Avec l'accumulation de chaleur, le thioether devient progressivement actif et reagit avec l'oxygene pour former un sulfoxyde, liberant une enorme quantite de chaleur (248,09 kJ/mol). Ce sulfoxyde peut etre oxyde davantage en sulfone, produisant une augmentation de temperature. Nous avons propose des modeles pour les reactions des groupes thiol et thioether se produisant au cours de la combustion spontanee du charbon qui comportent huit sequences principales de reaction (R1~R8). Ces modeles indiquent que les reactions des groupes thiol et thioether jouent un role crucial au cours du processus de combustion du charbon, tant au stade d'oxydation lente a basse temperature qu'au stade d'oxydation accelere a des temperatures elevees. [Traduit par la Redaction] Mots-cles : groupes contenant du soufre, calcul de chimie quantique, modele de reaction, combustion spontanee du charbon., Introduction Coal self-heating seriously endangers coal mining, storage, and transportation. (1) Under certain conditions, the phenomenon of coal self-heating will be converted into coal self-ignition, which can cause huge safety [...]