Quantum Chemistry Calculation Study on Chain Reaction Mechanisms and Thermodynamic Characteristics of Coal Spontaneous Combustion at Low Temperatures

[Image: see text] The coal spontaneous combustion phenomenon seriously affects the safety production of coal mines. Aiming at the problem of complex coal molecular structure and incomplete reaction sequences at present, the mechanisms and thermodynamic parameters of coal spontaneous combustion chain reactions were explored by combining experimental detections and molecular simulations. First, the active groups on the surface of coal were obtained by Fourier transform infrared spectroscopy (FTIR), mainly including methyl (−CH(3)), methylene (−CH(2)), methyne (−CH), phenolic hydroxyl (−ArOH), alcohol hydroxyl (−ROH), carboxyl (−COOH), aldehyde (−CHO), and ether (−O−), and the coal molecular models containing functional groups and radicals were established. According to the charge density, electrostatic potential, and frontier orbital theories, the active sites and active bonds were obtained, and a series of reactions were given. The thermodynamic and structural parameters of each reaction were explored. In the chain initiation reaction stage, O(2) chemisorption and the self-reaction of radicals play a leading role. In this stage, heat gradually accumulates and various radicals begin to generate, where the intramolecular hydrogen transfer reaction of a peroxide radical (−C–O–O·) can produce the key hydroxyl radical (−O·). In the chain propagation reaction stage, O(2) and −O· continuously consume active sites to accelerate the reaction sequences and increase the temperature of coal, and index gases such as CO and CO(2) generate, causing the chain cycle reactions to gradually form. The chain termination reaction stage is the formation of stable compounds such as ethers, esters, and quinones, which can inhibit the development of chain reactions. The results can further explain the reaction mechanism of coal spontaneous combustion and provide references for the development and utilization of chemical inhibitors.