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Solvent extraction of coals has been practiced extensively for various purposes including the determination of coal structure. It is generally assumed that the extraction is mainly a physical process involving little change in covalent bonds. But different opinions were reported. This work studies the behavior of radicals during extraction of 3 low rank bituminous coals using 5 solvents, including hexane, toluene, tetrahydrofuran (THF), 1,2,3,4-tetrahydronaphthalene (THN), and N -methyl-2-pyrrolidinone (NMP), using electron spin resonance (ESR). The extractions are carried out at temperatures from the ambient temperature to temperatures somewhat higher than the boiling points of the solvents, as well as under ultrasound. It is found that the radical concentration of the coals changes during the extraction, and the change is influenced by temperature and varies with the solvent. The decrease in radical concentration in most solvents at temperatures lower than their boiling points is attribute to coupling of free radicals dissolved from the coals, while the increase in radical concentration at high temperatures and in NMP is attributed to the cleavage of weak bonds in coals by the solvents. [ABSTRACT FROM AUTHOR]