A series of coal-related model compounds (CRMCs) were analyzed with an atmospheric solids analysis probe/time of flight-mass spectrometer (ASAP/TOF-MS). Pyrene, anthracene, and phenanthrene were ionized to generate stable radical molecular cation (M+center dot) and protonated molecular cation ([M+H](+)). The ratio of [M+H](+) to M+center dot is positively related to the superdelocalizability of the condensed arenes (CAs), indicating that the CA ionizations rely on the intrinsic reactivities of the CA to a certain extent. Fragmental ions were formed via cleavage and/or rearrangement of [M+H](+)/M+center dot from bridged bond-containing CRMCs during ASAP/TOF-MS analysis. Their formation is related to drying gas temperature and the stabilities of fragmental species. Using ASAP/TOF-MS, a reaction mixture from di(1-naphthyl)methane hydrocracking was directly and rapidly analyzed, and as coal derivates succinic acid and polymethyl benzenepolycarboxylates were identified in the water-soluble portions from a coal and char oxidation within short time, respectively. The fact suggests that ASAP/TOF-MS could be used for real-time monitoring organic mixtures during the reactions of CRMCs and coal conversion. (C) 2014 Elsevier Ltd. All rights reserved.