Formation of radicals in coal pyrolysis examined by electron spin resonance

Electron spin resonance (ESR) spectroscopy is used to study materials with unpaired electrons, such as organic radicals and metal complexes. This method can also be used to follow radical reactions during pyrolysis of carbonaceous materials. However, the temperature dependence of ESR measurement should be considered. To enable reasonable comparisons, results measured at different temperatures must be converted. In this study, we investigated the behavior of free radicals in the process of coal pyrolysis using in situ and ex situ ESR. The ESR data were collected at both pyrolysis and room temperatures, and apparent differences were analyzed. The differences were diminished when our data were converted to the same measurement temperature level based on the Boltzmann distribution law. Furthermore, we investigated the effects of process conditions on the behavior of free radicals in the solid phase of coal. We found that temperature is the most important factor determining the formation and behavior of free radicals in the solid phase, followed by the residence time. Relatively active radicals were quenched by hydrogen-donor solvents to some degree, while stable radicals remained.