Thermolysis mechanisms. Evidence for an alternative pathway for radical migration in diffusionally constrained environments

In this paper, the authors present the first study of thermolysis of silica surfaces containing two covalently anchored model compounds (Si-O-Caryl linkages). The results provide evidence that under appropriate conditions, although mass transport is prohibited on the surface, radical centers can be relayed across the surface by a series of rapid hydrogen-transfer reactions. This novel discovery implies that diffusional limitations for reactive intermediates in coal may also be overcome by similar processes.