The time-dependent chemisorption of 2-chlorophenol on a fumed silica surface was studied in situ from 200 to 500 degrees C using a temperature-controlled dosing cell and FTIR absorption spectroscopy. 2-Chlorophenol was found to chemisorb at isolated and geminal surface hydroxyl sites. 2-Chlorophenol chemisorption and subsequent surface oxidation resulted in a mixture of chlorophenolate and partial oxidation products, such as formates and acetates. The rates of chemisorption were measured, and the activation energy of adsorption was found to be 15 +/- 4 kJ mol(-1) for a fast, initial reaction and 22 +/- 2 kJ mol(-1) for a slower reaction at higher surface coverage. This work was motivated by the observation that combustion-generated fly ash mediates the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) at temperatures between 250 and 450 degrees C. Although transition metals such as copper are known to catalyze or mediate this reaction, silica is the major component of fly ash and chemisorption at higher concentration surface sites of silica must have a significant impact on the surface-mediated PCDD/F formation on fly ash surfaces.