A method to characterize the surface sites of catalysts in their active state by adsorption microcalorimetry was developed. A calorimeter cell was used as a flow-type reactor, and the skeletal isomerization of n-butane (1kPa) at 378K and atmospheric pressure proceeded at comparable rates and with the same states of induction period, maximum and deactivation phase as in a tubular reactor. The reaction was run for selected times on stream and after the removal of weakly adsorbed species, n-butane or isobutane were adsorbed at 313K. The surface of activated sulfated zirconia was characterized by at least two different sites for n-butane adsorption, a small group of sites (about 20μmolg −1 ) that yielded heats of 50–60kJmol −1 and sites that were populated at higher pressures (above about 5hPa n-butane) and yielded heats of about 40kJmol −1 . The strongly interacting sites disappear during the induction period and are proposed to be the sites where the isomerization reaction is initiated.