The present work presents the design, assembly and experimental validation of a microcalorimetric device coupled to a volumetric adsorption setup applied to the characterisation of adsorbents for carbon dioxide (CO2) capture. Three adsorbents were evaluated for CO2 adsorption at 273 K in the pressure range of vacuum to 101 kPa. The data for CO2 on zeolite 13X agreed well with the available data reported in the literature, thus validating the device, which also provided reproducible results with an activated carbon sample. For the amine-modified zeolite, the differential enthalpy at lower coverage was increased by a factor of 1.7 as compared to the zeolite matrix. This points out to the potential of such technique to characterise heterogeneities introduced by amine impregnation. However, the adsorption uptake was decreased by factor of 2.7 at 101 kPa. This fact suggests that amino groups may be blocking some physisorption sites, leading to restricted chemisorption on the outer surface. Thus, the main novelty of this study is the simultaneous measurement of adsorption isotherms and respective differential enthalpy curves for amine-impregnated adsorbents, which may be considered a fingerprint of the modified surface chemistry. This work has been carried out in the framework of a cooperation project between three South American universities and is part of the effort to develop and fully characterise adsorbent materials intended for CO2 capture. (c) 2012 Canadian Society for Chemical Engineering