A mathematical model is developed to examine the sensitivity of the breakthrough of adsorption beds to system parameters. As the process model is integrated a single time, sensitivities are simultaneously calculated. The impact of mass and energy transfer effects and adsorbent layer thicknesses are determined by calculating the derivatives of the outlet concentration and outlet temperature. Several examples are considered. To establish a basis, the breakthrough of single beds is considered first. The adsorption of hexane on BPL activated carbon is contrasted with the adsorption of nitrogen on carbon molecular sieve, and combined mass and energy effects are considered by studying the adsorption of nitrogen on BPL activated carbon. The sensitivity data are then applied to determine the optimum bed layering of a two-layer, two-bed PSA system. The solution method presented can be adapted for the sensitivity analysis and subsequent optimization of a large number of adsorption systems. (C) 2008 Elsevier Ltd. All rights reserved.