The sulfur-iodine (S-I) thermochemical water splitting cycle is one of the most studied cycles for hydrogen (H-2) production. S-I cycle consists of four sections: (1) acid production and separation and oxygen purification, (11) sulfuric acid concentration and decomposition, (111) hydroiodic acid (HI) concentration, and (IV) III decomposition and H-2 purification. Section II of the cycle is an endothermic reaction driven by the heat input from a high temperature source. Analysis of the S-I cycle in the past thirty years have been focused mostly on the utilization of nuclear power as, the high temperature heat source for the sulfuric acid decomposition step. Thermodynamic as well as kinetic considerations indicate that both the extent and rate of sulfuric acid decomposition can be improved at very high temperatures (in excess of 1000 degrees C) available only from solar concentrators. The beneficial effect of high temperature solar heat for decomposition of sulfuric acid in the S-I cycle is described in this paper. We used Aspen Technologies' HYSYS chemical process simulator (CPS) to develop flowsheets for sulfuric acid (H2SO4) decomposition that include all mass and heat balances. Based on the HYSYS analyses, two new process flowsheets were developed, These new sulfuric acid decomposition processes are simpler and more stable than previous processes and yield higher conversion efficiencies for the sulfuric acid decomposition and sulfur dioxide and oxygen formation. (c) 2004 Elsevier Ltd. All rights reserved.