A two-step thermochemical cycle for solar production of hydrogen from water has been developed and investigated. It is based on metal oxide redox pair systems, which can split water molecules by abstracting oxygen atoms and reversibly incorporating them into their lattice. After successful experimental demonstration of several cycles of alternating hydrogen and oxygen production, the present work describes a thermodynamic study aiming at the improvement of process conditions and at the evaluation of the theoretical potential of the process. In order to evaluate the maximum hydrogen production potential of a coating material, theoretical considerations based on thermodynamic laws and properties are useful and faster than actual tests. Through thermodynamic calculations it is possible to predict the theoretical maximum output of H-2 from a specific redox-material under certain conditions. Calculations were focussed on the two mixed iron oxides nickel-iron-oxide and zinc-iron-oxide. In the simulation the amount of oxygen in the redox-material is calculated before and after the water-splitting step on the basis of laws of thermodynamics and available material properties for the chosen mixed iron oxides. For the simulation the commercial Software FactSage and available databases for the required material properties were used. The analysis showed that a maximum hydrogen yield is achieved if the reduction temperature is raised to the limits of the operation range, if the temperature for the water splitting is lowered below 800 degrees C and if the partial pressure of oxygen during reduction is decreased to the lower limits or the operational range. The predicted effects of reduction temperature and partial pressure of oxygen could be confirmed in experimental studies. The increased hydrogen yield at lower splitting temperatures of about 800 degrees C could not be confirmed in experimental results, where a higher splitting temperature led to a higher hydrogen yield. As a consequence it can be stated that kinetics must play an important role especially in the splitting step. Copyright (C) 2009 John Wiley & Sons, Ltd.