In Sweden, it is proposed that spent fuel should be encapsulated in sealed cylindrical canisters for disposal in a geologic repository. The canisters would consist of a thick ferrous inner container and a copper overpack. If mechanical failure of the copper overpack occurred, allowing water to enter, the ferrous inner container would corrode anaerobically and liberate hydrogen. The rate of hydrogen generation due to the anaerobic corrosion of steel in anoxic groundwater has been measured using barometric cells. The aim of the work presented in this paper was to measure the redox potential, Eh and pH in the presence of anaerobically corroding steel, in a barometric cell. Two specially designed barometric cells were constructed. They were equipped with a silver chloride or calomel reference electrode, a gold Eh electrode, a glass electrode, and a steel electrode. The electrodes were allowed to stabilize in anoxic artificial groundwater and then a mass of pickled steel wire was introduced into the test cell. As the wires were added, the redox potential rapidly became more negative due to the rapid consumption of the residual oxygen. The corrosion potential of the steel was stable and a slow drift in pH was observed. The results are compared with the results of geochemical modelling. Extension of the work to investigate the electrochemical parameters in the presence of dissolved uranium species is discussed.