Improved kinetic model for water splitting thermochemical cycles using Nickel Ferrite

•Water splitting thermochemical cycles with increased duration over a Ni-ferrite.•A new extended model for the water splitting and thermal reduction reactions.•Two oxygen storage regions of the redox material are considered.•Inclusion of two state variables instead of one has an effect on reaction dynamics.•The model explains the dynamics of the cycles towards a periodic steady state.

In a previous work of the authors (AIChE Journal 2013; 59(4): 1213-1225) on the characterization of the performance of redox material compositions during two-step thermochemical splitting of water, it was observed that fitting of the obtained hydrogen and oxygen concentration profiles with a reaction model based on simple first order reaction rates could describe adequately only the first part of the evolution curves. This suggested that more complicated reaction models taking into account the structure of the redox material are needed to describe the whole extent of the experimental data. Based on the above, a minimum set of experiments for water splitting thermochemical cycles over a Nickel-ferrite was deigned and performed involving an increased duration of the reaction steps. A new extended model was derived for the water splitting and thermal reduction reactions, which considers two oxygen storage regions of the redox material communicating to each other by a solid state diffusion mechanism. The inclusion of two state variables instead of one has a significant effect on the reaction dynamics and renders the model capable to explain the dynamics of the convergence of the thermochemical cycles to a periodic steady state, observed experimentally in the previous work.