The atmospheric concentration of CO 2 has recently exceeded 400 (ppm) (up from 285 (ppm) in 1850), largely because of the burning of fossil fuels. Despite the growth of alternatives, these fuels will continue to play a major role in the energy sector for many decades. In accordance with international agreements, action to curtail C02 emissions is necessary, including carbon capture, reuse and storage. For this purpose, some of the leading technologies are oxy-combustion for power generation and partial oxidation for syngas production. Both require significant quantities of oxygen, whose production can impose considerable energy and economic penalties. Alternative technologies, such as intermediate-temperature ceramic membranes, operating under reactive conditions, promise to ameliorate both. Challenges include the long term stability of the material, reactor design and integration into the overall system. The goal of this thesis is to develop a framework for the thermochemical and electrochemical modeling of oxygen-conducting membranes that can be used in reactor design, based on experimental measurements and detailed surface exchange kinetics and charged species transport. La0. 9Ca0.1Fe03-[delta] (LCF) perovskite membranes have been used because of their long term stability in a reducing environment. Using experimental measurements, we examine the impact of hydrogen, carbon monoxide and methane on oxygen permeation and defect chemistry. While LCF exhibits low flux under non-reactive conditions, in the presence of fuel oxygen permeation increases by more than one order of magnitude. Our experiments confirm that hydrogen surface oxidation is faster compared to carbon monoxide. With methane, syngas production is slow and oxygen permeation is limited by surface exchange on the permeate side. Adding C02 to the fuel stream doubles the oxygen flux and increases syngas production by an order of magnitude. Our modeling analysis shows that different oxidation states of Fe participate in the electron transfer process. To account for this dependency, oxygen transport is modeled using a multi-step (fuel dependent) surface reaction mechanism that preserves thermodynamic consistency and conserves site balance and electroneutrality. Charged species diffusion is modeled using the dilute-limit Poisson-Nernst-Planck formulation that accounts for transport due to concentration gradient as well as electromigration. We use the experimental data to extract kinetic parameters of the model. We couple the aforementioned model with CFD of the gas-phase transport and thermochemistry in an effort to develop a numerical tool that allows the design of membrane reactors that exhibit high oxygen permeation and fuel conversion.;
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