Following a review of thermodynamic processes in a generalized fossil-fuelled power system, the theoretical efficiencies of systems based on the isothermal oxidation of methane are discussed. The fuel cell is introduced as a device that convertsthe change of Gibbs free energy (△G) in isothermal oxidation directly to electricity. Ideal efficiencies of fuel cell systems are presented.The Gibbs free energy change in isothermal oxidation of methane is 99 per cent of its lower heating value (LHV). However, direct electrochemical oxidation is not practical yet. Taking this and other factors into account the reversible electrical work from an internally reforming fuel cell could represent ~79 per cent of the lower heating value at 600℃, falling to 67 percent at 1000℃. With a bottoming heat engine the combined reversible work could be >80 per cent of LHV over this range. Adding such adevice as a topping element to a conventional heat engine based system seems a logical next step in the evolution of the efficient fossil-fuelled power plant.
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