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Fuel Cell Handbook (Seventh Edition)

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Fuel Cell Handbook (Seventh Edition) ( fuel-cell-handbook-seventh-edition )

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The purpose of this section is to describe the chemical and thermodynamic relations governing fuel cells and how operating conditions affect their performance. Understanding the impacts of variables such as temperature, pressure, and gas constituents on performance allows fuel cell developers to optimize their design of the modular units and it allows process engineers to maximize the performance of systems applications. A logical first step in understanding the operation of a fuel cell is to define its ideal performance. Once the ideal performance is determined, losses arising from non-ideal behavior can be calculated and then deducted from the ideal performance to describe the actual operation. 2.1 The Role of Gibbs Free Energy and Nernst Potential The maximum electrical work (Wel) obtainable in a fuel cell operating at constant temperature and pressure is given by the change in Gibbs free energy (∆G) of the electrochemical reaction: (2-1) Wel = ∆G = − nF E where n is the number of electrons participating in the reaction, F is Faraday's constant (96,487 coulombs/g-mole electron), and E is the ideal potential of the cell. The Gibbs free energy change is also given by the following state function: ∆G = ∆H − T∆S (2-2) where ∆H is the enthalpy change and ∆S is the entropy change. The total thermal energy available is ∆H. The available free energy is equal to the enthalpy change less the quantity T∆S which represents the unavailable energy resulting from the entropy change within the system. The amount of heat that is produced by a fuel cell operating reversibly is T∆S. Reactions in fuel cells that have negative entropy change generate heat (such as hydrogen oxidation), while those with positive entropy change (such as direct solid carbon oxidation) may extract heat from their 2-1 2. FUEL CELL PERFORMANCE

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