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Chapter 1. Introduction 7 partial pressures could be included. It is important to note that the equilibrium composition becomes more complicated due to interactions between the gasses via the water-gas shift reaction (CO + H2O CO2 + H2). (1.1) (1.2) is the reversible potential at the operating temperature, which is defined by the Gibbs free energy of the reaction (in this case the net cell reaction H2O H2 + 1⁄2 O2). is a function of temperature as shown in Figure 3-4; =1.23 V at 25 °C and =0.96 V at 850 °C. is the ideal gas constant, is the operating temperature, n is the number of electrons transferred per mole product H2 or CO (n = 2 for these reactions, see Figure 1-2 where 2 moles of product are produced per 4 electrons), is Faraday’s number, and pH2 and pH2O are the equilibrium gas partial pressures at the negative electrode and pO2 is the oxygen partial pressure at the positive electrode. The electrodes are referred to as ―negative‖ and ―positive‖ electrodesii because it has not yet been defined which mode the cell will be operated in, fuel cell or electrolysis. In electrolysis, the negative electrode is the cathode because it is where electrochemical reduction is occurring and the positive electrode is the anode where oxidation is occurring. In fuel cell mode, the negative and positive electrodes are named oppositely, as the ―anode‖ and ―cathode‖ respectively. Another useful thermodynamic property of electrolysis cells is the thermoneutral voltage, as defined in equation (1.3). (1.3) For the cell reactions shown in Figure 1-2 (H2O H2 + 1⁄2 O2 and CO2 CO + 1⁄2 O2) which are the main focus of this thesis, . To operate below , heat must be supplied to the cell from an external source because the cell is self-cooling. Operating above results in heat production from the cell, which arises from the ohmic ―Joule‖ heating in the cell, and the cell must be cooled. Note, however, that there are some possible reactions, such as CO2 C + O2, for which has an opposite sign, and so . In that case, any applied electrolysis potential would produce heat. ii based on their electrical terminal connections to either the power supply or electrical load; see Figure 1-2.PDF Image | Electrolysis of CO2 and H2O
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