Oxygen gas electrodes

If the oxygen electrode were reversible, what change of e.m.f. would be expected when an oxygen gas electrode at 1 atm. pressure replaced (i) a hydrogen electrode at 1 atm., and (ii) a quinhydrone electrode, in a given cell at 25° ... 

The standard (oxidation) potential of the oxygen gas electrode is thus — 0.401 volt at 26 C. 

The following half-reaction takes place at the oxygen gas electrode 02(g) + 2H+(aq) -1- 2e = H20(l). If one uses the data of CRC Handbook, the standard electrode potential corresponding to this half-reaction at 100°C and 1 bar is... 

Some battery designs have a one-way valve for pressure rehef and operate on an oxygen cycle. In these systems the oxygen gas formed at the positive electrode is transported to the negative electrode where it reacts to reform water. Hydrogen evolution at the negative electrode is normally suppressed by this reaction. The extent to which this process occurs in these valve regulated lead —acid batteries is called the recombination-efficiency. These processes are reviewed in the Hterature (50—52). 

Another application is in tire oxidation of vapour mixtures in a chemical vapour transport reaction, the attempt being to coat materials with a tlrin layer of solid electrolyte. For example, a gas phase mixture consisting of the iodides of zirconium and yttrium is oxidized to form a thin layer of ytnia-stabilized zirconia on the surface of an electrode such as one of the lanthanum-snontium doped transition metal perovskites Lai j.Srj.M03 7, which can transmit oxygen as ions and electrons from an isolated volume of oxygen gas. 

If the circuit is broken after the e.m.f. has been applied, it will be observed that the reading on the voltmeter is at first fairly steady, and then decreases, more or less rapidly, to zero. The cell is now clearly behaving as a source of current, and is said to exert a back or counter or polarisation e.m.f., since the latter acts in a direction opposite to that of the applied e.m.f. This back e.m.f. arises from the accumulation of oxygen and hydrogen at the anode and cathode respectively two gas electrodes are consequently formed, and the potential difference between them opposes the applied e.m.f. When the primary current from the battery is shut off, the cell produces a moderately steady current until the gases at the electrodes are either used up or have diffused away the voltage then falls to zero. This back e.m.f. is present even when the current from the battery passes through the cell and accounts for the shape of the curve in Fig. 12.1. 

Indicator electrodes for anions may take the form of a gas electrode (e.g. oxygen electrode for OH- chlorine electrode for Cl-), but in many instances consist of an appropriate electrode of the second kind thus as shown in Section 15.1, the potential of a silver-silver chloride electrode is governed by the chloride-ion activity of the solution. Selective-ion electrodes are also available for many anions. 

Fig. 10-12. Anodic photoexcited current of oxidation of water mole cules to produce oxygen gas as a function of electrode potential of an n-type tungsten oxide electrode in an acidic solution X. = wave length of photons. [From Butler, 1977.]...

Mkaline Fuel Cell The electrolyte for NASA s space shnttle orbiter fuel cell is 35 percent potassinm hydroxide. The cell operates between 353 and 363 K (176 and I94°F) at 0.4 MPa (59 psia) on hydrogen and oxygen. The electrodes contain platinnm-palladinm and platinum-gold alloy powder catalysts bonded with polytetraflnoro-ethylene (PTFE) latex and snpported on gold-plated nickel screens for cnrrent collection and gas distribution. A variety of materials, inclnding asbestos and potassinm titanate, are used to form a micro-porous separator that retains the electrolyte between the electrodes. The cell structural materials, bipolar plates, and external housing are nsnally nickel-plated to resist corrosion. The complete orbiter fuel cell power plant is shown in Fig. 24-48. 

An improved electrochemical cell for in situ studies is presented in Figure 14.2. In this method a platinized Pt electrode located in the anode compartment serves as the reference electrode. This cell can be installed in a test station. Such a station can have facilities for temperature and pressure control, humidification of reactant gases (e.g., hydrogen and oxygen), gas flow rate measurement, and measurement of half- and... 

The electrodes and electrode protective coating of the oxygen sensor play a crucial role in determining the performance characteristics and durability (2). The electrodes used are the inner or air-reference electrode and the outer or exhaust gas electrode. The protective coating goes over the outer or exhaust electrode. While a complete discussion of the requirements and properties of the electrodes and electrode protective coating is beyond the scope of this paper, a brief description will be given. 

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