Cell voltages

2 Operation with Constant Cell Current (Calvanostatic Operation) 

Constant current electrolysis is an easy way to operate an electrochemical cell. Usually, it is also applied in industrial scale electrolysis. For laboratory scale experiments, inexpensive power supplies for constant current operation are available (also a potentiostat normally can work in galvanostatic operation). The transferred charge can be calculated directly by multiplication of cell current and time (no integration is needed). 

The electrode potentials (exactly the overvoltages) are dependant on the current density. Thus, using the galvanostatic operation mode, optimal results are attained only if a well-defined current density can be chosen with a clear difference between desired and undesired reactions, as in Fig. 1. This precondition is favored 

For batch operation (see Sect. 2.3.4), the limiting current density is going to zero for increasing degree of conversion (see reactant 1 in Fig. 1). Here, the galvanostatic operation may only be acceptable if exclusively unproblematic side reactions occur, such as water electrolysis as solvent decomposition. In all other cases, better results can be expected using the potentiostatic operation (see next section). 

In some problematic cases, there will be no obvious limits available for the choice of the current density in galvanostatic operation. Concurrent reactions take place, resulting in a poor selectivity. But here the potentiostatic operation also cannot demonstrate its advantages, and probably the simpler galvanostatic operation may be applied. To find relatively suitable operation conditions, an experimental optimization of the current density should be carried out, perhaps including parameters 

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In fact, some care is needed with regard to this type of concentration cell, since the assumption implicit in the derivation of A2.4.126 that the potential in the solution is constant between the two electrodes, caimot be entirely correct. At the phase boundary between the two solutions, which is here a semi-pemieable membrane pemiitting the passage of water molecules but not ions between the two solutions, there will be a potential jump. This so-called liquid-junction potential will increase or decrease the measured EMF of the cell depending on its sign. Potential jumps at liquid-liquid junctions are in general rather small compared to nomial cell voltages, and can be minimized fiirther by suitable experimental modifications to the cell. 

Table 8. Components of Chlor—Alkali Cell Voltages...

Ohmic Drops. Another irreversible contribution to the measured cell voltage is the ohmic or JR drop across the electrolyte, separator, and cell hardware. The JR drop across the hardware can be estimated from Ohm s law and the relationship... 

The components of the diaphragm, membrane, and mercury cell voltages presented ia Table 8 show that, although the major component of the cell voltage is the term, ohmic drops also contribute to the irreversible energy losses duting the operation of the cells. 

However, the iadustry s popular terminology is the energy consumption expressed ia terms of kilowatt hours per ton of (Pq[) oi of NaOH An estimate of this value requires a knowledge of cell voltage, current efficiency, and the efficiency of the rectifier used to convert a-c power to d-c. The energy consumption for producing a ton of is... 

Westinghouse Electric Corp. initiated a program to develop air-cooled PAFC stacks, containing cooling plates at six-ceU intervals. Full size 100-kW stacks (468 cells, 0.12-m electrode area) were built, and a module containing four of these stacks was tested. An air-cooled stack operated at 0.480 MPa yielded a cell voltage of 0.7 V at 267 m A /cm (187 mW/cm ). Demonstration of this technology is plarmed for a site in Norway. 

The Japanese Government initiated a program in 1992 to promote the development of PFFCs for both portable and stationary appHcations. The goal is to demonstrate a 1-kW module having a power density of 0.3 W/cm at a cell voltage greater than 0.75 V by 1995. A few research projects are under way in Japan. 

Eig. 6. Comparison of current density and cell voltage characteristics of the electrolysis systems where lines A and B represent steam electrolysis and the use of SPE, respectively, the conventional KOH water electrolysis, and, 2ero-gap cell geometry employing 40% KOH, at 120—140°C. 

A layer of oil or paraffin wax is floated on top of the electrolyte to minimize heat and water losses. Cell voltages vary between 1.8 and 2.5 V. In one mode of operation (83) the electrolyte is circulated through the cell at a rate of about 3% of the total volume per minute with the solution usually being introduced at the bottom of the cell. The electrolyte is replenished every one to two hours by drawing off about 10—20% of the total electrolyte volume for treatment with MnCO or MnO, followed by filtration, and is then returned to the electrolysis cycle. 

The anode and cathode chambers are separated by a cation-permeable fluoropolymer-based membrane (see Membrane technology). Platinum-electroplated high surface area electrodes sold under the trade name of TySAR (Olin) (85,86) were used as the anode the cathode was formed from a two-layer HasteUoy (Cabot Corp.) C-22-mesh stmcture having a fine outer 60-mesh stmcture supported on a coarse inner mesh layer welded to a backplate. The cell voltage was 3.3 V at 8 kA/m, resulting ia a 40% current efficiency. The steady-state perchloric acid concentration was about 21% by weight. 

The individual components of smelting-cell voltage and energy are shown in Figure 5. The electrical energy required to decompose aluinina Fj = 2.233 V in a cryoHte bath 65% saturated with alumina is given by... 

An electrorefining plant may operate with either an acid or an alkaline bath. The acid bath contains stannous sulfate, cresolsulfonic or phenolsulfonic acids (to retard the oxidation of the stannous tin in the solution), and free sulfuric acid with P-naphthol and glue as addition agents to prevent tree-like deposits on the cathode which may short-circuit the cells. The concentration of these addition agents must be carefliUy controlled. The acid electrolyte operates at room temperature with a current density of ca 86—108 A/m, cell voltage of 0.3 V, and an efficiency of 85%. Anodes (95 wt % tin) have a life of 21 d, whereas the cathode sheets have a life of 7 d. Anode slimes may be a problem if the lead content of the anodes is high the anodes are removed at frequent intervals and scmbbed with revolving bmshes to remove the slime (7). 

The more negative the value of AG, the more energy or useful work can be obtained from the reaction. Reversible processes yield the maximum output. In irreversible processes, a portion of the useful work or energy is used to help carry out the reaction. The cell voltage or emf also has a sign and direction. Spontaneous processes have a positive emf the reaction, written in a reversible fashion, goes in the forward direction. 

System/Reaction Cell voltage, V Energy content, Wh/kg... 

Because the nickel—iron cell system has a low cell voltage and high cost compared to those of the lead—acid battery, lead—acid became the dorninant automotive and industrial battery system except for heavy-duty appHcations. Renewed interest in the nickel—iron and nickel—cadmium systems, for electric vehicles started in the mid-1980s using other cell geometries. 

Discharging to this lower cell voltage usually results ia shorter cycle life. Enough excess iron should be provided ia the cell design to avoid this problem. Active iron ia the metallic state is slowly attacked by the alkaline electrolyte according to... 

In the sodium—sulfur storage battery above 300°C, the overall chemical reaction occurs between molten sodium metal and sulfur to form sodium polysulfide. The cell voltage is related to the activity of the sodium ( Aia) sulfide relative to its activity in the metal. 

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