Principles of Electrochemical Cell Operation

All flashlight batteries, button batteries, compact rechargeable batteries and vehicle storage batteries operate under the same basic principles. An electrochemical cell is constructed of two chemicals with different electron-attracting capabilities. Called an electrochemical couple, these two chemicals, itntncrscd in an electrolyte (material that carries the flow of energy between electrodes), are connected to each other through an external circuit. 

In this chapter, we ll look at the principles involved in the design and operation of electrochemical cells. In addition, we ll explore some important connections between electrochemistry and thermodynamics. 

Generation of photocurrent at the semiconductor/electrolyte interface upon its illumination makes it possible to carry out photoelectrochemical reactions which can be used either for chemical fuel production, or purification of waters. Principles of operation of electrochemical cells with semiconductor electrodes for solar energy conversion to electrical and chemical energy are formulated. Most efficient cells for electricity and hydrogen production are surveyed. Certain processes for photo-destruction of pollutants, recovery of metals, etc. with making use of semiconductor dispersions are briefly discussed. 

The industrial economy depends heavily on electrochemical processes. Electrochemical systems have inherent advantages such as ambient temperature operation, easily controlled reaction rates, and minimal environmental impact (qv). Electrosynthesis is used in a number of commercial processes. Batteries and fuel cells, used for the interconversion and storage of energy, are not limited by the Carnot efficiency of thermal devices. Corrosion, another electrochemical process, is estimated to cost hundreds of millions of dollars aimuaUy in the United States alone (see Corrosion and CORROSION control). Electrochemical systems can be described using the fundamental principles of thermodynamics, kinetics, and transport phenomena. 

Electric current, 78 Electric dipoles, see Dipoles Electric discharge, 239 Electric force, 76, 77 Electricity, fundamental unit, 241 Electrochemical cell chemistry of, 199 and Le Chatelier s Principle. 214 operation, 206 standard half cell, 21C Electrodes, 207 Electrolysis, 220, 221 apparatus, 40 cells, 238 of water, 40, 115 Electrolytes, 169, 179 strong, 180 weak,180... 

Special electrochemical sensors that operate on the principle of the voltammetric cell have been developed. The area of chemically modified solid electrodes (CMSEs) is a rapidly growing field, giving rise to the development of new electroanalytical methods with increased selectivity and sensitivity for the determination of a wide variety of analytes [490]. CMSEs are typically used to preconcentrate the electroactive target analyte(s) from the solution. The use of polymer coatings showing electrocatalytic activity to modify electrode surfaces constitutes an interesting approach to fabricate sensing surfaces useful for analytical purposes [491]. 

A DMFC is an electrochemical cell that generates electricity based on the oxidation of methanol and reduction of oxygen. Figure 37 illustrates the cell construction and operating principle of a DMFC. An... 

DMFCs and direct ethanol fuel cells (DEFCs) are based on the proton exchange membrane fuel cell (PEM FC), where hydrogen is replaced by the alcohol, so that both the principles of the PEMFC and the direct alcohol fuel cell (DAFC), in which the alcohol reacts directly at the fuel cell anode without any reforming process, will be discussed in this chapter. Then, because of the low operating temperatures of these fuel cells working in an acidic environment (due to the protonic membrane), the activation of the alcohol oxidation by convenient catalysts (usually containing platinum) is still a severe problem, which will be discussed in the context of electrocatalysis. One way to overcome this problem is to use an alkaline membrane (conducting, e.g., by the hydroxyl anion, OH ), in which medium the kinetics of the electrochemical reactions involved are faster than in an acidic medium, and then to develop the solid alkaline membrane fuel cell (SAMFC). 

After rehearsing the working principles and presenting the different kinds of fuel cells, the proton exchange membrane fuel cell (PEMFC), which can operate from ambient temperature to 70-80 °C, and the direct ethanol fuel cell (DEFC), which has to work at higher temperatures (up to 120-150 °C) to improve its electric performance, will be particularly discussed. Finally, the solid alkaline membrane fuel cell (SAMFC) will be presented in more detail, including the electrochemical reactions involved. 

Special electrochemical sensors that operate on the principle of the voltammetric cell have been developed to measure substrates such as oxygen and glucose. In the Clark oxygen sensor, a 1.5 V potential difference is applied between a silver anode and a platinum cathode which are both in contact with a KCl solution separated from the sample by a membrane permeable to oxygen (Fig. 19.6). 

Field-Effect Transistors (FETs) are part of all modern pH meters. With the introduction of ion-sensitive field-effect transistors, they have both been brought to the attention of chemists. In order to understand the principles of operation of these new electrochemical devices, it is necessary to include the FET in the overall discussion of the electrochemical cell. The outline of the operation of an insulated gate field-effect transistor is given in Appendix C. 

Aside from the original assumption of a lumped analysis, thus far there have been no other assumptions or approximations to the model. The model relies completely on basic thermodynamic principles, a known cell performance R(I), and rigorous mathematical operations. To solve the model, we need to know the bulk mass and heat capacity of the cell, M and C, respectively the reactant supply flow rate (m = fuel flow + air flow) the inlet temperature and pressure and the change in stream composition due to the electrochemical reaction, AX, so that the change in enthalpy can be calculated the electrical load current, / and the inlet and exit temperatures, Tm and rout. 

In Part II we have seen that electrochemical cells based on solid materials are useful for a variety of electrochemical applications involving energy and information transformation. Many of these applications cannot be replaced by electronic devices and will play an increasingly important role in our future life. The same principles and cells being operative for electrochemical devices can... 

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