Electrochemical Processes Galvanic Cells

Electrochemical systems convert chemical and electrical energy through charge-transfer reactions. These reactions occur at the interface between two phases. Consequendy, an electrochemical ceU contains multiple phases, and surface phenomena are important. Electrochemical processes are sometimes divided into two categories electrolytic, where energy is supplied to the system, eg, the electrolysis of water and the production of aluminum and galvanic, where electrical energy is obtained from the system, eg, batteries (qv) and fuel cells (qv). 

Galvanic cells in which stored chemicals can be reacted on demand to produce an electric current are termed primaiy cells. The discharging reac tion is irreversible and the contents, once exhausted, must be replaced or the cell discarded. Examples are the dry cells that activate small appliances. In some galvanic cells (called secondaiy cells), however, the reaction is reversible that is, application of an elec trical potential across the electrodes in the opposite direc tion will restore the reactants to their high-enthalpy state. Examples are rechargeable batteries for household appliances, automobiles, and many industrial applications. Electrolytic cells are the reactors upon which the electrochemical process, elec troplating, and electrowinning industries are based. 

Even single metals, however, are subject to aqueous corrosion by essentially the same electrochemical process as for bimetallic corrosion. The metal surface is virtually never completely uniform even if there is no preexisting oxide film, there will be lattice defects (Chapter 5), local concentrations of impurities, and, often, stress-induced imperfections or cracks, any of which could create a local region of abnormally high (or low) free energy that could serve as an anodic (or cathodic) spot. This electrochemical differentiation of the surface means that local galvanic corrosion cells will develop when the metal is immersed in water, especially aerated water. 

Electrolysis is the process of driving a reaction in a nonspontaneous direction by using an electric current. An electrolytic cell is an electrochemical cell in which electrolysis takes place. The arrangement of components in electrolytic cells is different from that in galvanic cells. Specifically, the two electrodes usually share the same compartment, there is usually only one electrolyte, and concentrations and pressures are usually far from standard. 

Thus far, we ve been concerned only with galvanic cells—electrochemical cells in which a spontaneous redox reaction produces an electric current. A second important kind of electrochemical cell is the electrolytic cell, in which an electric current is used to drive a nonspontaneous reaction. Thus, the processes occurring in galvanic and electrolytic cells are the reverse of each other A galvanic cell converts... 

Both of these processes are carried out in electrochemical cells which are forced to operate in the reverse , or non-spontaneous direction, as indicated by the negative for the above cell reaction. The free energy is supplied in the form of electrical work done on the system by the outside world (the surroundings). This is the only fundamental difference between an electrolytic cell and the galvanic cell in which the free energy supplied by the cell reaction is extracted as work done on the surroundings. 

The mechanism of sulphation has been explained [11] by means of an electrochemical process described by a galvanic cell formed between CaCOa acting as a negative pole and the corrosive environment (SO2 -I-air -I- water vapour) activy as the electrolyte. 

Where might this be important As discussed above, biological activity can result in the simultaneous precipitation of mixtures of nanoscale sulfide minerals under certain conditions. Each mineral will exhibit a particular particle size distribution, dependent on the solution composition, bacterial activity, rate of crystal growth, and the nature of electrochemical interactions between the particles. These electrochemical reactions could lead to oxidation of one type of nanophase sulfide mineral of a certain size, and reduction of another type of nanophase sulfide particle or other species in the solution. In this way, a tremendous number of mineral-solution-mineral galvanic cells could develop, with potentially significant impact on dissolution kinetics, growth kinetics, and the mixture of phases observed. In addition to environmental relevance, these processes may shape the mineralogy of low-temperature ore deposits. 

The dry cell battery is a typical example of galvanic corrosion, or two metal corrosion as it is otherwise called. When two dissimilar metals are immersed in a conductive or corrosive medium, there is always the potential for a change in them. Once these metals are connected this difference induces electron flow between them. The less corrosion resistant metal is attacked more than the more resistant metal. This is an electrochemical process. In the case of a dry cell battery, the carbon electrode acts as the cathode (the more resistant materials) and zinc as the corroding anode. The natural phenomenon of corrosion is used in this case for producing electricity. 

Every galvanic cell contains two electrodes, which must be metallic conductors in the general sense outlined on page 16. At each of these electrodes an electrochemical reaction takes place. One of these reactions yields electrons to an electrode and one absorbs electrons from the other electrode. In certain important cases these electrochemical reactions may be the same process acting in reverse directions. We have already considered the reactions... 

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