Electric current galvanic cell

There are two types of electrochemical cell. A galvanic cell uses a spontaneous chemical reaction to produce an external electric current. Galvanic cells are called batteries in colloquial speech. Electrolytic cells, employed for electrolysis and electroplating, use external electrical power to force nonspontaneous chemical reactions to take place. 

If the electrochemical system generates a current (galvanic cell), then the experimentally observed cell potential decreases with the passage of current. In this case, the resistance in the galvanic cell controls the voltage drop, which compensates for the resistance inside the cell and introducing a loss in electrical energy production. When a net current... 

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. 

Although iron pipes suffer from the same corrosion risk as steel pipelines, associated with the generation of a galvanic cell with a small anode and a large cathode, the risk is mitigated for iron pipelines because the electrical continuity is broken at every pipe joint. For this reason long-line currents are uncommon in iron lines and cathodic protection is rarely necessary. It also accounts for the ability to protect iron lines by the application of nonadherent polyethylene sleeving . 

In the predominantly electronically conducting electrodes it is the chemical diffusion of the ions which controls the electrical current of the galvanic cell. This includes the internal electric field which is built up by the simultaneous motion of ions and electrons to establish charge neutrality [14] ... 

FIGURE 12.5 The cell potential is measured with an electronic voltmeter, a device designed to draw negligible current so that the composition of the cell does not change during the measurement. The display shows a positive value when the + terminal of the meter is connected to the cathode of the galvanic cell. The salt bridge completes the electric circuit within the cell. 

The electrical current needed to start an automobile engine is provided by a lead storage battery. This battery contains aqueous sulfuric acid in contact with two electrodes. One electrode is metallic lead, and the other is solid Pb02. Each electrode becomes coated with solid PbSOq as the battery operates. Determine the balanced half-reactions, the overall redox reaction, and the anode and cathode in this galvanic cell. 

Galvanic cells use redox reactions to generate electrical current. Electrical current can also drive redox reactions, and the same stoichiometric relationships apply to such processes, as we describe in Section 19-1. 

A battery is a galvanic cell that generates electrical current to power a practical device. Batteries can be as small as the buttons that power cameras and hearing aids or large charge storage banks like those of electric automobiles. 

In a galvanic cell, a spontaneous chemical reaction generates an electrical current. It is also possible to use an electrical current to drive a nonspontaneous chemical reaction. The recharging of a dead battery uses an external electrical current to drive the batteiy reaction in the reverse, or uphill, direction. 

Two directions of current flow in galvanic cells are possible a spontaneous direction and an imposed direction. When the cell circuit is closed with the aid of electronic conductors, current will flow from the cell s positive electrode to its negative electrode in the external part of the circuit, and from the negative to the positive electrode within the cell (Fig. 2.2a). In this case the current arises from the cell s own voltage, and the cell acts as a chemical source of electric current or battery. But when a power source of higher voltage, connected so as to oppose the cell, is present in the external circuit, it will cause current to flow in the opposite direction (Fig. 2.2b), and the cell works as an electrolyzer. 

This equation links the EMF of a galvanic cell to the Gibbs energy change of the overall current-producing reaction. It is one of the most important equations in the thermodynamics of electrochemical systems. It follows directly from the first law of thermodynamics, since nF% is the maximum value of useful (electrical) work of the system in which the reaction considered takes place. According to the basic laws of thermodynamics, this work is equal to -AG . 

The first observations of photoelectrochemical phenomena were made in 1839 by Antoine Becquerel (1788-1879). He used symmetric galvanic cells consisting of two identical metal electrodes in a dilute acid. When illuminating one of the electrodes he observed current flow in the closed electric circuit. 

This can be accomplished by applying an electrical potential in the external circuit in such a manner that an emf occurs in opposition to that of the galvanic cell. The opposing emf is varied by means of a potentiometer until the current flow from the cell is essentially zero. Under these conditions, the cell may very well approach reversibility. This is readily tested by changing the direction of the current and allowing an infinitesimally small current flow in the opposite direction. If the cell is reversible, the cell reaction will proceed in the reverse direction with the same efficiency as in the forward direction. For a reversible reaction... 

In case (a), the galvanic cell under non-faradaic conditions, one obtains an emf of 0.34 - (-0.76) = 1.10 V across the Cu electrode ( + pole) and the Zn electrode (- pole). In case (b), the galvanic cell with internal electrolysis, the electrical current flows in the same direction as in case (a) and the electrical energy thus delivered results from the chemical conversion represented by the following half-reactions and total reaction, repsectively ... 

The dissolution of zinc in a mineral acid is much faster when the zinc contains an admixture of copper. This is because the surface of the metal contains copper crystallites at which hydrogen evolution occurs with a much lower overpotential than at zinc (see Fig. 5.54C). The mixed potential is shifted to a more positive value, E mix, and the corrosion current increases. In this case the cathodic and anodic processes occur on separate surfaces. This phenomenon is termed corrosion of a chemically heterogeneous surface. In the solution an electric current flows between the cathodic and anodic domains which represent short-circuited electrodes of a galvanic cell. A. de la Rive assumed this to be the only kind of corrosion, calling these systems local cells. 

Galvanic cell action Chemical reaction causes electric current, as in a battery. 

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