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Chapter 19 Electrochemistry

In oxidation–reduction (redox) reactions, electrons are transferred from one species (the reductant) to another (the oxidant). This transfer of electrons provides a means for converting chemical energy to electrical energy or vice versa. The study of the relationship between electricity and chemical reactions is called electrochemistryThe study of the relationship between electricity and chemical reactions., an area of chemistry we introduced in Chapter 4 "Reactions in Aqueous Solution" and Chapter 5 "Energy Changes in Chemical Reactions". In this chapter, we describe electrochemical reactions in more depth and explore some of their applications.

In the first three sections, we review redox reactions; describe how they can be used to generate an electrical potential, or voltage; and discuss factors that affect the magnitude of the potential. We then explore the relationships among the electrical potential, the change in free energy, and the equilibrium constant for a redox reaction, which are all measures of the thermodynamic driving force for a reaction. Finally, we examine two kinds of applications of electrochemical principles: (1) those in which a spontaneous reaction is used to provide electricity and (2) those in which electrical energy is used to drive a thermodynamically nonspontaneous reaction. By the end of this chapter, you will understand why different kinds of batteries are used in cars, flashlights, cameras, and portable computers; how rechargeable batteries operate; and why corrosion occurs and how to slow—if not prevent—it. You will also discover how metal objects can be plated with silver or chromium for protection; how silver polish removes tarnish; and how to calculate the amount of electricity needed to produce aluminum, chlorine, copper, and sodium on an industrial scale.

A view from the top of the Statue of Liberty, showing the green patina coating the statue. The patina is formed by corrosion of the copper skin of the statue, which forms a thin layer of an insoluble compound that contains copper(II), sulfate, and hydroxide ions.