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Chemistry LibreTexts

20: Electrochemistry

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  • 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 electrochemistry. In this chapter, we describe electrochemical reactions in more depth and explore some of their applications. We start by describing 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.

    • 20.1: Oxidation States & Redox Reactions
      Oxidation state is a useful tool for keeping track of electron transfers. It is most commonly used in dealing with metals and especially with transition metals. Oxidation signifies a loss of electrons and reduction signifies a gain of electrons. Balancing redox reactions is an important step that changes in neutral, basic, and acidic solutions.
    • 20.2: Balanced Oxidation-Reduction Equations
      Oxidation–reduction reactions are balanced by separating the overall chemical equation into an oxidation equation and a reduction equation. In oxidation–reduction reactions, electrons are transferred from one substance or atom to another. We can balance oxidation–reduction reactions in solution using the oxidation state method, in which the overall reaction is separated into an oxidation equation and a reduction equation.
    • 20.3: Voltaic Cells
      A galvanic (voltaic) cell uses the energy released during a spontaneous redox reaction to generate electricity, whereas an electrolytic cell consumes electrical energy from an external source to force a reaction to occur. Electrochemistry is the study of the relationship between electricity and chemical reactions. The oxidation–reduction reaction that occurs during an electrochemical process consists of two half-reactions, one representing the oxidation process and one the reduction process.
    • 20.4: Cell Potential Under Standard Conditions
      Redox reactions can be balanced using the half-reaction method. The standard cell potential is a measure of the driving force for the reaction. \(E°_{cell} = E°_{cathode} − E°_{anode} \] The flow of electrons in an electrochemical cell depends on the identity of the reacting substances, the difference in the potential energy of their valence electrons, and their concentrations. The potential of the cell under standard conditions is called the standard cell potential (E°cell).
    • 20.5: Gibbs Energy and Redox Reactions
      A coulomb (C) relates electrical potential, expressed in volts, and energy, expressed in joules. The faraday (F) is Avogadro’s number multiplied by the charge on an electron and corresponds to the charge on 1 mol of electrons.  Spontaneous redox reactions have a negative ΔG and therefore a positive Ecell. Because the equilibrium constant K is related to ΔG, E°cell and K are also related. Large equilibrium constants correspond to large positive values of E°.
    • 20.6: Cell Potential Under Nonstandard Conditions
      The Nernst equation allows us to determine the spontaneous direction of any redox reaction under any reaction conditions from values of the relevant standard electrode potentials. Concentration cells consist of anode and cathode compartments that are identical except for the concentrations of the reactant. Because ΔG = 0 at equilibrium, the measured potential of a concentration cell is zero at equilibrium (the concentrations are equal).
    • 20.7: Batteries and Fuel Cells
      Commercial batteries are galvanic cells that use solids or pastes as reactants to maximize the electrical output per unit mass. A battery is a contained unit that produces electricity, whereas a fuel cell is a galvanic cell that requires a constant external supply of one or more reactants to generate electricity. One type of battery is the Leclanché dry cell, which contains an electrolyte in an acidic water-based paste.
    • 20.8: Corrosion
      Corrosion is a galvanic process that can be prevented using cathodic protection. The deterioration of metals through oxidation is a galvanic process called corrosion. Protective coatings consist of a second metal that is more difficult to oxidize than the metal being protected. Alternatively, a more easily oxidized metal can be applied to a metal surface, thus providing cathodic protection of the surface. A thin layer of zinc protects galvanized steel. Sacrificial electrodes can also be attached
    • 20.9: Electrolysis
      In electrolysis, an external voltage is applied to drive a nonspontaneous reaction. Electrolysis can also be used to produce \(H_2\) and \(O_2\) from water. Electroplating is the process by which a second metal is deposited on a metal surface. The amount of material consumed or produced in a reaction can be calculated from the stoichiometry of an electrolysis reaction, the amount of current passed, and the duration of the electrolytic reaction.
    • 20.E: Electrochemistry (Exercises)
      These are homework exercises to accompany the Textmap created for "Chemistry: The Central Science" by Brown et al.

    Thumbnail: Schematic of Zn-Cu galvanic cell. Image used with permission (CC BY-SA 3.0; Ohiostandard).