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11: Electrochemistry

Last updated

Jun 23, 2019
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- 10.12: Free Energy and Work
- Front Matter

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Topic hierarchy

11.1: Galvanic Cells
An electric current consists of moving charge. The charge may be in the form of electrons or ions. Current flows through an unbroken or closed circular path called a circuit. The current flows through a conducting medium as a result of a difference in electrical potential between two points in a circuit. Electrical potential has the units of energy per charge. In SI units, charge is measured in coulombs (C), current in amperes, and electrical potential in volts.
11.2: Standard Reduction Potential
Electrochemical cells typically consist of two half-cells. The half-cells separate the oxidation half-reaction from the reduction half-reaction and make it possible for current to flow through an external wire. One half-cell contains the anode. Oxidation occurs at the anode. The anode is connected to the cathode in the other half-cell. Reduction occurs at the cathode. Adding a salt bridge completes the circuit allowing current to flow.
11.3: Cell Potential, Electrical Work, and Gibbs Energy
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°.
11.4: Dependence of Cell Potential on Concentration
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).
11.5: Batteries
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.
11.6: 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
11.7: Electrolysis
In electrolysis, an external voltage is applied to drive a nonspontaneous reaction. Electrolysis can also be used to produce hydrogen and oxygen gases 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.
11.8: Commercial Electrolytic Processes

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