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18: Electrochemistry

Last updated

Dec 26, 2024
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- 17.7: Exercises
- 18.1: Introduction

Marco Zimmer-De Iuliis and Anna Galang
University of Toronto Scarborough

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Electrochemistry deals with chemical reactions that produce electricity and the changes associated with the passage of electrical current through matter. The reactions involve electron transfer, and so they are oxidation-reduction (or redox) reactions. Many metals may be purified or electroplated using electrochemical methods. Devices such as automobiles, smartphones, electronic tablets, watches, pacemakers, and many others use batteries for power. Batteries use chemical reactions that produce electricity spontaneously and that can be converted into useful work. All electrochemical systems involve the transfer of electrons in a reacting system. In many systems, the reactions occur in a region known as the cell, where the transfer of electrons occurs at electrodes.

This chapter introduces the fundamental principles of electrochemistry, a field that explores the relationship between electrical energy and chemical reactions. Understanding these principles is crucial for a variety of applications, including the development of advanced technologies in energy storage, corrosion prevention, and medical diagnostics.

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18.1: Introduction
18.2: Review of Redox Chemistry
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.
18.3: Galvanic Cells
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.
18.4: Electrode and Cell Potentials
Assigning the potential of the standard hydrogen electrode (SHE) as zero volts allows the determination of standard reduction potentials, E°, for half-reactions in electrochemical cells. As the name implies, standard reduction potentials use standard states (1 bar or 1 atm for gases; 1 M for solutes, often at 298.15 K) and are written as reductions (where electrons appear on the left side of the equation).
18.5: Potential, Free Energy, and Equilibrium
Electrical work is the negative of the product of the total charge (Q) and the cell potential (Ecell). The total charge can be calculated as the number of moles of electrons (n) times the Faraday constant (F = 96,485 C/mol e−). Electrical work is the maximum work that the system can produce and so is equal to the change in free energy. Thus, anything that can be done with or to a free energy change can also be done to or with a cell potential.
18.6: Batteries and Fuel Cells
Batteries are galvanic cells, or a series of cells, that produce an electric current. When cells are combined into batteries, the potential of the battery is an integer multiple of the potential of a single cell. There are two basic types of batteries: primary and secondary. Primary batteries are “single use” and cannot be recharged. Dry cells and (most) alkaline batteries are examples of primary batteries. The second type is rechargeable and is called a secondary battery.
18.7: Electrolysis
Using electricity to force a nonspontaneous process to occur is electrolysis. Electrolytic cells are electrochemical cells with negative cell potentials (meaning a positive Gibbs free energy), and so are nonspontaneous. Electrolysis can occur in electrolytic cells by introducing a power supply, which supplies the energy to force the electrons to flow in the nonspontaneous direction. Electrolysis is done in solutions, which contain enough ions so current can flow.
18.8: Key Terms
18.9: Key Equations
18.10: Summary
18.11: Exercises
These end-of-chapter exercises are for practice to help you both understand concepts from the course and for practice for tests and exams.

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