16: Electrochemistry

Last updated
Save as PDF

Page ID: 333777

\( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \) \( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash {#1}}} \)\(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\) \(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\)\(\newcommand{\AA}{\unicode[.8,0]{x212B}}\)

16.1: Pulling the Plug on the Power Grid
16.2: Balancing 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.
16.3: Voltaic (or Galvanic) Cells- Generating Electricity from Spontaneous Chemical Reactions
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.
16.4: Standard Reduction Potentials
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).
16.5: Cell Potential, Gibbs Energy, and the Equilibrium Constant
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°.
16.6: Cell Potential and 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).
16.7: Batteries- Using Chemistry to Generate Electricity
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.
16.8: Electrolysis- Driving Non-spontaneous Chemical Reactions with Electricity
In electrolysis, an external voltage is applied to drive a nonspontaneous reaction. Electrolysis can also be used to produce hydrogen and oxygen gas 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.
16.9: Corrosion- Undesirable Redox Reactions
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