Chapter 18 – Summary

18.1 – Redox Reactions and Oxidation Numbers

Redox reactions involves the transfer of electrons and are defined by changes in reactant oxidation numbers. The oxidation number represents the charge of an atom if it were in an ionic compound. There are general guidelines that can be followed to determine the oxidation number of each element in a redox reaction. Oxidation is the loss of electrons and reduction is the gain of electrons. Whatever is oxidized in the reaction is considered to be the reducing agent and whatever is reduced is considered to be the oxidizing agent.

18.2 Balancing Redox Reactions

Oxidation is the loss of electrons, and the species that is oxidized is also called the reducing agent. Reduction is the gain of electrons, and the species that is reduced is also called the oxidizing agent. Oxidation-reduction reactions can be balanced using the half-reaction method. In this method, the oxidation-reduction reaction is split into an oxidation half-reaction and a reduction half-reaction. The oxidation half-reaction and reduction half-reaction are then balanced separately. Each of the half-reactions must have the same number of each type of atom on both sides of the equation and show the same total charge on each side of the equation. Charge is balanced in oxidation half-reactions by adding electrons as products; in reduction half-reactions, charge is balanced by adding electrons as reactants. The total number of electrons gained by reduction must exactly equal the number of electrons lost by oxidation when combining the two half-reactions to give the overall balanced equation. Balancing oxidation-reduction reaction equations in aqueous solutions frequently requires that oxygen or hydrogen be added or removed from a reactant. In acidic solution, hydrogen is added by adding hydrogen ion (H⁺) and removed by producing hydrogen ion; oxygen is removed by adding hydrogen ion and producing water, and added by adding water and producing hydrogen ion. A balanced equation in basic solution can be obtained by first balancing the equation in acidic solution, and then adding hydroxide ion to each side of the balanced equation in such numbers that all the hydrogen ions are converted to water.

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, normally depicted on the left side in a figure, contains the anode. Oxidation occurs at the anode. The anode is connected to the cathode in the other half-cell, often shown on the right side in a figure. Reduction occurs at the cathode. Adding a salt bridge completes the circuit allowing current to flow. Anions in the salt bridge flow toward the anode and cations in the salt bridge flow toward the cathode. The movement of these ions completes the circuit and keeps each half-cell electrically neutral. Electrochemical cells can be described using cell notation. In this notation, information about the reaction at the anode appears on the left and information about the reaction at the cathode on the right. The salt bridge is represented by a double line, ‖. The solid, liquid, or aqueous phases within a half-cell are separated by a single line, │. The phase and concentration of the various species is included after the species name. Electrodes that participate in the oxidation-reduction reaction are called active electrodes. Electrodes that do not participate in the oxidation-reduction reaction but are there to allow current to flow are inert electrodes. Inert electrodes are often made from platinum or gold, which are unchanged by many chemical reactions.

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). The reduction reactions are reversible, so standard cell potentials can be calculated by subtracting the standard reduction potential for the reaction at the anode from the standard reduction for the reaction at the cathode. When calculating the standard cell potential, the standard reduction potentials are not scaled by the stoichiometric coefficients in the balanced overall equation.

18.5 –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. Examples of secondary batteries include nickel-cadmium (NiCd), lead acid, and lithium ion batteries. Fuel cells are similar to batteries in that they generate an electrical current, but require continuous addition of fuel and oxidizer. The hydrogen fuel cell uses hydrogen and oxygen from the air to produce water, and is generally more efficient than internal combustion engines.

18.6 – Corrosion

Corrosion is the degradation of a metal caused by an electrochemical process. Large sums of money are spent each year repairing the effects of, or preventing, corrosion. Some metals, such as aluminum and copper, produce a protective layer when they corrode in air. The thin layer that forms on the surface of the metal prevents oxygen from coming into contact with more of the metal atoms and thus “protects” the remaining metal from further corrosion. Iron corrodes (forms rust) when exposed to water and oxygen. The rust that forms on iron metal flakes off, exposing fresh metal, which also corrodes. One way to prevent, or slow, corrosion is by coating the metal. Coating prevents water and oxygen from contacting the metal. Paint or other coatings will slow corrosion, but they are not effective once scratched. Zinc-plated or galvanized iron exploits the fact that zinc is more likely to oxidize than iron. As long as the coating remains, even if scratched, the zinc will oxidize before the iron. Another method for protecting metals is cathodic protection. In this method, an easily oxidized and inexpensive metal, often zinc or magnesium (the sacrificial anode), is electrically connected to the metal that must be protected. The more active metal is the sacrificial anode, and is the anode in a galvanic cell. The “protected” metal is the cathode, and remains unoxidized. One advantage of cathodic protection is that the sacrificial anode can be monitored and replaced if needed.

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. If the solution contains only one material, like the electrolysis of molten sodium chloride, it is a simple matter to determine what is oxidized and what is reduced. In more complicated systems, like the electrolysis of aqueous sodium chloride, more than one species can be oxidized or reduced and the standard reduction potentials are used to determine the most likely oxidation (the half-reaction with the largest [most positive] standard reduction potential) and reduction (the half-reaction with the smallest [least positive] standard reduction potential). Sometimes unexpected half-reactions occur because of overpotential. Overpotential is the difference between the theoretical half-reaction reduction potential and the actual voltage required. When present, the applied potential must be increased, making it possible for a different reaction to occur in the electrolytic cell. The total charge, Q, that passes through an electrolytic cell can be expressed as the current (I) multiplied by time (Q = It) or as the moles of electrons (n) multiplied by Faraday’s constant (Q = nF). These relationships can be used to determine things like the amount of material used or generated during electrolysis, how long the reaction must proceed, or what value of the current is required.