electrolysis

CE5

Electrolysis: In a typical reaction electrodes are placed in a solution of hydrogen chloride, HCl, which contains both hydrogen and chlorine ions. The battery removes electrons from the anode, making it positive and causing it to attract chlorine ions, Cl⁻, which combine and are liberated as chlorine gas, Cl₂. The battery supplies electrons to the cathode, making it negative and causing it to attract hydrogen ions, H⁺, which evolve as hydrogen gas, H₂, at the cathode.

electrolysis ĭlĕktrŏlˈəsĭs [key], passage of an electric current through a conducting solution or molten salt that is decomposed in the process.

Sections in this article:

• Introduction
• Electric Cells
• Electroplating
• Commercial Applications of Electrolysis
• The Electrolytic Process

An electric cell is an electrolytic system in which a chemical reaction causes a current to flow in an external circuit; it essentially reverses electrolysis. A battery is a single electric cell (or two or more such cells linked together for additional power) used as a source of electrical energy. Metal corrosion can take place by electrolysis in an unintentionally created electric cell. The Italian physicist Alessandro Volta discovered the principle of the electric cell (see voltaic cell) in 1800. Within a few weeks William Nicholson and Sir Anthony Carlisle, English scientists, performed the first electrolysis, breaking water down into oxygen and hydrogen.

In electroplating, the plating metal is generally the anode, and the object to be plated is the cathode. A solution of a salt of the plating metal is the electrolyte. The plating metal is deposited on the cathode, and the anode replenishes the supply of positive ions, thus gradually being dissolved. Electrotype printing plates, silverware, and chrome automobile trim are plated by electrolysis.

The English scientist Michael Faraday discovered that the amount of a material deposited on an electrode is proportional to the amount of electricity used. The ratio of the amount of material deposited in grams to the amount of electricity used is the electrochemical equivalent of the material. Actual electric consumption may be as high as four times the theoretical consumption because of such factors as heat loss and undesirable side reactions.

Various substances are prepared commercially by electrolysis, e.g., chlorine by the electrolysis of a solution of common salt; hydrogen by the electrolysis of water; heavy water (deuterium oxide) for use in nuclear reactors, also by electrolysis of water. A metal such as aluminum is refined by electrolysis. A solution of aluminum oxide in a molten mineral decomposes into pure aluminum at the cathode and into oxygen at the anode. In these examples the electrodes are inert.

The electrolytic process requires that an electrolyte, an ionized solution or molten metallic salt, complete an electric circuit between two electrodes. When the electrodes are connected to a source of direct current one, called the cathode, becomes negatively (−) charged while the other, called the anode, becomes positively (+) charged. The positive ions in the electrolyte will move toward the cathode and the negatively charged ions toward the anode. This migration of ions through the electrolyte constitutes the electric current in that part of the circuit. The migration of electrons into the anode, through the wiring and an electric generator, and then back to the cathode constitutes the current in the external circuit.

For example, when electrodes are dipped into a solution of hydrogen chloride (a compound of hydrogen and chlorine) and a current is passed through it, hydrogen gas bubbles off at the cathode and chlorine at the anode. This occurs because hydrogen chloride dissociates (see dissociation) into hydrogen ions (hydrogen atoms that have lost an electron) and chloride ions (chlorine atoms that have gained an electron) when dissolved in water. When the electrodes are connected to a source of direct current, the hydrogen ions are attracted to the cathode, where they each gain an electron, becoming hydrogen atoms again. Hydrogen atoms pair off into hydrogen molecules that bubble off as hydrogen gas. Similarly, chlorine ions are attracted to the anode, where they each give up an electron, become chlorine atoms, join in pairs, and bubble off as chlorine gas.

The Columbia Electronic Encyclopedia, 6th ed. Copyright © 2025, Columbia University Press. All rights reserved.

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