Physical Chemistry And Thermodynamics Codexery

Half-cell

A half-cell is an electrode-electrolyte structure generating a potential difference.

Half-cell

A half-cell is a structure in electrochemistry that contains a conductive electrode and a surrounding conductive electrolyte, separated by a naturally occurring Helmholtz double layer. Chemical reactions within this layer momentarily pump electric charges between the electrode and the electrolyte, resulting in a potential difference. Half-cells are fundamental components of Galvanic cells, where two dissimilar half-cells are appropriately connected.

field
Electrochemistry
known_for
Fundamental unit of Galvanic cells; standard hydrogen electrode; electrochemical series

Lore & Background

In a half-cell, the typical anode reaction involves a metal atom in the electrode being dissolved and transported as a positive ion across the double layer, causing the electrolyte to acquire a net positive charge while the electrode acquires a net negative charge. The growing potential difference creates an intense electric field within the double layer, and the potential rises until the field halts the net charge-pumping reactions. This self-limiting action occurs almost instantly in an isolated half-cell.

Reader's Guide

In the case of the standard hydrogen electrode (SHE), a platinum electrode is used and is immersed in an acidic solution where the concentration of hydrogen ions is 1M, with hydrogen gas at 1 atm being bubbled through solution. The electrochemical series, which consists of standard electrode potentials and is closely related to the reactivity series, was generated by measuring the difference in potential between the metal half-cell in a circuit with a standard hydrogen half-cell, connected by a salt bridge. The half-cells of a Daniell cell illustrate the anode reaction (Zn → Zn2+ + 2e−) and the cathode reaction (Cu2+ + 2e− → Cu). The significance of the half-cell lies in its role as the building block for all Galvanic cells, enabling the measurement and tabulation of standard electrode potentials that predict the direction of redox reactions.

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