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Frost diagram


A Frost diagram or Frost-Ebsworth diagram is a type of graph used by inorganic chemists in electrochemistry to illustrate the relative stability of a number of different oxidation states of a particular substance. The graph illustrates the oxidation state vs free energy of a chemical species. This effect is dependent on pH, so this parameter also must be included. The free energy is determined by the oxidation–reduction half-reactions. The Frost diagram allows easier comprehension of these reduction potentials than the earlier-designed Latimer diagram, because the “lack of additivity of potentials” was confusing. The free energy ΔG° is related to reduction potential E in the graph by given formula: ΔG° = −nFE° or nE° = −ΔG°/F, where n is the number of transferred electrons, and F is Faraday constant (F = 96,485 J/(V·mol)). The Frost diagram is named for Arthur Atwater Frost, who originally created them as a way to "show both free energy and oxidation potential data conveniently" in a 1951 paper.

The pH dependence is given by the factor −0.059m/n per pH unit, where m relates to the number of protons in the equation, and n the number of electrons exchanged. Electrons are always exchanged in electrochemistry, but not necessarily protons. If there is no proton exchange in the reaction equilibrium, the reaction is said to be pH-independent. This means that the values for the electrochemical potential rendered in a redox half-reaction, whereby the elements in question change oxidation states are the same whatever the pH conditions under which the procedure is carried out.

The Frost diagram is also a useful tool for comparing the trends of standard potentials (slope) of acidic and basic solutions. The pure, neutral element transitions to different compounds depending whether the species is in acidic and basic pHs. Though the value and amount of oxidation states remain unchanged, the free energies can vary greatly. The Frost diagram allows the superimposition of acidic and basic graphs for easy and convenient comparison.


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