Difference between revisions of "Frost diagram"
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The vertical axis on a Frost diagram is a measure of [[free energy]]: a chemical system will always tend to towards the state of lowest free energy so, ''other things being equal'', species at the bottom of the diagram will tend to be "more stable" than those higher up. Hence, in the Frost diagram from [[manganese]] at pH 0, the Mn<sup>2+</sup> cation is the "most stable" species at that pH. | The vertical axis on a Frost diagram is a measure of [[free energy]]: a chemical system will always tend to towards the state of lowest free energy so, ''other things being equal'', species at the bottom of the diagram will tend to be "more stable" than those higher up. Hence, in the Frost diagram from [[manganese]] at pH 0, the Mn<sup>2+</sup> cation is the "most stable" species at that pH. | ||
| − | If a species is at a concave point on the curve, such as Mn<sup>2+</sup> and MnO<sub>2</sub>, that species is stable towards [[disproportionation]]. On the other hand, species which are at convex points on the curve, such as Mn<sup>3+</sup>, H<sub>3</sub>MnO<sub>4</sub> and HMnO | + | If a species is at a concave point on the curve, such as Mn<sup>2+</sup> and MnO<sub>2</sub>, that species is stable towards [[disproportionation]]. On the other hand, species which are at convex points on the curve, such as Mn<sup>3+</sup>, H<sub>3</sub>MnO<sub>4</sub> and HMnO{{su|b=4|p=−}}, will tend to disproportionate until they reach the species at concave points. It is important to remember that this "tendency to disproportion" is a thermodynamic description, and says nothing about the kinetics of the reaction: the [[hypochlorite]] ion, for example, is unstable with respect to disproportionation to [[perchlorate]] and [[chloride]], but the reaction is very slow below 70 °C and, even then, gives [[chlorate]] as the oxidized product and not perchlorate.<ref>{{Greenwood&Earnshaw1st|page=1002}}.</ref> |
| + | |||
| + | Frost diagrams may be drawn with oxidation number either decreasing or increasing from left to right. In the examples shown, the highest oxidation numbers (e.g., [[permanganate]], MnO{{su|b=4|p=−}}) are on the left-hand side of the diagram: these species tend to get reduced as they move towards the "most stable" species, i.e. they are [[oxidizing agent]]s. | ||
| + | |||
| + | ==Construction== | ||
| + | The first step in the construction of a Frost diagram is to identify the different species which might be present under the chosen conditions and the [[electrode potential]]s which relate them. These are conveniently summarized in a [[Latimer diagram]], and Latimer diagrams for most elements at pH 0 and pH 14 are available from a number of sources. Only the central line of the Latimer diagram and the oxidation numbers of the species are required. | ||
| + | |||
| + | {| | ||
| + | | '''Oxidation number''' || align=center | +7 || || align=center | +5 || || align=center | +4 || || align=center | +3 || || align=center | +1 || || align=center | 0 || || align=center | −1 | ||
| + | |- | ||
| + | | '''''E''<sup><s>o</s></sup>/V''' || || align=center | +1.20 || || align=center | +1.18 || || align=center | +1.19 || || align=center | +1.67 || || align=center | +1.63 || || align=center | +1.36 || | ||
| + | |- | ||
| + | | '''Species''' || ClO{{su|b=4|p=−}} || ——— || ClO{{su|b=3|p=−}} || ——— || ClO<sub>2</sub> || ——— || HClO<sub>2</sub> || ——— || HClO || ——— || Cl<sub>2</sub> || ——— || Cl<sup>−</sup> | ||
| + | |- | ||
| + | | colspan=14 | Abbreviated Latimer diagram for chlorine at pH 0. | ||
| + | |- | ||
| + | |} | ||
==See also== | ==See also== | ||
Revision as of 13:30, 11 April 2010
A Frost diagram is a graphical representation of the relative stability of different oxidation states of an element: specifically a plot of the Gibbs free energy of formation of different species, in or from aqueous solution, against oxidation number. Such diagrams were first introduced by American chemist Arthur A. Frost.[1]
Interpretation
The vertical axis on a Frost diagram is a measure of free energy: a chemical system will always tend to towards the state of lowest free energy so, other things being equal, species at the bottom of the diagram will tend to be "more stable" than those higher up. Hence, in the Frost diagram from manganese at pH 0, the Mn2+ cation is the "most stable" species at that pH.
If a species is at a concave point on the curve, such as Mn2+ and MnO2, that species is stable towards disproportionation. On the other hand, species which are at convex points on the curve, such as Mn3+, H3MnO4 and HMnO−4, will tend to disproportionate until they reach the species at concave points. It is important to remember that this "tendency to disproportion" is a thermodynamic description, and says nothing about the kinetics of the reaction: the hypochlorite ion, for example, is unstable with respect to disproportionation to perchlorate and chloride, but the reaction is very slow below 70 °C and, even then, gives chlorate as the oxidized product and not perchlorate.[2]
Frost diagrams may be drawn with oxidation number either decreasing or increasing from left to right. In the examples shown, the highest oxidation numbers (e.g., permanganate, MnO−4) are on the left-hand side of the diagram: these species tend to get reduced as they move towards the "most stable" species, i.e. they are oxidizing agents.
Construction
The first step in the construction of a Frost diagram is to identify the different species which might be present under the chosen conditions and the electrode potentials which relate them. These are conveniently summarized in a Latimer diagram, and Latimer diagrams for most elements at pH 0 and pH 14 are available from a number of sources. Only the central line of the Latimer diagram and the oxidation numbers of the species are required.
| Oxidation number | +7 | +5 | +4 | +3 | +1 | 0 | −1 | ||||||
| E |
+1.20 | +1.18 | +1.19 | +1.67 | +1.63 | +1.36 | |||||||
| Species | ClO−4 | ——— | ClO−3 | ——— | ClO2 | ——— | HClO2 | ——— | HClO | ——— | Cl2 | ——— | Cl− |
| Abbreviated Latimer diagram for chlorine at pH 0. | |||||||||||||
See also
References
- ↑ Frost, Arthur A. Oxidation Potential–Free Energy Diagrams. J. Am. Chem. Soc. 1951, 73 (6), 2680–82. DOI: 10.1021/ja01150a074.
- ↑ Greenwood, Norman N.; Earnshaw, A. Chemistry of the Elements; Pergamon: Oxford, 1984; p 1002. ISBN 0-08-022057-6.
External links
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See also the corresponding article on Wikipedia. |
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