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Pourbaix diagram of iron

Figure 1. Pourbaix diagram of iron (Source)

The line between $\ce{Fe}$ and $\ce{Fe^2+}$ is there because the potential $\ce{Fe/Fe^2+}$ is $\pu{-0.44 V}$. The same applies for $\ce{Fe^2+/Fe^3+}$ with $\pu{0.77 V}$. But $\ce{Fe/Fe^3+}$ is $\pu{-0.03 V}$, but it's not on the graph as a line.

How do I know which species have a line, and which don't? And if I'm drawing a graph, how do I know that I also shouldn't include this line?

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  • $\begingroup$ As a hint, it's easier to understand a Pourbaix diagram (or any other phase diagram) not as a set of lines where transformations take place, but as a set of areas where one species is thermodynamically the most stable and therefore preponderant - when two neighbouring areas meet, their boundary happens to lie at the line that describes their equilibrium. However, while you can write standard reduction potentials for any reaction that you can imagine, that doesn't imply that the species involved are preponderant at both sides of the line that describes said equilibrium. $\endgroup$ – user41033 Mar 18 '18 at 19:33
  • $\begingroup$ In other words, while at $\mathrm{pH=0}$, the $\ce{Fe^{3+}/Fe^{0}}$ standard potential of -0.03V means that below it $\ce{Fe^{0}}$ is more stable than $\ce{Fe^{3+}}$, and the opposite is true above that standard potential, $\ce{Fe^{2+}}$ is actually more stable than both between -0.44V and +0.77V - which is what the area labelled $\ce{Fe^{2+}}$ represents in the diagram. $\endgroup$ – user41033 Mar 18 '18 at 19:37
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Pourbaix Diagram In Environmental Chemistry

Pourbaix diagrams are very useful to identify the nature chemical species in different pH environment.

The figure contains additional information on the stability of water. The lines at 1.23 V and 0.00 V represent the redox chemistry of water. At 1.23 V water is being oxidised to oxygen. At 0.00 V the water is reduced to hydrogen. As labelled in Fig.1, there are 3 regions where behaviour of water is represented. The middle region is where the water in "stable state".

Note: These voltages are obtained at 298 K. In order to derive these lines, you can use Nernst Equation (where gradient is: -RT/nF, as the both reactions involve 2 electrons the gradient is the same in both cases.)

F

Figure 1: Stability of water.

Now moving on to iron. Overlapping water behaviour and iron as in Fig.2. (The dashed lines - redox chemistry of water). In the case of water, knowing the pH given you can predict the behaviour of iron. For the sake of understanding how to utilise the Pourbaix diagrams.

Assuming you are analysing alkaline lake (high pH: 10-12) and assume there is not much oxygen content (to utilise also the y-axis, low oxygen level - E decreases). In Fig.2, the region of your interest is pH 10-12 and since low oxygen, and region around 0.00 V. The Pourbaix indidicates that at these conditions you can have some amounts of Fe(OH)2, Fe(OH)3.

enter image description here

Figure 2: Analysis of Iron species in 1 M of water (298 K).

To see different behaviour of other species: http://www.crct.polymtl.ca/ephweb.php

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