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natural waters can be summarized with predominance diagrams such as that for
phosphorous (V) shown below.
However, if suitable reducing agents are present, the phosphorous may not remain in the +5
oxidation state.
Knowledge of the pH condition of the environment is not sufficient for predicting the form
in which an element will exist in natural waters. You must also take into consideration
whether the aqueous environment is well aerated (oxidizing) or polluted with organic
wastes (reducing). In order to add this variable, we must expand the predominance diagram
to include the reduction potential of the environment as well as the pH. This type of
predominance diagram is known as a Pourbaix diagram.Eo-pH diagram, or pE-pH diagram.
o line a shows the pH at which half of the 1 M iron is Fe3+ and half is
precipitated as Fe(OH)2
reducing the total concentration of Fe3+ will reduce the driving force
of the precipitation
reducing the total iron concentration from 1 M to 10-6 M (more
realistic concentrations for geochemists and corrosion engineers)
shifts the boundary from pH 1.7 to pH 4.2
Solid double lines separate species related by redox equilibria (lines c & d)
Longer dashed lines enclose the theoretical region of stability of the water to
oxidation or reduction ((lines d & f) while shorter dashed lines enclose the practical
region of stability of the water (e & g)
o Dashed line d represents the potential of water saturated with dissolved O2at
1 atm (very well aerated water).
Dashed line f represents the potential of water saturated with dissolved H2 at 1 atm
pressure (high level or reducing agents in solution).
2 H+ + 2 e- Eo = +1.229 V
Any point on the diagram will give the termodynamically most stable (theoretically
the most abundant) form of the element for that E and pH.
o E=+0.8 V and pH = 14
predominant form is FeO42-.
The diagram gives a visual representation of the oxidizing and reducing abilities of
the major stable compounds of an element
o Strong oxidizing agents and oxidizing conditions are found ONLY at the top
of the diagram.
The lower boundaries of strong oxidizing agents are high on the diagram.
o Reducing agents and reducing conditions are found at the bottom of a
diagram and nowhere else.
Strong reducing agents have boundaries that are low on the diagram.
EXAMPLE
On the Pourbaix diagram for iron find:
For some elements, the predominance area for a given oxidation state may disappear
completely above or below a given pH.
If the element is in an intermediate oxidation state, the element will undergo
disproportionation at appropriate pH's.
Notice that predominance areas are missing for hypochlorite, chlorite and chlorate ions.
This is due to either lack of electrochemical data for a species or (in this case) the fact that
the ions are thermodynamically unstable to disproportionation. In the case of chlorine the
rates of disproportionation reactions are slow enough that these chlorine species can be
observed and used.
In predicting when cations and anions would react to form precipitates, we only considered
the most stable oxidation states of the elements so that interference of redox reactions
between the anion and cation could be avoided.
Ferrate ion is expected to be a feebly basic anion which should precipitate with feebly
acidic cations. Ferrate gives the expected precipitate with Ba2+ but not with Eu2+.
Eu2+ is a good reducing agent having no part of its predominance area above a potential of
-0.429 V. There is no overlap of this region with that of ferrate ion. A redox reaction will
occur between the two species to yield species that do have overlapping predominance
areas -- Eu3+ and Fe3+
Pourbaix diagrams allow for more
accurate predictions of the forms in
which the different elements will
exist in natural waters.
o for a swamp