This is the author’s version of the conference paper

УДК 544.653:544.016:544.313.2.031

THE POTENTIAL – pH DIAGRAM FOR Fe – H2O SYSTEM

P. A. Nikolaychuk

Chelyabinsk State University, Chelyabinsk, Russia. E-mail: npa@csu.ru

Thermodynamic information on aqueous iron species is systematized. The

reactions between various species are discussed. The activity – pH diagram for
FeIII species and the revised potential – pH diagram of Fe – H2O system at 25ºC, 1
bar and a[Fe] = 10–6 mol l–1 are plotted.

Aqueous chemistry of iron is studied very widely. Several papers

were focused on plotting a Pourbaix diagram for iron. However, the
diagrams presented in various sources [1–3] aren’t consistent with each
other. This paper aims to collect and analyze available data on Gibbs
energies of formation of iron species and revise the diagram.
Elemental iron has bcc lattice at standard conditions. Iron forms
two well-known oxides, Fe3O4 and Fe2O3 [4]. Iron monoxide FeO is
thermodynamically unstable and decomposes spontaneously according
to the reaction 4FeO (s) → Fe (bcc) + Fe3O4 (s). Since iron can form
mixed oxides with oxidation state equal to IV [5], it is interesting to
make thermodynamic prediction of oxidation properties of hypothetical
compound “FeO2”. The standard Gibbs energy of formation of “FeO2”
was estimated using methods proposed earlier [6,7]. In aqueous solution
iron forms a variety of unhydrolyzed and hydrolyzed species with
oxidation degrees II (Fe2+, FeOH+, HFeO2 , FeO22 ), III (Fe3+, FeOH2+,
Fe(OH) 2 , Fe(OH) 4 ) and VI ( FeO24 ). Polymerized species like
Fe2 (OH)24 and Fe3 (OH)54 and oxyhydrate FeOOH aren’t considered.
The standard Gibbs energies of formation used in calculations are
presented in Table 1.
Calculations show that domains of thermodynamic stability of Fe II
species with respect to pH don’t depend on activities of ions in solution.
However, in diluted media, when a[Fe] < 10–8 mol l–1, the domain of
stability of Fe3O4 vanishes and FeOH+ is oxidized directly to HFeO2 .
Table 1. The standard Gibbs energies of formation of iron species.
Compound f G o298 ,J mol1 Reference Compound f G o298 ,J mol1 Reference
Fe3O4 (s) –1 014 160 [8,9] FeOH2+(aq) –244 800 [3]
Fe2O3 (s) –742 200 [8,9] Fe(OH)2 (aq) –427 800 [3]
“FeO2” (s) –360 000 [6,7] Fe(OH)4 (aq) –842 200 [10]
2+ 
Fe (aq) –86 600 [3] HFeO (aq)
2 –405 800 [3]
2
Fe3+ (aq) –12 100 [3] FeO (aq)
2 –295 300 [9]
2
FeOH+ (aq) –290 000 [3] FeO (aq)
4 –352 300 [3]

Figure 1. The activity – pH diagram for FeIII species.

Figure 1 shows the predominance diagram of FeIII species. The

following order of oxidation is possible depending on ion activities:
lg a[Fe] > –2,91: Fe3+ (aq) → Fe2O3 (s) → Fe(OH)4 (aq);
–2,91 > lg a[Fe] > –4,56: Fe3+ (aq) → FeOH2+(aq) → Fe2O3 (s) →
→ Fe(OH)4 (aq);
–4,56 > lg a[Fe] > –12,15: Fe3+ (aq) → FeOH2+(aq) → Fe(OH)2 (aq) →
→Fe2O3 (s) → Fe(OH)4 (aq);
lg a[Fe] < –12,15: Fe3+ (aq) → FeOH2+(aq) → Fe(OH)2 (aq) →
→ Fe(OH)4 (aq).
Figure 2. The potential – pH diagram for Fe – H2O system.
 In very diluted solutions the domain of stability of solid Fe2O3 also
vanishes. Calculations show that among all FeVI species only FeO24 is
thermodynamically stable. The revised potential – pH diagram of Fe –
H2O system at 25ºC, 1 bar and a[Fe] = 10–6 mol l–1 is presented at Figure
2. Dashed lines represent the hydrogen and oxygen electrodes and
border the domain of electrochemical stability of water at atmospheric
conditions. Dotted lines border the hypothetical domain of stability of
“FeO2”. It isn’t thermodynamically stable at standard conditions and
doesn’t form a separate oxide layer.

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