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DOI 10.1007/s10800-009-0026-9
ORIGINAL PAPER
Received: 22 June 2009 / Accepted: 25 September 2009 / Published online: 10 October 2009
Ó Springer Science+Business Media B.V. 2009
Abstract The free energy change is calculated for the persistence of the chromate ion, as evidenced by its intense
interaction of 19 different oxyanions (metalates) with iron yellow color [1, 2].
(steel) or aluminum surfaces. The oxyanions considered Thus, there is an ongoing effort to identify effective
here are those of the transition metals in the fourth through chromate replacements. One approach is to use analogous
sixth periods of the periodic table. The oxyanions which oxyanions of transition metals other than chromium.
produce more negative values of DGo (per mole of oxy- Experimental studies have been done on the use of
anion) than that of chromate (CrO4-2) are permanganate molybdates [3–7], vanadates [3, 8], tungstates [3, 4, 6], and
(MnO4-), nickelate (NiO4-2), ruthenate (RuO4- or RuO4-2), permanganate [9]. Other related approaches have involved
and rhodate (RhO4-2). The oxyanions which produce values the use of cerium salts [10], phosphates [11], hydrotalcite
of DGo (per mole of oxyanion) similar to CrO4-2 are osmate inorganic coatings [12], the addition of non-chromates to
(OsO4-2), and iridate (IrO4-2). organic coatings [13], and the use of alkoxy-titanates
[14, 15] or alkoxy-zirconates [15].
Keywords Chromate replacements Oxyanions The purpose of this communication is to consider the
Metalates Thermodyamics Corrosion thermodynamics of various oxyanions of transition metals
in their interaction with iron (steel) or aluminum surfaces.
The oxyanions considered here are those of the transition
metals shown in Fig. 1, which is a portion of the periodic
1 Introduction table. Appropriate thermodynamic data are available
(or can be estimated) for the elements which are shaded
Chromates are effective corrosion inhibitors when added to gray in Fig. 1.
aqueous solutions and are also useful as conversion coat- The oxyanions considered here are titanate (HTiO3-),
ings. That is, surface treatment of a metal with chromates vanadate (VO4-3), chromate (CrO4-2), permanganate
produces a mixed oxide of Cr2O3 and the oxide of the (MnO4-), nickelate (NiO4-2), zirconate (HZrO3-), niobate
underlying substrate. In the past, chromates have been (NbO3-), molybdate (MoO4-2), pertechnetate (TcO4-),
used to treat surfaces of steel, aluminum, and galvanized ruthenate (RuO4-2 and RuO4-), rhodate (RhO4-2), hafnate
steel. (HfO3-2), tantalate (TaO3-), tungstate (WO4-2), rhenate
However, it is now widely understood that the use of (ReO4-2 and ReO4-), osmate (OsO4-2), and iridate
chromates presents health and environmental problems due (IrO4-2).
to the toxicity of the Cr?6 species and due to the These thermodynamic calculations are intended to assist
further experimental studies. Oxide films which form under
thermodynamically spontaneous conditions are candidates
for further studies involving reaction kinetics, surface
E. McCafferty (&)
analysis, the use of oxyanion surface treatments prior to the
Science Applications International Corporation, Naval Research
Laboratory, Washington, DC 20375, USA application of organic coatings, and long-term corrosion
e-mail: mccafferty@anvil.nrl.navy.mil testing and evaluation.
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544 J Appl Electrochem (2010) 40:543–549
2.0
Group Group Group Group Group
4B 5B 6B 7B 8B pH 7
1.5
4th 22 23 24 25 26 27 28 MnO4 -
Period Ti V Cr Mn Fe Co Ni
1.0
OsO4 -2
40 41 42 43 44 45 46
2.1 Cathodic half-cell reactions Fig. 2 Results of calculations for the formation of oxides by the
electrochemical reduction of various oxyanions at pH 7
Half-cell cathodic reactions for several familiar oxyanions
and the corresponding expressions for the cathodic elec-
trode potential are given in Table 1, and are taken from 2.0
Pourbaix’s Atlas [16]. The form of the resulting oxide in MnO4 -
each half-cell reaction is based on the oxide stability 1.5
according to the Pourbaix diagram [16] or is taken from
available surface analysis by X-ray photoelectron spec- 1.0 VO 4 -3
TcO4 -
troscopy (XPS) [9, 17–25]. The reduction of tungstate
0.5
(WO4-2) was considered to form either WO2 or W2O5.
E/V vs. S.H.E.
The section above pertains to the cathodic half-cell reaction Fig. 3 Results of calculations for the formation of oxides by the
alone, but the anodic half-cell reaction also must be electrochemical reduction of various oxyanions at pH 0
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546 J Appl Electrochem (2010) 40:543–549
Oxyanion on Iron
0 4th Period
from Pauling [29]. TaO3 -
HZrO3 - NbO3 -
It should be noted that in some cases, the formation of -100 WO4 -2
HfO3 -
MoO4 -2
the metal oxide from the oxyanion of the transition metal HTiO3 -
ReO4 -
-200
does not involve a reduction reaction but rather a chemical VO 3 -3 TcO 4 - ReO4 -2
(non-electrochemical) reaction. An example is: -300
OsO4 -2
-1
HZrO3 þ Hþ ! ZrO2 þ H2 O: ð6Þ
∆G o /kJ mole
-2
-400 CrO4
IrO4 -2
Thus the oxyanion can form its transition metal oxide -500 MnO4 - RuO4 -
Table 3 Calculated results for the free energy change DGo for the reduction of transition metal oxyanions on an iron surface
Metal atom Atomic Oxyanion Resulting DGo Number of DGo/oxyanion
number oxide (reaction) oxyanions in in kJ mole-1
in kJ overall reaction
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J Appl Electrochem (2010) 40:543–549 547
E in V vs. S.H.E
100
that of CrO4-2. These oxyanions are HTiO3-, VO4-3,
∆G/kJ
HZrO3-, NbO3-, MoO4-2, TcO4-, HfO3-2, TaO3-, 0 0.0
pH 7
WO4-2, ReO4-, and ReO4-2.
-100 0.20
Spontaneous
-200
0.40
2.3 Non-standard conditions pH 0
-300
0.60
For aqueous electrochemistry, standard conditions (which -400
refer to DGo) are unit activity for all dissolved ions (and 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 10 -1 10 0
298°K). This includes the hydrogen ion H?, so that pH = 0 Concentration of MoO 4 -2 /M L -1
is the pH in the standard state.
The free energy change DG for non-standard conditions Fig. 7 Calculated free energy change DG at various oxyanion
concentrations and pH values for the reaction of molybdate ions
is related to the free energy change DGo in the standard (MoO4-2) with iron surfaces
state by:
DG ¼ DGo þ 2:303 RT log Keq ð7Þ
-2 +
2 Fe + 3 MoO +6H = Fe 2 O3 + 3 MoO 2 + 3 H 2 O
where Keq is the equilibrium constant for the reaction as 10 0
4
1
Keq ¼ : ð8Þ 10 -2
2 3 6
MoO4 ½Hþ
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548 J Appl Electrochem (2010) 40:543–549
40 10 0
NbO3 - to NbO
Spontaneous
-40 10 -4
TcO 4 -, RuO4 -,
-60 pH 0 10 -5
RuO4 -2 , RhO4 -2
-80 10 -6
0 2 4 6 8 10 12 14
pH
-100
10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 10 -1 100 Fig. 11 Regions of spontaneity for the reaction of iron with
- -1
Concentration of HZrO3 /M L oxyanions of the fifth period of the periodic table
10 -1 WO4 -2
HfO3 -2
10 0
-2
10
TaO3 -
HTiO3 -, CrO4 -2 , MnO4 -, NiO4 -2
10 -1
Concentration of Oxyanion/M L-1
10 -3
10 -2 10 -4
10 -3 10 -5 ReO4 -, ReO4 -2
OsO4 -2 , IrO 2 -2
-6
10 -4 VO 4 -3 10
0 2 4 6 8 10 12 14
pH
10 -6
0 2 4 6 8 10 12 14
pH chemical potential lo(Al2O3) is more negative than that for
lo(Fe2O3). These values are -1,576 and -740 kJ mole-1,
Fig. 10 Regions of spontaneity for the reaction of iron with
oxyanions of the fourth period of the periodic table respectively [16].
All the corresponding electrochemical reactions on
aluminum given in Table 2 are spontaneous over the entire
2.4 The case for aluminum pH range of 0 to 14. On aluminum, the chemical (i.e., non-
electrochemical reactions have the same regions of stability
If the substrate metal is aluminum rather than iron, the as for iron and have been given in Figs. 8, 10, and 11.
overall reactions are similar. For molybdates, for example,
Eq. 3 is replaced by: 2.5 Limitations
2Al þ 3MoO4 2 þ 6Hþ ! Al2 O3 þ 3MoO2 þ 3H2 O: ð11Þ
These calculations carry with them all the usual limitations
Values of DGo for the case of aluminum are of thermodynamics. That is, thermodynamics is the realm
considerably more negative than for iron because the of what is possible, but gives no information on the rates of
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J Appl Electrochem (2010) 40:543–549 549
reactions. Moreover, the actual corrosion properties of the This thermodynamic approach gives no information on
resulting oxides on iron or aluminum must be determined the rates of reactions. Moreover, the actual corrosion
by experimental measures. properties of the resulting oxides on iron or aluminum must
be determined by experimental measures.
3 Conclusions
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