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J Appl Electrochem (2010) 40:543–549

DOI 10.1007/s10800-009-0026-9

ORIGINAL PAPER

Thermodynamics of chromate replacements by various


homologous transition metal oxyanions
E. McCafferty

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

E/V vs. S.H.E.


5th
Period Zr Nb Mo Tc Ru Rh Ti
0.5 CrO4 -2
TcO 4 -, VO 4 -3
72 73 74 75 76 77 78
0.0
6th
Period Hf Ta W Re Os Ir Pt
-0.5
WO4 -2 to W 2 O5
Fig. 1 A portion of the periodic table showing metallic elements for -1.0
which oxyanions were considered as chromate replacements. Atomic MoO4 -2 WO4 -2 to WO 2
numbers are given for each element shown. Thermodynamic data are -
-1.5 ReO4
available or can be estimated for the elements shaded gray in the figure
-2.0
10 -7 10 -6 10 -5 10 - 4 10 -3 10 -2 10 -1 10 0
2 Thermodynamic calculations and results
Concentration/M L-1

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.

Calculations for each of the oxyanions listed in Table 1 WO4 -2 to WO 2


0.0
were performed for pH 0, 7, and 14 and for oxyanion
concentrations ranging from 1 9 10-6 to 1 M. Figure 2 -0.5
shows calculated results for pH 7.
Figures 3 and 4 show results for pH 0 and pH 14, -1.0
respectively. It can be seen that the calculated half-cell
pH 0
reduction potential depends markedly on the pH and also -1.5
on the concentration of the oxyanion.
-2.0
2.2 Overall reactions with iron 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 10 -1 10 0
-1
Concentration/M L

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

Table 1 Reduction reactions of


MnO4- ? 4H? ? 3e- ? MnO2 ? 2H2O E = 1.692 - 0.0788 pH ? 0.0197 log [MnO4-]
various oxanions of transition
metals and the reduction TcO4- ? 4H? ? 3e- ? TcO2 ? 2H2O E = 0.738 - 0.0788 pH ? 0.0197 log [TcO4-]
potential ReO4- ? 4H? ? 3e- ? ReO2 ? 2H2O E = 0.510 - 0.0788 pH ? 0.0197 log [ReO4-]
2CrO4-2 ? 10H? ? 6e- ? Cr2O3 ? 5H2O E = 1.386 - 0.0985 pH ? 0.0197 log [CrO4-2]
MoO4-2 ? 4H? ? 2e- ? MoO2 ? 2H2O E = 0.606 - 0.1182 pH ? 0.0295 log [MoO4-2]
OsO4-2 ? 4H? ? 2e- ? OsO2 ? 2H2O E = 1.607 - 0.1182 pH ? 0.0295 log [OsO4-2]
WO4-2 ? 4H? ? 2e- ? WO2 ? 2H2O E = 0.386 - 0.1182 pH ? 0.0295 log [WO4-2]
2WO4-2 ? 6H? ? 2e- ? W2O5 ? 3H2O E = 0.801 - 0.1773 pH ? 0.0591 log [WO4-2]
2VO4-3 ? 10H? ? 4e- ? V2O3 ? 5H2O E = 1.238 - 0.1477 pH ? 0.0295 log [WO4-2]

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J Appl Electrochem (2010) 40:543–549 545

2.0 Table 2 Overall reactions of various transition metal oxyanions with


pH 14 an iron surface
1.5 Oxyanions of transition metals of the fourth period
MnO4 -
HTiO3- ? H? ? TiO2 ? H2O
1.0
6VO4-3 ? 4Fe ? 18H? ? 3V2O3 ? 2Fe2O3 ? 9H2O
CrO4 -2 2CrO4-2 ? 2Fe ? 4H? ? Cr2O3 ? Fe2O3 ? 2H2O
0.5 -2
E/V vs. S.H.E.

OsO4 TcO 4 - ReO - VO -3 2MnO4- ? 2Fe ? 2H? ? 2MnO2 ? Fe2O3 ? H2O


4 4
0.0 3NiO4-2 ? 4Fe ? 6H? ? 3NiO ? 2Fe2O3 ? 3H2O
Oxyanions of transition metals of the fifth period
-0.5 HZrO3- ? H? ? ZrO2 ? H2O
6NbO3- ? 2Fe ? 6H? ? 6NbO2 ? Fe2O3 ? 3H2O
-1.0 2NbO3- ? 2H? ? Nb2O5 ? H2O
3MoO4-2 ? 2Fe ? 6H? ? 3MoO2 ? Fe2O3 ? 3H2O
-1.5 2TcO4- ? 2Fe ? 2H? ? 2TcO2 ? Fe2O3 ? H2O
MoO4 -2 WO4 -2
2RuO4-2 ? 2Fe ? 4H? ? Ru2O3 ? Fe2O3 ? 2H2O
-2.0
10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 10 -1 10 0 2RuO4- ? 2Fe ? 2H? ? 2RuO2 ? Fe2O3 ? H2O
Concentration M L
-1 2RhO4-2 ? 2Fe ? 4H? ? Rh2O3 ? Fe2O3 ? 2H2O
Oxyanions of transition metals of the sixth period
Fig. 4 Results of calculations for the formation of oxides by the HfO3-2 ? 2H? ? HfO2 ? H2O
electrochemical reduction of various oxyanions at pH 14
2TaO3- ? 2H? ? Ta2O5 ? H2O
3WO4-2 ? 2Fe ? 6H? ? 3WO2 ? Fe2O3 ? 3H2O
considered. In the interaction of molybdate inhibitors with 6WO4-2 ? 2Fe ? 12H? ? 3W2O5 ? Fe2O3 ? 6H2O
iron, for example, the cathodic half-cell reaction is: 2ReO4- ? 2Fe ? 2H? ? 2ReO2 ? Fe2O3 ? H2O
2 þ  3ReO4-2 ? 2Fe ? 6H? ? 3ReO2 ? Fe2O3 ? 3H2O
MoO4 þ 4H þ 2e ! MoO2 þ 2H2 O ð1Þ
3OsO4-2 ? 2Fe ? 6H? ? 3OsO2 ? Fe2O3 ? 3H2O
and the anodic reaction is: 3IrO4-2 ? 2Fe ? 6H? ? 3IrO2 ? Fe2O3 ? 3H2O
þ 
2Fe þ 3H2 O ! Fe2 O3 þ 6H þ 6e : ð2Þ
The overall reaction is the sum of these two half-cell were estimated as follows. For the oxyanions where data
reactions: are available, a plot of lo versus the radius of the central
2Fe þ 3MoO4 2 þ 6Hþ ! Fe2 O3 þ 3MoO2 þ 3H2 O: ð3Þ cation in the oxyanion gave a linear plot, from which
lo(HfO3-2) and lo(TaO3-) were calculated (Fig. 5). The
The standard free energy change for the overall reaction calculated results are: lo(HfO3-2) = -1,169 kJ mole-1
is given by:
X X
DGo ¼ mi loi ðproductsÞ  mi loi ðreactantsÞ: ð4Þ -200
i i y = 628.73 - 2531.4 x
Chemical Potential, µo , of Oxyanion/kJ

Correlation coeff. = 0.91


where mi are the stoichiometric coefficients and are the loi -400
MnO4 -
chemical potentials (also called partial molar free energies
of formation DGof ) of the various species in their standard -600
ReO4 -
states. For this example,
CrO4 -2
DGo ¼ ½lo ðFe2 O3 Þ þ 3lo ðMoO2 Þ þ 3lo ðH2 OÞ -800 MoO4 -2 WO4 -2
   
 2lo ðFeÞ þ 3lo MoO4 2 þ 6lo ðHþ Þ ð5Þ VO4 -3 NbO3 -
o o ? o -1000 HTiO3 -
where l (Fe) = 0 and l (H ) = 0. Values of l for the
other chemical species in Eq. 5 were taken from Pourbaix’s
Atlas [16]. The result is: DGo = -380 kJ. Normalized per -1200 HZrO3 -
TaO3 -
mole of inhibitor, DGo = -380 kJ per 3 moles MoO4-2, or HfO3 -2
-127 kJ mole-1 MoO4-2. -1400
Similar calculations were performed for oxyanion spe- 0.4 0.5 0.6 0.7 0.8
Radius of Central Cation in Oxyanion Complex/Å
cies of various transition elements, as shown in Table 2.
Values of loi were taken from Pourbaix [16] or Bard [26]. Fig. 5 Estimation of the chemical potentials, lo, for TaO3- and
Values for lo(HfO3-2) and lo(TaO3-) are not available but HfO3- anions

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546 J Appl Electrochem (2010) 40:543–549

and lo(TaO3-) = -990 kJ mole-1. Ionic radii used in this 100


6th Period
approach were taken from Shannon and Prewitt [27, 28] or 5th Period

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 -

without the participation of the underlying iron substrate in RuO4 -2


NiO4 -2
an electrochemical reaction. -600
RhO4 -2
Other instances considered here of chemical (i.e., non-
-700
electrochemical) reactions to form the metal oxide of the 20 30 40 50 60 70 80
oxyanion are the reaction of HTiO3- to TiO2, of NbO3- to Atomic Number of Central Metal Atom in Oxyanion
Nb2O5, of HfO3-2 to HfO2, and of TaO3- to Ta2O5.
Fig. 6 Calculated standard free energy change DGo for the reaction
Table 3 shows the calculated standard free energies DGo of various oxyanions with iron surfaces
for the formation of transition metal oxides from their
oxyanions. These values of DGo per mole of oxyanion are
plotted in Fig. 6, as a function of the atomic number of the Figure 6 shows that surface treatment of iron (steel)
central atom in the oxyanion. Values of DGo per mole of with any of the oxyanions considered here under standard
oxyanion decrease with atomic number within a given conditions leads to a spontaneous reaction, as evidenced by
period in the periodic table. Moreover, values of DGo per negative values of DGo. The oxyanions which produce
mole of oxyanion are periodic in the sense that this pattern more negative values of DGo (per mole of oxyanion) than
is repeated for the fourth through sixth periods of the that of CrO4-2 are MnO4-, NiO4-2, RuO4-, RuO4-2, and
periodic table. RhO4-2.

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

Ti 22 HTiO3- TiO2 -170 1 -170


V 23 VO4-3 V2O3 -1492 6 -249
Cr 24 CrO4-2 Cr2O3 -788 2 -394
Mn 25 MnO4- MnO2 -1,009 2 -505
Ni 28 NiO4-2 NiO -1,659 3 -553
Zr 40 HZrO3- ZrO2 -70 1 -70
Nb 41 NbO3- NbO2 -278 6 -47
Nb2O5 -69 2 -35
Mo 42 MoO4-2 MoO2 -380 3 -127
Tc 43 TcO4- TcO2 -457 2 -229
Ru 44 RuO4-2 Ru2O3 -1,268 2 -634
RuO4- RuO2 -1,154 2 -577
Rh 45 RhO4-2 Rh2O3 -1,310 2 -655
Hf 72 HfO3-2 HfO2 -123 1 -123
Ta 73 TaO3- Ta2O5 -83 2 -42
W 74 WO4-2 WO2 -253 3 -84
W2O5 -493 6 -82
Re 75 ReO4- ReO2 -332 2 -166
ReO4-2 ReO2 -686 3 -229
Os 76 OsO4- OsO2 -960 3 -320
Ir 77 IrO4-2 IrO2 -1,214 3 -405

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J Appl Electrochem (2010) 40:543–549 547

The oxyanions which produce values of DGo (per mole 300


of oxyanion) similar to CrO4-2 are OsO4-2, and IrO4-2. -0.40
200 pH 14
The other oxyanions considered here produce values of
DGo (per mole of oxyanion) which are less negative than Non-spontaneous -0.20

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

written. For example, for the reaction of molybdates with


iron:
10 -1
2Fe þ 3MoO4 2 þ 6Hþ ! Fe2 O3 þ 3MoO2 þ 3H2 O ð3Þ
Concentration of MoO 4-2 /M L -1

1
Keq ¼   : ð8Þ 10 -2
2 3 6
MoO4 ½Hþ 

Use of Eq. 8 in 7 gives: 10 -3


 
DG ¼ 380:1  17:118 log MoO4 2 þ 34:276 pH ð9Þ
10 -4
where all free energy values are in kJ. Figure 7 shows
how the free energy change DG varies with the concen-
tration of molybdate ion (MoO4-2) and with the pH 10 -5 Spontaneous Non-
according to Eq. 9. The free energy change becomes more spontaneous
negative with increasing concentration of MoO4-2
10 -6
(at fixed pH) and with decreasing pH (at fixed MoO4-2 0 2 4 6 8 10 12 14
concentration). pH
Note from Fig. 7 that Eq. 9 proceeds spontaneously at
Fig. 8 Regions of spontaneity and non-spontaneity for the reaction of
pH 7 and pH 0, but not at pH 14. The borderline between molybdate ions with an iron surface
regions of spontaneity and non-spontaneity can be deter-
mined by setting DG = 0 in Eq. 9 and solving for pH. The
result is: involve a reduction reaction but rather a chemical (non-
  electrochemical) reaction. For the zirconate ion on iron,
pH ¼ 11:102 þ 0:5 log MoO4 2 : ð10Þ
mentioned earlier, results are shown in Fig. 9. Again, the
This straight line is shown in Fig. 8. free energy change becomes more negative with increasing
The corresponding values of electrode potential E for concentration of oxyanion (at fixed pH) and with
the reaction in Eq. 3 are also given in Fig. 7. These values decreasing pH (at fixed oxyanion concentration). Note
of E are given by DG = -nFE, where all terms have their from Fig. 9 that Eq. 6 proceeds spontaneously at pH 7 and
usual meaning. pH 0, but not at pH 14.
Calculations for the change in free energy were also Regions of spontaneity (for iron) are shown in Figs. 10,
performed for the case in which the formation of the metal 11, and 12 for oxyanions of metals in the fourth through
oxide from the oxyanion of the transition metal does not sixth periods of the periodic table.

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548 J Appl Electrochem (2010) 40:543–549

40 10 0

NbO3 - to NbO

Concentration of Oxyanion/M L-1


2
20 pH 14 10 -1
MoO4 -2
Non-spontaneous
0 10 -2
NbO3 - to Nb 2 O5
-20 pH 7 10 -3
HZrO3 -
∆G/kJ

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

Fig. 9 Calculated free energy change DG at various oxyanion


concentrations and pH values for the reaction of zirconate ions 10 0
(HZrO3-) with iron surfaces Concentration of Oxyanion/M L-1

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 -5 Fig. 12 Regions of spontaneity for the reaction of iron with


oxyanions of the sixth period of the periodic table

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

Thermodynamic calculations have been made for the References


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are MnO4-, NiO4-2, RuO4-, RuO4-2, and RhO4-2. 23. Asami K, Chen S-C, Habazaki H, Hashimoto K (1993) Corros Sci
For iron, the oxyanions which produce values of DGo 35:43
24. Hoppe H-W, Strehblow H-H (1990) Surf Interface Anal 16:271
(per mole of oxyanion) similar to CrO4-2 are OsO4-2, and
25. Patrito EM, Torresi RM, Leiva EPM, Macagno VA (1992)
IrO4-2. Electrochim Acta 37:281
For iron, the other oxyanions considered here produce 26. Bard AJ, Parsons R, Jordan J (eds) (1985) Standard electrode
values of DGo (per mole of oxyanion) which are less potentials in aqueous solution. Marcel Dekker, Inc., New York
27. Shannon RD, Prewitt CT (1970) Acta Crystallogr B26:1046
negative than that of CrO4-2. These oxyanions are
28. Shannon RD, Prewitt CT (1969) Acta Crystallogr B25:925
HTiO3-, VO4-3, HZrO3-, NbO3-, MoO4-2, TcO4-, 29. Pauling L (1948) The nature of the chemical bond. Cornell
HfO3-2, TaO3-, WO4-2, ReO4-, and ReO4-2. University Press, Ithaca, p 343

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