Ccwrosion Science, Vol. 39, No. 1,pp.

43-57, 1997
Copyright 0 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
001&938X/97 %17.00+0.00

PII: s~l~9~x(%~lol-l

REVISED

POURBAIX

DIALOGS
25300C

B. BEVERSKOG

FOR CHROMIUM

AT

and I. PUIGDOMENECH

Stud&k Material AB, S-61 1 82 Nykoping, Sweden

Abstract-The
Pourbaix diagrams (potential-pH diagrams) for chromium at 25-300C have been revised. The
diagrams were calculated for two concentrations: 10- and IO-* molal. Extrapolation of thermochemical data to
elevated temperatures has been performed with the revised model of Helgeson-~rkh~-Flowers,
which also
allows uncharged aqueous complexes, such as Cr(OH)X(aq), to be handled. The calculations show that the
hydroxides Cr(OH)a, Cr(OH)s, and the oxides CrOz and Cr03 are not stable at the investigated temperature and
concentration interval. CraOs is the only stable solid chromium compound in aqueous solution in the environment
studied, with the exception of very diluted solutions such as lo-smolal at T> 150C where no solid chromium
compound is stable. The dichromate ion does not predominate anywhere within the calculated concentration range.
Copyright @ 1996 Elsevier Science Ltd
Keywords:

A. chromium, C. Pourbaix diagram.

INTRODUCTION
Chromium is a metallic element well known for its good corrosion properties. The reason
for this is not due to the element itself, which is a very base metal, but to one of its solid
reaction products, Cr203. The element is protected in oxidising conditions by the formation
of Cr203, which acts as a barrier between the metal and the environment. This oxide, which
is a p-type semiconductor, grows by diffusion of cations from the metal to the oxide/solution
interface, the transport path being cation vacancies. The diffusion coefficients are very low,
which means low growth rates of the oxide. The good corrosion behaviour of chromium is
the reason to alloy metals with chromium thereby making corrosion resistant alloys. The use
of these corrosion resistant alloys containing chromium, such as stainless steels, has
increased continuously in recent years. Knowledge of the limits for the good corrosion
resistance is therefore quite important. One way to predict the corrosion resistance of
chromium is to consider the the~odynamics
(equilibrium relations) for the system.
Chemical and electrochemical equilibria are elegantly summarised in a Pourbaix
diagram, which is a potential-pH diagram, The diagram is a map of the multidimensional
thermochemical space and predicts areas of immunity (no corrosion, by definition),
passivity (a solid reaction product) and corrosion (a dissolved reaction product), The
Pourbaix diagram for chromium has been studied by many authors-2 and these diagrams
Manuscript received 27 February 1996.
43

44

B. Beverskog and I. Puigdomenech

are particularly useful for studying the corrosion behaviour of many corrosion resistant
alloys, including stainless steel, as chromium plays an important part in their corrosion
resistance. Diagrams for elevated temperatures have also been reported by several
workers 2,6&i i,t4,1%17,2swhic h in general have uncritically used the species that Pourbaix
used in his thesis in 1945. Since the work of Pourbaix, new findings have taken place which
makes it relevant to once again revise the Pourbaix diagram for chromium. Concentrations
of dissolved chromium species below 10M6 have only been reported in one work,s but
showing only the stability area of Cr203 at 25C.
The aim of this work is threefold. First, a partly new set of aqueous species, which has
not been used in earlier Pourbaix diagrams, has been used in the present calculations.
Secondly, a new method (in the context of Pourbaix diagrams) to extrapolate
the~o~hemical
data from 25C to elevated temperatures has been used. Previous studies
had in general used the conventional correspondence principle of Criss and Cobble. The
third aim of this work is to calculate Pourbaix diagrams also for lo-* molal concentration
of dissolved species at elevated temperatures.

CHOICE

OF CHROMIUM

SPECIES

Chromium has the electron configuration [Ar]3d54s. The relatively low energy in the sand d-levels cause chromium compounds to have the oxidation numbers O-VI. The
oxidation numbers that are most common and stable in water solutions are II, III and VI.
The oxidation numbers IV and V exist as intermediates in redox reactions. However, these
products are unstable with respect to disproportionation
to III and VI or react with the
solvent. The most important and most stable oxidation number in water solution is III and
Cr(I1) is a strong reducing agent, which is not particularly stable in aqueous solutions, not
even at low potentials. Cr(I1) is easily oxidised by oxygen to Cr(II1). All Cr(V1) compounds
are oxycompounds in aqueous solutions and very strong oxidation agents in acidic
solutions.
Table 1 shows 40 chromium species that have been considered in this work for the
aqueous system of chromium. Six solids and 10 aqueous chromium complexes have been
included in the calculations, Cr20s, CrOz and CrOs are the only oxides of importance.22
CrOz has been included although it is unstable in aqueous solution because it has been
claimed to exist at elevated temperatures. Nothing is known about the hydrolysis reactions
of Cr* + .23 Thirteen solids, one gaseous and 10 aqueous complexes have been excluded
since they are not stable in equilibrium with aqueous solutions. The reasons for the
exclusions are the following: thermodynamic data for the chromium hydride system have
been reported in the literature.24-26 However, no chromium hydride is included in our
calculations owing to the kinetic effects involved in this system.25 Of the oxides, GO(s) is
not stable in aqueous solution and Cr304 is a powerful reducing agent. The tetra and penta
oxides are also unstable in aqueous solutions. Hydrous Cr203 (Cr203 *H20) is commonly
called chromium(II1) hydroxide, although its water content is variable. This solid is less
stable than the oxide and Cr(OH)3. The solid Cr(OH)3*nH20 is not considered because its
stability is expected to be lower than that of the unhydrous hydroxide. Only the enthalpies
are available for the hydrated forms of Cr203. CrOOH(s) has been excluded from this
study,because we believe, as discussed in the Results and Discussion, that this solid is not

45

Pourbaix diagrams for Cr

Table 1. Considered species in the aqueous system of chromium
Condition

Oxidation number

Included

crystalline
solid
crystalline
solid
9,

0
I

Cr

gaseous
crystalline

3,
7.
9.
,,
,,
3,
3.

solid
crystalline

3,
dissolved

>,
7,
7,
7,
,,
,,
,.

7,
1,
1.
z

II
1

CrH
cro

CrW-02
CrH2
CrH2

31

II/III
III

cr304

Cr203

Cr203. H20
CrzOs. 2 Ha0
Cr203. 3 Hz0

WOW3
Cr(OH)s

VI
VIII
X
II
III
1

V
VI

n Hz0

CrOOH
Cr2H7

III/IV
IV
..

Excluded

CrOz
Cr(OH)4
CrOs

Cr*+
Cr3 +
CrOH+
Cr(OH):
Cr(OHMaq)
Cr(OH); (?)

H2Cr04
HCrOi
CrOiCr@
6+10=16

Cr04
Cr05
CrHAaq)
CrO:Cr(OH)i-

Crz(OH)i
Cr@H),
CrO:Cr04 +
CrOz+
CrsOf,
Cr40&
14+ lo=24

thermodynamically stable with respect to the oxide. The existence of a hydrated Cr(IV)
oxide (Cr(OH)4) has not been verified.22,23,39CrOi-(aq) and Cr(OH)z-(aq), if they form at
all, would only be stable in unusually high alkaline media and are therefore not considered
here. The polynuclear hydrolysis products of chromium(II1) have not been included as
they are stable only in concentrated solutions.23 The dioxide and the tetra hydroxide as
well as the ion CrOi-(aq) have the oxidation numbers I, IV and V, respectively, and are
thereby not stable in water solutions as they disproportionate.** The six valent ions Cr04+
and CrO:+(aq) are not consistent with modern electrostatic theory of chromium
hydrolysis.
The anionic hydroxo chromium(II1) complex in alkaline solutions is denoted as

B. Beverskog and 1. Puigdomenech

46

Table 2. Thermodynamic data at 25C for the system chromium-water. In general more digits than required by
the expected uncertainty are given in order to retain the values for the changes in the reactions among individual
species
c(T)/(J

Species
Cr(cr)
Cr(OHMs)
Cr203W

Cr(OHX(s)
CrOa(cr)
CQfcr)
Cr2 +
Cr+
CrOH*

Cr(OH)z +
Cr(OH)s(aq)
chromite aniod
CrO:HCrO;

H$XUaq)
Cr_@-

S
(J K-t mol-)

Arc0
(kJ mol-)
0.

23.6
El.
81.2
105
54
73.2

- 585.57
- 1053.09
-873.17
- 548
-510.04
-174
-215
-431.8
-633.19
-834.13
- 1005.89

21.76
116.064
119.37
127.612
94.6
71.76

-100

-11

-293
-151
-92
-38
-83.8

-30
160
340
480
410

50.21
195.2
311
299.5

- 727.75
-765.14
- 764.00
- 1302.23

a*

K- mol-)
=a+bT+cT-=
bx IO3

cxw6

8.98
8.648
9.20
41.639
17.2
87.86

-0.096:
-2.874
- 1.565
-4.217
- 1.674

-251
-50
84
- 175

+For aqueous species a corresponds to the standard partial molar heat capacity at 25C and the revised
Helgeson-Kirkham-Flowers
model has been used to obtain its temperature dependence.
XC$Cr(cr), T)/(J K- mol-) = o + bT + CT-~ + dT*, with d = 2.26 x IO-.
8 Data obtained

using stoichiometry

Cr(OH);,

see text,

Cr(OH); and not the traditional notation of CrO, generally used in Pourbaix diagrams.
The difference is two water molecules. This is also in agreement with the nomenclature used
by Baes and Mesmer.23

THERMOCHEMICAL

DATA

A critical review of published thermodynamic data has been performed for the solids
and aqueous species described in the previous section, and best values have been selected as
described below. Data is usually available only for a reference temperature of 25C in the
form of standard molar Gibbs free energy of formation from the elements (A@) and
standard molar entropy (So). Equations for the temperature dependency of the standard
molar heat capacity (Cj) are usually available for solid and gaseous compounds. For
aqueous species, the standard partial molar properties are usually available. Extrapolation
of the~odynamic
data to other temperatures is performed with the methodology described
elsewhere.* For aqueous species T-extrapolations have been based on the electrostatic
and our methodology requires a value of Cj at 25C.
model of Helgeson et uZ.28--31

Pourbaix diagrams for Cr

47

The data selected for the calculations performed in this work are summarised in Table 2.
The selection criteria behind the values in this table are discussed below.

SOLIDS
The data for Cr(cr), CrzOa(cr) and CrOs(cr) are those in Kubaschewski et aL3* For
have been used. The parameters for the T-equation of
Cr02(s), the values listed in 33Y34
C,O(CrOz) are those estimated by35.
For the Cr(I1) hydroxide, the value of AfG has been derived from the only available
solubility equilibrium constant,36Y37while for Cr(OH)3(s) the upper limit for the solubility
constant proposed in the careful study of Rai et al.38 has been used. Of the estimates for
s(Cr(OH)3(s))34,37,39 that in the most recent review by Niki34 is adopted, while for
Cr(OH)*(s) the only estimate for s available39 is accepted. The approximation has been
made here that the parameters for the q(T) equations for Cr(OH)*(s) and Cr(OH)3(s) are
equal to those of their iron(I1) and (III) analogues as reported in 4o because there are no
literature values available. This corresponds to q(25C) of 86.3 and 92.6 J K- mol- for
Cr(OH)*(s) and Cr(OH)3(s), respectively.

AQUEOUS

SPECIES

The thermodynamic properties of H,O(l) at 25C recommended by CODATA4 have

been used in this work. The temperature dependence of these properties has been calculated
with the model of Saul and Wagner.42 The dielectric constant of water (which is needed for
the revised Helgeson-Kirkham-Flowers
model that describes the temperature dependency
of the thermodynamic properties of aqueous solutes) has been obtained with the equations
given by Archer and Wang.43
The data for Cr*+ and Cr3+ are those selected in the review by Niki.34 The value of
AfZ#(Cr3+) thus selected is that obtained by Dellien and Heplera (Af@ = -251 kJ mol-)
and agrees also with the values obtained by Vasilev et a1.45 Because Cr3+ is a key species in
the process of deriving the other thermodynamic
data, it is unfortunate that the
uncertainties in AfG and s for Cr3+ in Table 2 are quite large. For example, ,S(Cr3+)
data (mostly estimates) in the range - 37@-- 270 J K- mol- have been published in
the literature.57Y33,34,45-47Values of q(Cr3+) w -30 J K- mol- and C?(C$+)
x - 11
P
J K-t mol- have been derived from the work of Spitzer et al.48-50
Cr(II1) solutions in the presence of excess hydroxide contain the chromite ion, which
appears to be a polynuclear complex as it does not pass through semipermeable
and chromatographic
study has confirmed the
membranes.5 A spectroscopic
polynuclear nature of this complex (or complexes), and has established that no Cr(OH&
ions are formed as the result of Cr(II1) hydrolysis in aqueous solutions. The exact
stoichiometry of the chromite ion is therefore still unknown, but for the purpose of drawing
the Pourbaix diagrams, the formula Cr(OH); is used in this work, and data for this
hypothetical stoichiometry are given in Table 2. It must be pointed out, however, that this
assumption results necessarily in erroneous T-extrapolations of the thermodynamic data for

48

B. Beverskog and I. Puigdomenech

the chromite ion, and therefore in erroneous Pourbaix diagrams at elevated temperatures,
because this extrapolation relies (among other parameters) on the electric charge of the
aqueous species, which is unknown for the chromite ion.
The equilibrium constants (or lower limits) for the hydrolysis reactions of Cr(III)
reported
by
Rai
et a1.38 have
been
used to obtain
the values
of
AfGforCrOH2+, Cr(OH)l, Cr(OH),(aq), and Cr(OH), . The standard entropy changes for
Cr3+ + HzO(1) + CrOH2+ + H+
CrOH2+ + H20(1) $ Cr(OH)l

+ H+

proposed by Dellien et ~1.~~(A,@ = 41.8 and 32.6 kJ . mol-, respectively) are used to
obtain the entropies of the corresponding hydrolysis complexes. The data of Schug and
King are used to obtain the standard entropy of the chromite ion (assuming the
stoichiometry Cr(OH);). The value of S(Cr(OH),(aq)) has been estimated by assuming a
smooth variation of A,@ for the stepwise hydrolysis reactions. The values of q for the
hydrolysis products of Cr(II1) have been obtained by assuming the same standard heat
capacity changes as for the hydrolysis of Fe(III).27
Values for the chromate ion, CrOi-, are those in Refs 34 and 29. The data for HCrO;
and Cr@
have been calculated from the values for CrOz- and the values of A$ and the
equilibrium constants in the temperature range 255175C obtained by Palmer et d5 It must
be noted that the resulting values of S differ from those in Ref. 34 and the C; values differ
by as much as + 50 J K.-l mol- with those determined in Ref. 54. For H$ZrO,+(aq), the
equilibrium constant at I= 0 recommended by Baes and Mesmer23 has been used to obtain
ArG(H2Cr04(aq)), and the reaction enthalpy quoted in Table 10.9 of the same reference
has been used to obtain ~(H~~rO~(aq)), and a value for ($ for this aqueous complex has
been estimated from the heat capacities of dissociation for oxy-acids proposed by Smith et
aI.s5

CALCULATIONS
The methods and assumptions used to caiculate the chemical equilibrium diagrams
(including Pourbaix diagrams) have been described elsewhere. Calculations to draw the
Pourbaix diagrams presented in this work have been performed for eight temperatures in the
interval 25-300C (i.e. at 25,50,100, 150,200,250,285 and 3OOCj.Pourbaix diagrams have
been calculated in this work at two concentration levels, 10m6 and 10-8molal, at every
temperature. The former is the conventional corrosion limit stipulated by Pourbaix, and the
latter is intended to be used in high purity waters, such as in nuclear reactors of the boiling
water type. These concentrations are total concentration, i.e. the sum of all aqueous species
containing chromium at each coordinate point (Es&pH-value).
All values of pH given in this work are values at the specified temperature. The neutral
pH value of pure water changes with the tem~rature
with the ion product of water
(HzO(Q e H + OH-, ~Hneutra~ = 1/2pK,,r). To facilitate reading the Pourbaix diagrams,
the neutral pH value at the temperature of each diagram is given as a vertical dotted line.

Pourbaix diagrams for Cr

49

The thermodynamic calculations have been summarised in two types of equilibrium

diagrams: Pourbaix diagrams and predominance diagrams for dissolved species. Both types
of diagrams are predominance diagrams, but the former contains solid as well as dissolved
metallic species (and sometimes also gaseous species), while the latter only contains
dissolved species. Stability areas for solids in a Pourbaix diagram must be calculated with all
the dissolved species included. Omitted metallic species often result in diagrams with
misleading information, and it is therefore of vital importance that Pourbaix diagrams are
based on the species that represent todays knowledge of the chemical system in question.
Predominance diagrams for dissolved species are useful because they contain only dissolved
species, and they reveal the most stable aqueous species below the area hidden by a stable
solid phase. This type of diagram contributes additional information (as compared to the
corresponding Pourbaix diagrams) only when the metal in question has more than one
oxidation states. Otherwise the predominance for most of the aqueous species is already
predicted by a Pourbaix diagram, because the predominance areas of dissolved species when
the metal has only one oxidation state are pH-dependent and not dependent on the
potential. It would seem that predominance diagrams for dissolved species are independent
of the concentration level at which they are constructed. However, this might not be true as
concentrated solutions can contain polynuclear metallic aqueous ions, which in general do
not exist in diluted solutions. Therefore, predominances diagram for dissolved species
calculated for concentrated solutions often deviate from those for diluted solutions. In the
case of very diluted solutions such as 10m6and lo- molal, the predominant
diagrams for
dissolved species are the same. Pourbaix diagrams and predominance diagrams for
dissolved species are often superimposed to show the predominating dissolved species in
each part of the solid stability areas in a Pourbaix diagram. However, this can make the
diagram unclear and difficult to read, and it is avoided in this work by separating the
Pourbaix diagrams and the pr~ominan~
diagrams for dissolved species.

EXPERIMENTAL

RESULTS

AND DISCUSSION

There is unfortunately no experimental data in the literature on the stability of Cr(II1)

hydrolysis complexes at temperatures above 25C and the Pourbaix diagrams reported here
at T > 25C are therefore of a tentative nature. This is further increased by the uncertainty in
the the~odynamic
data for the C?+ and Cr3+ ions, and by the unknown stoichiometric
composition of the species occurring in alkaline solutions of Cr(II1). Nevertheless, the
diagrams presented here correspond to the best knowledge available today on the chemistry
of chromium.
Another source of uncertainty is the relative stability of the oxides and hydroxides of
Cr(II1). Deltombe et af. report a lower solubility, i.e. a higher stability, for Cr(OH)3(cr,hex)
than for Cr2Os(cr). Their data apparently originate from the work of Latimer37 who
estimated a value for S(Cr(OH)3, cr, hex). These data have later been extensively used.57Y8
Our values reflect instead the solubility of precipitated solid hydroxide and of crystalline
dichromium(II1) trioxide, with a higher stability for the oxide than for the hydroxide, which
agrees with the behaviour of other metal cations.
Lee,8 based on the data in Ref. 56, presented Pourbaix diagrams for chromium drawn
with the assumption that CrOOH(s) predominates in the temperature range 60-500C.

50

B. Beverskog

and I. Puigdomenech

Ziemniak5 also gives calculated solubilities for CrOOH(s) based on unpublished results by
Ziemniak et al. According to Laubengayer and Macune 58the oxyhydroxide of chromium is
a meta stable phase. The passive film on chromium consists of a bilayered structure with an
outer hydroxide layer, Cr(OH)s, and an inner oxide layer, Cr.203.59 Immediately after
immersion in an aqueous solution, the hydroxide layer has been found to be three times
thicker than the the oxide layer, and 20 h later the thicknesses of the layers were equa1.59
Nevertheless, the thickness of the hydrated layer after prolonged exposure is still unclear,
although it is reasonable to assume that the hydrated layer would be a minor part of the

~Hac

7
PH~wo~~

pHam%
Fig. 1.

Pourbaix

diagram

for chromium

and [Cr(aq)bt

= 10m6 m at 25, 100,200

and 300C.

Pourbaix diagrams for Cr

51

passive film at prolonged exposures. This view is indirectly confirmed by several studies
which show that the passive film on chromium consists of Cr203.606 CrOOH has been
found in short time experiments analysing the passive layer ex situ by XPS (X-ray
Photoelectron Spectroscopy).62 In situ reflectance spectroscopy studies have been unable to
obtain any evidence of either Cr(OH)s or Cr02 in the passive film.60 The latter has been
claimed by Sukhotin et al. to be the main compound in the passive film,6x5 although this
has not been confirmed by other researchers. However, the same study with reflectance
spectroscopy6 was not able to exclude the existence of the oxyhydroxide in the passive
layer. In conclusion, it appears that CrOOH(cr) is possibly formed during short time
experiments and that the oxyhydroxide is not thermodynamically stable compared to
Cr203(cr), a behaviour similar to that displayed by the corresponding iron compounds.
Consequently, CrOOH(cr) has been excluded from our calculations. More experimental
studies are needed before the thermodynamic stability of the oxyhydroxide of chromium is
fully established.
Some previously published Pourbaix diagrams879Y5incorrectly report CrO as the solid
Cr(I1) phase in neutral solutions. This apparently originates from the work of Deltombe et
al. where in their Table 1 the hydroxide of chromium(I1) is denoted by the formula CrO
hydr..
Wolf points out2 that chromium hydride may be formed either electrochemically, or
from gaseous hydrogen at Prr2(s) > lo4 atm, which corresponds to EsHE < - 0.65 V in
neutral aqueous solutions at 25C and a comparison with Fig. 1 shows that the CrH(s)
would predominate over Cr(cr). Nevertheless, chromium hydrides have not been included in
our calculations due to the predominance of kinetic effects in this system, and therefore no
hydrides appear in the Pourbaix diagrams presented in this work.
Two general remarks can be concluded regarding the temperature and concentration

Table 3. Calculated thermodynamic stability of chromium species in the system of chromium-water

(P = predominates at 10e6 molal; p = predominates at lo- molal; d = appears in the predominance diagram for
dissolved species)
25C

50C

100C

150C

200C

250C

285C

3WC

Cr(cr)
Cr(OHMcr)
Cr(OHMcr)

Pp

PP

PP

PP

PP

Pp

PP

Cr203@d

PP

PP

PP

PP

PP

PP

Pp

Species

Cfl2W
C*3W

C;L+(aq)
Cr3 + (aq)
CrOH+(aq)
Cr(OH):(aq)
Cr(OHMas)
Cr(OH);(aq)
HDWaq)
HCrWaq)
Cro2,-(aq)
CrzO:-(aq)

Ppd
W
W
Ppd
d
Ppd
Ppd
F$

Ppd

Ppd

W
W

4d
Ppd
4d

&

W
Ppd
Ppd

:d

Ppd
Ppd
4d

B. Beverskog

and I. Puigdomenech

c5

t
L

W
-1

14

-2

Mnc

Fig. 2.

diagram

14

PHlaJS

7
PHNOOOC
Pourbaix

for chromium

7
PHsEos

and [Cr(aq)ltot

= lo-

m at 25, 100,200

and 300C.

dependence in the calculated diagrams. First, the temperature changes the size of the
different stability areas of immunity, passivity and corrosion. The immunity area (stability
of the metal itself) and the passive area (stability of solid compounds) decrease with
increasing temperature. The corrosion area (stability of dissolved species) at acidic pH
decreases, while the corrosion area at alkaline pH and the pH-independent corrosion area at
high potentials increase with temperature. The reason for this behaviour is related to the
temperature dependence of the ionic product of water. Secondly, the concentration of

53

Pourbaix diagrams for Cr

-2

14

pHz5c

7
PHNIOF

-1

-2
0

14

Pkc
Fig. 3. Predominance

diagram for dissolved chromium species and lCr(aq)]tOt < IO@ m at 25, 100, 200 and
3OQC.

dissolved chromium species changes also the size of the different stability areas. The
immunity and passivity areas increase with increasing concentration, while the corrosion
areas decrease.
Thermodynamic calculations have been performed resulting in 24 diagrams,% but as all
these can not be shown in this paper, the results are summarised in Table 3, where P stands
for stability in the Pourbaix diagram, d stands for dissolved and mpesents appearance in

54

B. Beverskogand I. Puigdomenech

the predominance diagram for dissolved species. Unmarked species do not show in the
diagrams at any temperature at the activity levels used.
The Pourbaix diagrams (10m6 and IO-*m) and predominance diagrams calculated
for 25, 100, 200 and 300C are shown in Figs l-3. Pourbaix diagrams for chromium in
these figures are in fair agreement with those previously published at elevated
temperatures, 2,6,8-11,14,15,17,20 and they show a very base metal, as the immunity region
is situated below the hydrogen (H+/H$ line, Fig. 1. The dissolved species of chromium,
which represent corrosion, are Cr2+ and Cr3+ together with its four hydrolysis steps.
Chromium corrodes in acidic solutions to form Cr2+, which is unstable and can oxidise
further to three or six valent forms. Depending on pH, temperature, and concentration,
Cr(II1) species can be either aqueous complexes or a solid compound (CrzOs) which
represents passivity. Alkaline solutions dissolve chromium to form the chromite species
(in this work represented by Cr(OH);,
cf. the discussion in the section on
Thermochemical data).
Cr02 has no stability field, which was expected as it is well known that Cr(IV) is not
stable in contact with aqueous solutions. This is also in agreement with the calculations of
Silverman. I3 None of the hydroxides, the dioxide or the trioxide is the~odynamically
stable, owing to the stability of Cr203, and the calculated solubility of the hydroxides is
higher than that of Cr20s (not shown in the figures). Cr203 is not stable in solutions
containing strong oxidising agents due to the formation of soluble chromate (Cr(V1))
species (H&rod, HCrO; and CrOi-), which establish a corrosion area at all pH-values.
The electrochemical potential for a given pH value at which there is equilibrium between
Cr203 and the aqueous chromate species is lowered with increasing temperature. Ferritic
stainless steel corrodes in aerated hot caustic solutions, and this is confirmed by our
calculations (Fig. 1). This figure also shows that the predominance of each chromium(V1)
species (HzCrOd, HCrO;, and&O-)
moves towards more alkaline pH-values with
increasing temperature. The passive area of chromium is below the upper limit of the
stability field of water (i.e. the oxygen/water line (OJH,O>) at all temperatures, implying
that chromium can corrode at potentials between the passive area and the oxygen line.
Potentials above this line dissolve chromium with oxygen evolution and formation of
Cr(VI) species inde~ndently
of pH. The formation of the dichromate ion (Cr20:-) is
negligible in the investigated concentration range of [Cr(aq)],,, 5 10m6molal. This result is
contradictory
to earlier published Pourbaix diagrams,9p12,8 but in agreement with
experimental evidence, 23 which shows that the dinuclear Cr(V1) anion is more stable than
HCrO; at high concentrations ( > lo-* M). The trioxide is very soluble in aqueous solution
and therefore does not have a stability field in the diluted concentrations used in this work.
Our diagrams calculated at elevated temperatures differ substantially from those in Refs
8,9, ll,20 and 2 1 in that previous studies predicted a substantially larger predominance of
the chromite anion over the stability of Crz03(cr). This arises from the uncertainty in the
nature and stoichiometry of the chromite ion, which is here denoted by CrfOH), but by
CrO; in Refs 8, 9, 1I, 20 and 21, the difference being two water molecules (see also the
discussion in the previous section). Temperature extrapolations of thermodynamic data for
this ion have been performed in this work on an entropy value based on calorimetric
results,51 while previous Pourbaix diagrams at elevated temperatures have been based on a
method to estimate s for oxyanions6 Unfortunately, no experimental data is available to
ascertain the relative stabilities of the chromite ion over Cr;?Os(cr) (or Cr(OH)3(cr)), and this
matter remains unsolved for the time being.

Pourbaix diagrams for Cr

55

The Pourbaix
diagrams
for chromium with lo-* molal concentration, Fig. 2, are very
similar to those at 10m6 molal, Fig. 1. The passive area (CrzOs) at lo-* molal is strongly
reduced, and at T > 150C no solid chromium compound is stable at these low
concentrations, in agreement with the calculated solubility of Cr203.0723
The predominance diagrams for dissolved chromium species, Fig. 3, contain the
oxidation numbers II, III and VI. The chromium species with valency two is C?. The
oxidation number III is represented by Cr3+, CrOH2+, Cr(OH)l, Cr(OH)3(aq), and
Cr(OH); . Six valent chromium species are H2Cr04(aq), HCrOiandCrOi-.
All mentioned
aqueous species predominate in the whole temperature interval, with the exception of
H2Cr04(aq) which does not appear in the diagrams at 25C.

CONCLUSIONS
The revised Pourbaix diagrams for the system chromium-water
concentrations of 10v6 and lo-* molal show that:

at 25-300C and

1. Cr(OH)2, Cr(OH)3, Cr02 and CrOs are not thermodynamically

stable at any
temperature.
2. Cr20s(cr) is the only chromium oxide stable at equilibrium in aqueous solution, with
the exception of lo-* molal and T > 150C where no solid chromium compound is stable.
3. The uncharged aqueous complex, Cr(OH)s(aq), predominate at the concentration of
lo-* m and appears in all the predominance diagrams for dissolved species.
4. The dichromate ion, Cr@-(aq),
does not predominate either in the Pourbaix or in
the predominance diagrams at [Cr(aq)ltot I 10e6 molal.
AcknowledgementsThe
authors express their gratitude to S.-O. Pettersson for his skilful computer and editorial
help. This work was financed by the Swedish Nuclear Power Utilities.

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