Distribucon Especies CR 3

Corrosion Science 51 (2009) 807819
Contents lists available at ScienceDirect
Corrosion Science
journal homepage: www.elsevier.com/locate/corsci
Pourbaix diagrams for chromium in concentrated aqueous lithium bromide

solutions at 25 C
M.J. Muoz-Portero, J. Garca-Antn *, J.L. Guin, V. Prez-Herranz
Departamento de Ingeniera Qumica y Nuclear, Universidad Politcnica de Valencia, P.O. Box 22012, E-46071 Valencia, Spain
a r t i c l e
i n f o
Article history:
Received 23 September 2008
Accepted 19 January 2009
Available online 23 January 2009
Keywords:
A. Chromium
A. Lithium bromide
C. Activity
C. Pourbaix diagram
a b s t r a c t
Pourbaix diagrams (electrode potential-pH diagrams) for CrBrH2O system at 25 C were developed in
400, 700, 850, and 992 g/L (4.61, 8.06, 9.79, and 11.42 M) LiBr solutions, common concentrations in different parts of absorption devices. The diagrams were compared with the simple CrH2O system at 25 C.
Equilibria for the CrBrH2O system at 25 C were determined for bromide ion activities of 15.61,
194.77, 650.06, and 2042.65, which corresponded to the 400, 700, 850, and 992 g/L LiBr solutions, respectively. Activities of all the dissolved species containing chromium were plotted for 106, 104, 102, and
100. Comparison of the simple CrH2O system at 25 C with the diagrams for CrBrH2O system at 25 C
showed that the dominant aqueous Cr(III) species in acid solutions was Cr+3 for Br activities of 15.61,
194.77, and 650.06, whereas it was CrBr+2 for Br activity of 2042.65. Aqueous CrBr+2 formed at a Br
activity higher than 943.05. The chromium solubility range in the acid area of the diagrams extended
slightly to higher pH values with increasing Br activity and decreasing water activity, as a result of
destabilization of Cr2O3.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Aqueous solutions containing high concentrations of lithium
bromide (LiBr) are used as absorbent solutions for almost all types
of heating and refrigerating absorption systems that use natural
gas or steam as energy sources [16]. Absorption units reduce
the use of chlorouorocarbon (CFC) refrigerants and eliminate concerns about lubricants in refrigerants. Although LiBr possesses
favourable thermophysical properties, it can cause serious corrosion problems on metallic components in refrigeration systems
and on heat exchangers in absorption plants [722].
With the advances in refrigeration technology new double effect LiBr absorption machines have been developed. These systems exhibit a higher energetic efciency than simple effect
machines, although they also reach higher temperatures, which
cause important corrosion problems. In recent years, a number
of new, highly alloyed materials have been developed to meet
the increasing demands placed on corrosion resistance. Developments have led to the introduction of alloys with higher chromium (Cr) and molybdenum (Mo) contents, which show much
promise of improved localized corrosion resistance. Cr is one of
the main elements responsible for the formation of the passive
lm in stainless steels. These alloys, such as the high-alloy
austenitic stainless steels Alloy 31 (UNS N08031) and Alloy 33
(UNS R20033), have been studied in LiBr heavy brine solutions
* Corresponding author. Tel.: +34 963877632; fax: +34 963877639.
E-mail address: jgarciaa@iqn.upv.es (J. Garca-Antn).
0010-938X/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.01.004
[13,15,20,21]. In these investigations the alloys showed greater

corrosion resistance and more effective passivation behaviour
than the baseline stainless steels.
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 reactive metal, but to one of its solid reaction products, Cr2O3. The element is protected in oxidising conditions by the
formation of Cr2O3, 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
coefcients are very low, which means low growth rates of the
oxide [23]. The good corrosion behaviour of chromium is the reason to alloy metals with chromium thereby making corrosion
resistant alloys. Knowledge of the limits for the good corrosion
resistance is therefore an important issue. One way to predict the
corrosion resistance of chromium is to consider the thermodynamics (equilibrium relations) of the system.
Chemical and electrochemical equilibria are commonly summarised in Pourbaix diagrams, which are electrode potential-pH diagrams. Pourbaix diagrams have been used extensively to predict
and rationalize corrosion-related processes. Pourbaix diagrams
predict areas of immunity (no corrosion, by denition), passivation
(a solid reaction product), and corrosion (a dissolved reaction product) [2430]. Pourbaix diagrams for chromium are particularly
useful to study the corrosion behaviour of many corrosion resistant
alloys, including stainless steel, as chromium plays an important
role in their corrosion resistance.
808
M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819
The goal of the present work was the prediction of the general
conditions of immunity, passivation, and corrosion for chromium
in concentrated aqueous LiBr solutions. Pourbaix diagrams (electrode potential-pH diagrams) for CrBrH2O system at 25 C were
developed in 400, 700, 850, and 992 g/L (4.61, 8.06, 9.79, and
11.42 M) LiBr solutions, common concentrations in different parts
of absorption devices. The diagrams were compared with the simple CrH2O system at 25 C.
2. Procedure
2.1. Standard Gibbs free energies of formation
Pourbaix diagrams were constructed from standard Gibbs free
energy of formation (DGof ) data at 25 C for all the species considered. Sixteen chemical species were considered for the CrH2O
system:
1. Six solid species: Cr, Cr(OH)2, Cr2O3, Cr(OH)3(s), CrO2, and CrO3.
2. Ten aqueous species: Cr+2, Cr+3, CrOH+2, Cr(OH)2+, Cr(OH)3(aq),
Cr(OH)4, CrO42, HCrO4, H2CrO4, and Cr2O72.
For the construction of the Pourbaix diagrams for the CrBr
H2O system, two additional species were considered, as well as
the sixteen species for the CrH2O system:
1. One solid species: CrBr2.
2. One aqueous species: CrBr+2.
The DGof values on which the equilibria were based are listed in
Table 1, together with the oxidation number, the state of the species, and the sources of the data [23,31,32]. A critical review of
published thermodynamic data has been performed for all the species by Beverskog and Puigdomenech [23], and the best values
have been selected. The data for solid CrBr2 and aqueous CrBr+2
are those selected by Bard et al. [31].
2.2. Reactions
Equations of different reactions were written between all species in the CrBrH2O system. Pairs of species (A and B) were considered in each reaction together with the H+ ion, the electrical
charge (e), H2O, and the Br ion. Thus, these reaction equations
had the following general form:
aA mH ne bB cH2 O dBr
Table 1
Standard Gibbs free energies of formation (DGof ) at 25 C for the CrBrH2O system.
Species
Oxidation numbera
H
H2
O2
H2O
OH
Cr
Cr(OH)2
Cr2O3
Cr(OH)3(s)
CrO2
CrO3
Cr+2
Cr+3
CrOH+2
Cr(OH)2+
Cr(OH)3(aq)
Cr(OH)4
CrO42
HCrO4
H2CrO4
Cr2O72
Br
CrBr2
CrBr+2
a
b
0
II
III
III
IV
VI
II
III
III
III
III
III
VI
VI
VI
VI
II
III
Stateb
DGof (KJ/mol)
Reference
aq
g
g
l
aq
s
s
s
s
s
s
aq
aq
aq
aq
aq
aq
aq
aq
aq
aq
aq
s
aq
0
0
0
237.178
157.293
0
585.57
1053.09
873.17
548
510.04
174
215
431.8
633.19
834.13
1005.89
727.75
765.14
764.00
1302.23
103.97
289
302
[31,32]
[31,32]
[31,32]
[31,32]
[31,32]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[31,32]
[31]
[31]
Oxidation number for the chromium species.

aq, aqueous; s, solid; l, liquid; and g, gas.
The number of reactions was 27 for the CrH2O system and

34 for the CrBrH2O system.
4. Chemical reactions not involving H+. These chemical reactions
were independent both of the potential and the pH; they could
not be represented in a Pourbaix diagram, but they could be
considered when calculating the equilibrium conditions. The
number of reactions was 5 for the CrH2O system and 7 for
the CrBrH2O system.
The reactions were classied as: (1) homogeneous reactions
(involving all the dissolved species), (2) heterogeneous reactions
with two solid species, and (3) heterogeneous reactions with one
solid species.
Equations of the reactions used for the construction of the Pourbaix diagrams for the CrBrH2O system are shown in Tables 25.
The reactions used for the simple CrH2O system are shaded.
Conventional procedures were followed to calculate the electrochemical and chemical equilibria from DGof data [24].
where A and B were the two species containing chromium involved

in the reaction.
For the CrH2O system, sixteen species were considered and the
number of reactions was 120. Eighteen species were considered for
the CrBrH2O system, so that the number of reactions increased
from 120 to 153. Reactions were divided into four types:
1. Electrochemical reactions involving H+. These electrochemical
reactions depended both on the potential and the pH; they
could be represented by oblique lines in a Pourbaix diagram.
The number of reactions was 83 for the CrH2O system and
102 for the CrBrH2O system.
2. Electrochemical reactions not involving H+. These electrochemical
reactions were dependent on the potential and independent of
the pH; they could be represented by horizontal lines in a Pourbaix diagram. The number of reactions was 5 for the CrH2O
system and 10 for the CrBrH2O system.
3. Chemical reactions involving H+. These chemical reactions were
independent of the potential and dependent on the pH; they
could be represented by vertical lines in a Pourbaix diagram.
3. Results
Equilibria for the CrBrH2O system at 25 C were determined for activities of bromide species representative of the test
Table 2
Electrochemical reactions not involving H+.
a
Solid species are typed in bold letters. Reactions used for the construction of the
Pourbaix diagram for the simple CrH2O system are shaded.
809
Table 3
Electrochemical reactions involving H+.
a
Table 4
Chemical reactions involving H+.
a
810
solutions. Activities of the Br ion were calculated to be 15.61,

194.77, 650.06, and 2042.65, which corresponded to the 400,
700, 850, and 992 g/L (4.61, 8.06, 9.79, and 11.42 M) LiBr solutions, respectively. These extremely high activities are a result
of the very large activity coefcients of the LiBr solutions. Calculation of activities of aqueous solutions of strong electrolytes
generally have been handicapped by a lack of activity coefcient
data. The DebyeHckel equation for predicting such activity
coefcients unfortunately applies only to dilute solutions having
concentrations far below those of common industrial interest.
Meissner and Kusik have developed a model to calculate the
activity coefcients of strong electrolyte in aqueous solutions
[3,3335], which was described in detail in a previous work
[36]. Activity coefcients of 400, 700, 850, and 992 g/L aqueous
LiBr solutions were calculated to be 2.973, 19.095, 49.472, and
124.78, respectively.
Activities of the Br ion were obtained by converting the molar
concentrations of 4.61, 8.06, 9.79, and 11.42 M to their corresponding molal concentrations of 5.25, 10.20, 13.14, and 16.37 m, and
using molality-dependent activity coefcients. The densities of

the 400, 700, 850, and 992 g/L LiBr solutions used for converting
the molarity to molality were 1.2766, 1.4904, 1.5948, and
1.6896 g/cm3, respectively, which were calculated using the correlation proposed by Patterson and Prez-Blanco [37].
Activities of water in 400, 700, 850, and 992 g/L LiBr solutions
were calculated to be 0.715, 0.358, 0.216, and 0.118, respectively,
according to the method proposed by Meissner and Kusik, which
is described in detail in the Appendix [34,35,38,39]. Activities of
water in 400, 700, 850, and 992 g/L LiBr solutions were obtained
using the ionic strength of 5.25, 10.20, 13.14, and 16.37, and the reduced activity coefcient of the pure solution at 25 C of 2.973,
19.095, 49.472, and 124.78, respectively. The activities of all the
dissolved species containing chromium were plotted for 106,
104, 102, and 100.
The Pourbaix diagram for the CrH2O system at 25 C is shown
in Fig. 1. The Pourbaix diagrams for CrBrH2O system at 25 C for
Br activities of 15.61, 194.77, 650.06, and 2042.65, and water
activities of 0.715, 0.358, 0.216, and 0.118 are presented in
Figs. 25, respectively. Lines on the diagrams delimit the stability
regions of the solid phases in equilibrium with 106, 104, 102,
and 100 activities of the soluble chromium species.
Simplied Pourbaix diagrams for chromium in H2O at 25 C are
shown in the absence of Br ion (Fig. 6a), for a Br activity of 15.61
(Fig. 6b), for a Br activity of 194.77 (Fig. 6c), for a Br activity of
650.06 (Fig. 6d), and for a Br activity of 2042.65 (Fig. 6e). These
diagrams were plotted for a 106 activity of the soluble chromium
species, which was used for demarcation between corrosion,
immunity, and passivation. The corrosion areas were shaded to differentiate them from immunity and passivation.
The predominance diagram for the dissolved chromium species
at 25 C in the absence of Br ions is shown in Fig. 7. The predominance diagrams for the dissolved chromium species at 25 C for
Table 5
Chemical reactions not involving H+.
a
2.0
1.8
1.6
_
HCrO 4
1.4
20
127
1.2
_2
CrO 4
1.0
0.8
0.6
10
Cr
E (VSHE )
0.4
+3
10
_2
24
10
_4
10
_6
80
134
0.2
CrOH
0.0
113
+2
79
135
-0.2
Cr 2 O 3
-0.4
10
_6
35
11
-0.6
Cr
10
_4
+2
Cr(OH) 4
-0.8
78
-1.0
137
-1.2
44
-1.4
Cr
-1.6
64
-1.8
-2.0
10
11
12
13
14
pH
Fig. 1. Pourbaix diagram for the CrH2O system at 25 C.
15
16
17
811

2.0
1.8
1.6
_
HCrO 4
1.4
20
127
1.2
_2
CrO 4
1.0
0.8
10
0
10
0.6
Cr
E (VSHE )
0.4
+3
_2
24
10
_4
10
_6
80
134
0.2
CrOH
+2
79
0.0
113
135
Cr 2 O 3
-0.2
-0.4
11
-0.6
Cr
10
_6
35
10
_4
+2
Cr(OH) 4
-0.8
78
-1.0
137
-1.2
44
-1.4
Cr
-1.6
64
-1.8
-2.0
0
10
11
12
13
14
15
16
17
pH
Fig. 2. Pourbaix diagram for the CrBrH2O system at 25 C for a Br activity of 15.61, and a water activity of 0.715 (equivalent to 400 g/L LiBr solution).
2.0
1.8
1.6
_
HCrO 4
1.4
20
127
1.2
_2
CrO 4
1.0
0.8
10
0.6
10
Cr
E (VSHE )
0.4
_2
24
10
+3
_4
10
_6
80
134
0.2
CrOH
0.0
113
+2
79
135
-0.2
Cr 2 O 3
-0.4
-0.6
Cr
11
10
_6
35
+2
_
78
-0.8
Cr(OH) 4
-1.0
4
137
-1.2
44
-1.4
Cr
-1.6
64
-1.8
-2.0
0
10
11
12
13
14
15
16
17
pH
812

2.0
1.8
1.6
_
HCrO 4
1.4
20
127
1.2
_2
CrO 4
1.0
0.8
10
0.6
Cr
E (VSHE )
0.4
10
+3
_2
24
10
_4
10
134
0.2
CrOH
0.0
80
_6
+2
79
113
135
-0.2
Cr 2 O 3
-0.4
10
11
-0.6
Cr
_6
35
+2
_
78
-0.8
Cr(OH) 4
-1.0
4
-1.2
137
44
-1.4
Cr
-1.6
64
-1.8
-2.0
0
10
11
12
13
14
15
16
17
pH
2.0
1.8
1.6
_
HCrO 4
1.4
40
127
1.2
_2
CrO 4
24
1.0
0.8
10
0.6
10
CrBr
E (VSHE )
0.4
+2
_2
10
80
_6
_4
10
120
0.2
CrOH
138
0.0
+2
79
135
11
-0.2
Cr 2 O 3
-0.4
2
35
-0.6
Cr
-0.8
+2
10
78
-1.0
_6
-1.2
Cr(OH) 4
44
137
-1.4
Cr
-1.6
64
-1.8
-2.0
0
10
11
12
13
14
15
16
17
pH
Br activities of 15.61, 194.77, 650.06, and 2042.65 and water

activities of 0.715, 0.358, 0.216, and 0.118 are shown in
Figs. 811, respectively. Lines on the diagrams only show equilibria

between the dissolved species. The Pourbaix diagrams and
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
-1.2
-1.4
-1.6
-1.8
-2.0
b 2.0
1.8
Corrosion
Corrosion
Corrosion
Passivation
Corrosion
Alkaline
corrosion
Immunity
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
pH
d
Corrosion
Corrosion
Corrosion
E (VSHE )
E (VSHE )
c 2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
-1.2
-1.4
-1.6
-1.8
-2.0
1.6
Corrosion
1.4
Corrosion
1.2
1.0
0.8
0.6
a
Corrosion
0.4
Corrosion
0.2
0.0
-0.2
Passivation
-0.4
-0.6
b
Corrosion
-0.8
-1.0
Alkaline
-1.2
corrosion
-1.4
Immunity
-1.6
-1.8
-2.0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
pH
Corrosion
E (VSHE )
E (VSHE )
813
Corrosion
Passivation
Corrosion
Alkaline
corrosion
Immunity
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
pH
E (VSHE )
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
-1.2
-1.4
-1.6
-1.8
-2.0
2.0
1.8
1.6
Corrosion
1.4
Corrosion
1.2
1.0
0.8
0.6
a
Corrosion
0.4
Corrosion
0.2
0.0
-0.2
Passivation
-0.4
-0.6
Corrosion
b
-0.8
-1.0
Alkaline
corrosion
-1.2
-1.4
Immunity
-1.6
-1.8
-2.0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
pH
Corrosion
Corrosion
Corrosion
Corrosion
Passivation
Corrosion
Alkaline
corrosion
Immunity
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
pH
Fig. 6. Simplied Pourbaix diagrams for chromium in H2O at 25 C (a) in the absence of Br ions, (b) for a Br activity of 15.61, (c) for a Br activity of 194.77, and (d) for a Br
activity of 650.06, and (e) for a Br activity of 2042.65, considering a 106 activity of the soluble chromium species.
predominance diagrams for the 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 difcult to read, and it is avoided in
this work by separating the Pourbaix diagrams and the predominance diagrams for the dissolved species.
Coarse broken lines in Figs. 111, labelled a and b, limit the
stability area of H2O at a partial pressure of gaseous species equal
814

2.0
1.8
1.6
_
HCrO 4
1.4
20
127
1.2
_2
CrO 4
1.0
0.8
28
24
0.6
a
Cr
0.4
+3
32
E (VSHE )
31
113
0.2
CrOH
0.0
+2
Cr(OH) 2
117
121
-0.2
-0.4
35
Cr(OH) 3 (aq)
1
11
-0.6
b
12
-0.8
124
-1.0
13
_
-1.2
Cr
Cr(OH) 4
+2
-1.4
-1.6
14
-1.8
-2.0
10
11
12
13
14
15
16
17
pH
Fig. 7. Predominance diagram for the dissolved chromium species at 25 C.
2.0
1.8
1.6
_
HCrO 4
1.4
20
127
1.2
_2
CrO 4
1.0
0.8
28
24
0.6
a
Cr
E (VSHE )
0.4
+3
32
113
0.2
CrOH
0.0
+2
31
Cr(OH) 2
117
121
35
-0.2
-0.4
Cr(OH) 3 (aq)
1
11
-0.6
b
12
-0.8
124
-1.0
13
_
-1.2
Cr
Cr(OH) 4
+2
-1.4
-1.6
14
-1.8
-2.0
10
11
12
13
14
15
16
17
pH
Fig. 8. Predominance diagram for the dissolved chromium species at 25 C for a Br activity of 15.61, and a water activity of 0.715 (equivalent to 400 g/L LiBr solution).
815

2.0
1.8
1.6
_
HCrO 4
1.4
20
127
1.2
_2
CrO 4
1.0
0.8
24
27
0.6
a
Cr
E (VSHE )
0.4
+3
23
113
0.2
31
CrOH
0.0
+2
+
Cr(OH) 2
117
121
-0.2
-0.4
35
Cr(OH) 3 (aq)
1
11
-0.6
12
-0.8
-1.0
124
13
-1.2
Cr
Cr(OH) 4
+2
-1.4
-1.6
14
-1.8
-2.0
0
10
11
12
13
14
15
16
17
pH
2.0
1.8
1.6
_
HCrO 4
1.4
20
127
1.2
_2
CrO 4
1.0
0.8
24
27
0.6
a
Cr
E (VSHE )
0.4
+3
23
113
0.2
CrOH
31
+2
+
Cr(OH) 2
0.0
117
121
-0.2
-0.4
35
Cr(OH) 3 (aq)
1
11
-0.6
12
-0.8
-1.0
124
13
-1.2
Cr
Cr(OH) 4
+2
-1.4
-1.6
14
-1.8
-2.0
10
11
12
13
14
15
16
17
pH
816

2.0
1.8
1.6
_
HCrO 4
1.4
40
127
1.2
_2
CrO 4
1.0
0.8
24
27
0.6
a
CrBr
0.4
+2
23
E (VSHE )
120
0.2
CrOH
0.0
31
+2
+
Cr(OH) 2
117
121
-0.2
-0.4
35
Cr(OH) 3 (aq)
2
11
-0.6
12
-0.8
-1.0
124
13
-1.2
Cr
Cr(OH) 4
+2
-1.4
-1.6
14
-1.8
-2.0
0
10
11
12
13
14
15
16
17
pH
to 1 atm. The upper line (a) represents the oxygen equilibrium line
(O2(g)/H2O(l)), and potentials above this line will oxidise H2O with
oxygen evolution. The lower line (b) represents the hydrogen equilibrium line (H+(aq)/H2(g)), and potentials below this line will result in hydrogen evolution. The potential values reported in this
work are always related to the standard hydrogen electrode
(SHE), which is considered to be zero at 25 C. All the diagrams
in Figs. 111 were drawn using Autocad program.
It must be remarked that the Pourbaix diagrams for chromium
in concentrated aqueous LiBr solutions of 400, 700, 850, and 992 g/
L at 25 C are not hitherto available in the literature, and are original in this work.
Thermodynamic stability of the chromium species in the Cr
BrH2O system is summarised in Tables 69, for 106, 104,
102, and 100 activities of the soluble chromium species, respectively, where P stands for stability in the Pourbaix diagram, and
d stands for stability in the predominance diagram for the dissolved chromium species. Unmarked species do not appear in the
diagrams at any Br activity at the activity values of the soluble
chromium species used.
Table 6
Calculated thermodynamic stability of chromium species in the CrBrH2O system, considering a 106 activity of the soluble chromium species (P, appears in the Pourbaix
diagram; d, appears in the predominance diagram for the dissolved chromium species).
Species
(Br) = 0
(H2O) = 1
[LiBr] = 0 g/L
(Br) = 15.61
(H2O) = 0.715
[LiBr] = 400 g/L
(Br) = 194.77
(H2O) = 0.358
[LiBr] = 700 g/L
(Br) = 650.06
(H2O) = 0.216
[LiBr] = 850 g/L
(Br) = 2042.65
(H2O) = 0.118
[LiBr] = 992 g/L
Cr
Cr(OH)2
Cr2O3
Cr(OH)3(s)
CrO2
CrO3
Cr+2
Cr+3
CrOH+2
Cr(OH)2+
Cr(OH)3(aq)
Cr(OH)4
CrO42
HCrO4
H2CrO4
Cr2O72
CrBr2
CrBr+2
Pd
Pd
Pd
d
d
Pd
Pd
Pd
Pd
Pd
Pd
d
d
Pd
Pd
Pd
Pd
Pd
Pd
d
d
Pd
Pd
Pd
Pd
Pd
Pd
d
d
Pd
Pd
Pd
Pd
Pd
d
d
Pd
Pd
Pd
Pd
817
Table 7
Species
(Br) = 0
(H2O) = 1
[LiBr] = 0 g/L
(Br) = 15.61
(H2O) = 0.715
[LiBr] = 400 g/L
(Br) = 194.77
(H2O) = 0.358
[LiBr] = 700 g/L
(Br) = 650.06
(H2O) = 0.216
[LiBr] = 850 g/L
(Br) = 2042.65
(H2O) = 0.118
[LiBr] = 992 g/L
Cr
Cr(OH)2
Cr2O3
Cr(OH)3(s)
CrO2
CrO3
Cr+2
Cr+3
CrOH+2
Cr(OH)2+
Cr(OH)3(aq)
Cr(OH)4
CrO42
HCrO4
H2CrO4
Cr2O72
CrBr2
CrBr+2
Pd
Pd
Pd
d
d
Pd
Pd
Pd
Pd
Pd
Pd
d
d
Pd
Pd
Pd
Pd
Pd
Pd
d
d
Pd
Pd
Pd
Pd
Pd
Pd
d
d
Pd
Pd
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
Table 8
Species
(Br) = 0
(H2O) = 1
[LiBr] = 0 g/L
(Br) = 15.61
(H2O) = 0.715
[LiBr] = 400 g/L
(Br) = 194.77
(H2O) = 0.358
[LiBr] = 700 g/L
(Br) = 650.06
(H2O) = 0.216
[LiBr] = 850 g/L
(Br) = 2042.65
(H2O) = 0.118
[LiBr] = 992 g/L
Cr
Cr(OH)2
Cr2O3
Cr(OH)3(s)
CrO2
CrO3
Cr+2
Cr+3
CrOH+2
Cr(OH)2+
Cr(OH)3(aq)
Cr(OH)4
CrO42
HCrO4
H2CrO4
Cr2O72
CrBr2
CrBr+2
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
Table 9
Species
(Br) = 0
(H2O) = 1
[LiBr] = 0 g/L
(Br) = 15.61
(H2O) = 0.715
[LiBr] = 400 g/L
(Br) = 194.77
(H2O) = 0.358
[LiBr] = 700 g/L
(Br) = 650.06
(H2O) = 0.216
[LiBr] = 850 g/L
(Br) = 2042.65
(H2O) = 0.118
[LiBr] = 992 g/L
Cr
Cr(OH)2
Cr2O3
Cr(OH)3(s)
CrO2
CrO3
Cr+2
Cr+3
CrOH+2
Cr(OH)2+
Cr(OH)3(aq)
Cr(OH)4
CrO42
HCrO4
H2CrO4
Cr2O72
CrBr2
CrBr+2
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
d
d
d
Pd
Pd
Pd
Pd
818
4. Discussion
The Pourbaix diagram for the simple CrH2O system at 25 C
(Fig. 1) shows that chromium is a very reactive metal, as the immunity region is situated below the hydrogen equilibrium line
(H+(aq)/H2(g)). Chromium corrodes in acid-to-neutral solutions to
form Cr+2, which is unstable and can oxidise further to three or
six valent forms. Depending on pH and activity of the dissolved
chromium species, Cr(III) species can be either aqueous species
(Cr+3 and CrOH+2), which represents corrosion, or a solid compound (Cr2O3), which represents passivation. An increase in the
activity of the dissolved chromium species from 106 to 100 results
in a decrease of pH value for the formation of Cr2O3. For 102 and
100 activities of the dissolved chromium species, CrOH+2 is not stable. For very strong alkaline solutions, chromium corrodes through
the formation of Cr(OH)4. At high potentials, Cr(III) species oxidises to form aqueous Cr(VI) species (HCrO4 and CrO42), which
establishes a corrosion area at all pH-values. An increase in the
activity of the dissolved chromium species from 106 to 100 results
in an increase of electrochemical potential for a given pH value at
which there is equilibrium between Cr2O3 and the aqueous Cr(VI)
species. It can be concluded that the activity of the dissolved chromium species changes the size of the different stability areas of
immunity, passivation, and corrosion. The immunity area (stability
of the metal itself) and the passivation area (stability of solid compounds) increase with increasing the activity of the dissolved chromium species. The corrosion area (stability of the dissolved
species) at acid-neutral pH, the corrosion area at alkaline pH, and
the pH-independent corrosion area at high potentials decrease by
increasing the activity of the dissolved chromium species.
Comparison of the simple CrH2O system at 25 C in Fig. 1 with
the diagrams for the CrBrH2O system at 25 C in Figs. 25 show
that the dominant aqueous Cr(III) species in acid solutions is Cr+3
for Br activities of 15.61, 194.77, and 650.06, whereas it is CrBr+2
for a Br activity of 2042.65.
Chemical equilibrium between Cr+3 and CrBr+2 is shown in Eq.
(2). The equilibrium constant (K) at 25 C is given by Eq. (3):
Cr3 Br CrBr2

"
#
CrBr2
1:0604 103
K
Cr3 Br
2
3
Consequently, aqueous CrBr+2 forms at a Br activity higher

than 943.05, which corresponds to the 896.3 g/L (10.32 M) LiBr
solution.
Figs. 25 show that the chromium solubility range in the acid
area of the diagrams extends slightly to higher pH values with
increasing Br activity and decreasing water activity, as a result
of destabilisation of Cr2O3. For a 106 activity of the dissolved
chromium species, the precipitation of Cr2O3 is governed by the
chemical equilibrium with CrOH+2. The pH value of the precipitation of Cr2O3 decreases with increasing activity of the dissolved
chromium species from 106 to 100. For Br activities of 15.61,
194.77, and 650.06, CrOH+2 is not stable for 102 and 100 activities of the dissolved chromium species, as shown in Figs. 24; in
these cases, the precipitation of Cr2O3 is governed by the chemical equilibrium with Cr+3. For a Br activity of 2042.65, CrOH+2 is
not stable for 104, 102, and 100 activities of the dissolved chromium species, as shown in Fig. 5; in these cases, the precipitation
of Cr2O3 is governed by the chemical equilibrium between CrBr+2
and Br species. At high potentials, the Cr(III) species in acid solutions (Cr+3 or CrBr+2) oxidise to form aqueous HCrO4. The oxidation of Cr+3 or CrBr+2 to form HCrO4 occurs at both higher
potentials and higher pH values with the increase of Br ions
activity and decrease of water activity, as shown in Figs. 25.
Comparison of the simplied Pourbaix diagrams for chromium

in H2O in the absence and presence of Br ions (Fig. 6ae) shows
that the increase in Br activity and the decrease in water activity
shift the corrosion area at acid pH to higher pH values. The size of
the passivation area increases with increasing Br activity and
decreasing water activity, because the corrosion area at alkaline
pH shifts to higher pH values with increasing Br activity. The
immunity area increases slightly and the pH-independent corrosion area at high potentials decreases slightly with increasing Br
activity and decreasing water activity.
Predominance diagram for the dissolved chromium species at
25 C (Fig. 7) contains oxidation numbers II, III, and VI. The chromium species with valency two is Cr+2. Oxidation number III is represented by Cr+3, CrOH+2, Cr(OH)2+, Cr(OH)3(aq), and Cr(OH)4. Six
valent chromium species are HCrO4 and CrO42.
Figs. 811 show that the dissolved chromium species at 25 C in
the presence and absence of Br ions are the same, except for Br
activity of 2042.65, where Cr+3 is not stable and CrBr+2 is the stable
dissolved chromium species with valency three in acid solutions.
Pourbaix diagrams for chromium in concentrated aqueous LiBr
solutions of 400, 700, 850, and 992 g/L at 25 C with precise delineation of immunity, passivation, and corrosion regions provide basic data for studying the corrosion behaviour of high-alloy stainless
steels in refrigeration systems, as chromium plays an important
part in their corrosion resistance, and to interpret the results obtained [13,15,20,21].
5. Conclusions
1. This article has described the construction of Pourbaix diagrams
for chromium in concentrated aqueous LiBr solutions of 400,
700, 850, and 992 g/L at 25 C, based on Br activities of
15.61, 194.77, 650.06, and 2042.65, and water activities of
0.715, 0.358, 0.216, and 0.118, respectively, and on dissolved
chromium species activities of 106, 104, 102, and 100, which
were not hitherto available in the literature. Pourbaix diagrams
for chromium in concentrated aqueous LiBr solutions could be
particularly useful to study the corrosion behaviour of alloys
with high chromium content in refrigeration systems.
2. Comparison of the Pourbaix diagrams for the CrBrH2O system at 25 C in 400, 700, 850, and 992 g/L LiBr with the simple
CrH2O system at 25 C shows that:
A. The dominant aqueous Cr(III) species in acid solutions is Cr+3
for Br activities of 15.61, 194.77, and 650.06 (equivalent to
the 400, 700, and 850 g/L LiBr solutions, respectively),
whereas it is CrBr+2 for a Br activity of 2042.65 (equivalent
to 992 g/L LiBr solution). Aqueous CrBr+2 forms at a Br activity higher than 943.05.
B. The chromium solubility range in the acid area of the diagrams extends slightly to higher pH values with increasing
Br activity and decreasing water activity, as a result of
destabilization of Cr2O3.
C. The size of the passivation area increases with increasing Br
activity and decreasing water activity, because the corrosion
area at alkaline pH shifts to higher pH values with increasing
Br activity. The immunity area increases slightly and the
pH-independent corrosion area at high potentials decreases
slightly with increasing Br activity and decreasing water
activity.
Acknowledgements
The authors acknowledge the DGI (Direccin General de Investigacin, Convention no. CTQ2006-07820) and FEDER (Fondo
Europeo de Desarrollo Regional) for the support of this work, Dra.

M. Asuncin Jaime for her translation assistance, and Antonio Juncos for his assistance in plotting the diagrams.
Appendix A
A.1. Activity of water in strong electrolyte solutions
The activity of water (aow ) is expressed as pw/pow , namely the ratio of the vapor pressures over the single electrolyte solution and
over pure water, all at the temperature of interest. For a pure solution of a single strong electrolyte in aqueous solution, aow can be
calculated at any temperature by rearrangement and integration
of the GibbsDuhem equation, according with the method proposed by Meissner and Kusik [34,35,38,39]:
log aow
0:0156I
0:036
z1 z2
Co
Id log Co
A:1
where I is the ionic strength, Co is the reduced activity coefcient of

the pure solution at 25 C, z1 is the number of charges on the cation,
and z2 is the number of charges on the anion (z1 = z2 = 1 for LiBr/H2O
solution).
The ionic strength of a single electrolyte 12 composed of ions 1
and 2 in aqueous solution is related to its molality as follows:
I 0:5m12 m12 z1 z2
A:2
where m12 is the molality (moles per kilogram of water), and m12 is
the moles the ions formed upon dissociation of one mole of electrolyte. For LiBr/H2O solution, I = m12.
For a single electrolyte solution at 25 C:
Co 1 B1 0:1Iq BC
A:3
with:
B 0:75 0:065q
p
0:5107 I
p
log C
1C I
C 1 0:055q exp0:023I 3
A:4
A:5
A:6
where q is the Meissners parameter (q = 7.27 for LiBr).

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Contents lists available at ScienceDirect

Pourbaix diagrams for chromium in concentrated aqueous lithium bromide

[13,15,20,21]. In these investigations the alloys showed greater

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

aA mH ne bB cH2 O dBr

Oxidation number for the chromium species.

The number of reactions was 27 for the CrH2O system and

where A and B were the two species containing chromium involved

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

solutions. Activities of the Br ion were calculated to be 15.61,

using molality-dependent activity coefcients. The densities of

Fig. 1. Pourbaix diagram for the CrH2O system at 25 C.

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

Br activities of 15.61, 194.77, 650.06, and 2042.65 and water

Figs. 811, respectively. Lines on the diagrams only show equilibria

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

Fig. 7. Predominance diagram for the dissolved chromium species at 25 C.

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

Cr3 Br CrBr2

Consequently, aqueous CrBr+2 forms at a Br activity higher

Comparison of the simplied Pourbaix diagrams for chromium

M.J. Muoz-Portero et al. / Corrosion Science 51 (2009) 807819

Europeo de Desarrollo Regional) for the support of this work, Dra.

where I is the ionic strength, Co is the reduced activity coefcient of

where q is the Meissners parameter (q = 7.27 for LiBr).

[10] A. Igual-Muoz, J. Garca-Antn, J.L. Guin, V. Prez-Herranz, Galvanic study

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