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

107-l 14, 1997

Pergamon Copyright 0 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0010-938x/97 %17.00+0.00



t Studsvik Material AB, S-61 1 82 Nykoping, Sweden

$ Studsvik Eco and Safety AB, S-61 1 82 Nykoping, Sweden

Abstract-Pourbaix diagrams (potential/pH diagrams) for zinc at 25300°C have been revised. The diagrams were
calculated for three concentrations, 10V5, 10K6 and lOpa molal, the latter for use in high purity water such as in
nuclear power reactors. Extrapolation of thermochemical data to elevated temperatures has been performed with
the revised model of Helgeson-Kirkham-Flowers, which also allows uncharged aqueous complexes, such as
Zn(OH)z(aq), to be handled. The calculations show that the hydroxide of zinc does not passivate at the
concentration of 10K6M, due to the uncharged zinc(I1) complex, Zn(OH)z(aq). However, at concentrations
z lO_‘.’ M zinc passivates by formation of ZnO, which is stable in the temperature interval investigated. Copyright
0 1996 Elsevier Science Ltd
Keywords: A. zinc, B. elevated temperatures, C. Pourbaix diagram.

The increasing interest in zinc in the nuclear power industry is due to several reasons.
Zinc injection into the cooling media has a positive effect on reducing the build-up of
radionuclides, especially Co-60, in the passive layers of the construction materials of nuclear
reactors.le7 Co-60 is a strong y-radiator with a long half life (T1’2= 5.272 y) and causes health
problems for maintenance personnel. IGSCC (Inter Granular Stress Cracking Corrosion)
has also been reported to decrease by zinc injection into the cooling media in LWRs (Light
Water Reactors).839 However, zinc injection has a drawback as Zn-64, which has a natural
abundance of 48.6%) transforms during irradiation to Zn-65. The latter is a y-radiator which
increases the radiation level in nuclear plants. The increased availability of zinc depleted in
Zn-64 on the world market has raised the interest for zinc-injection in nuclear power plants.
However, the mechanism for the benefits of zinc addition is not fully understood. Knowledge
of the thermodynamic stability of the system is a necessary base plate for a deeper
understanding of the advantages of zinc injection. Thermochemical data, which are difficult
to comprehend from a multi-dimensional room (i.e. potential, pH concentration and
temperature) can be drawn as two dimensional maps of the chemical system. One type of
such diagrams is called Pourbaix diagram, after the originator Marcel Pourbaix.iG
Pourbaix diagrams for zinc have been published by several authors,“-20 but only a few
at elevated temperatures.14*16,‘8 The species considered in the Pourbaix diagrams previously
published are summarised in Table 1. It is noteworthy that the uncharged aqueous complex
Zn(OH)z(aq) was not included in any of the calculations. The choice of species seems to be
very traditional in previous works. The selection of species is very important, because it
influences the results of the calculations.

Manuscript received 27 February 1996.

108 B. Beverskog and I. Puigdomenech

Table 1. Species considered in previously published Pourbaix diagrams for zinc

Species 1111 1121 [131 114,161 [151 [171 1181 [loI [201

Zn(cr) X X X X x X X

a-Zn(OH),(cr) X

B-Zn(OH)s(cr) X

r-Zn(OH)s(cr) X

&Zn(OH)2(cr) -
e-Zn(OH)2(cr) X X X X X -

Zn(OH)s(am) X -
ZnO(cr) X X X X X X X X
ZnOs(cr) -

Zn*+(aq) X X X X X X X X X
ZnOH + (aq) X X X X - -
Zn(OH)s(aq) -
Zn(OHK(aq) X* X* X* X* x* - - X
Zn(OH)d2-(aq) X** x** x** x** x** - - X
Zn(OH)3+(aq) - -
Zna(OH),*-(aq) -
No of species 11 4 5 6 7 7 3 3 5
Remarks a b c,d,e f g h i,c

X: the passive compound in the Pourbaix diagram, x*: HZn02-(aq), x**: Zno22- (aq), a: included NHs, b: included
NH3 - H2S04, c: the diagram was constructed for unit activity of dissolved species, d: 25, 100, 150 and 250°C e:
included sulphur, f: included sulphur and carbon, g: 10m4 M, h: 25 and 300°C i: only diagram and no tabulation of
species included in the calculations.

The aim of this work was twofold. Firstly, the Pourbaix diagram for zinc needed to be
revised and based on species which are consistent with thermochemical data as well as
experimental evidence of existence in aqueous solutions. Secondly, the interest in the high
temperature behaviour of zinc shows the need for calculations at T> 25°C.


Chemical species
After careful choice of zinc species in diluted aqueous solution eight species (three solids
and five aqueous complexes) were selected to be included in the calculations, Table 2.
Twelve zinc species (10 solids and two polynucleous aqueous complexes) were excluded
from the diluted aqueous system of zinc, Table 2. The reasons for the exclusions are the
following: the hydride is not stable in aqueous solution. Only the most stable of the six
hydroxides, s-Zn(OH)z, was selected while the others were omitted. Oxidation numbers > II
for zinc were excluded as they are not stable aqueous solution. The polynuclear hydrolysis
complexes were not included as they do not exist at the low levels of dissolved species
considered in this study.21
The hydrolysed zinc complexes with the charges - 1 and -2 in alkaline solutions are
denoted as Zn(OH)s- and Zn(OH)42-. These are not the traditional notations of HZnOz-
and Zn022- generally used in Pourbaix diagrams and the difference is one and two water
molecules, respectively. The new nomenclature is in agreement with the work of Baes and
Revised Pourbaix diagrams for Zn 109

Table 2. Considered species in the aqueous system of zinc

State Oxidation Included Excluded


crystalline 0 Zn
_“_ -11 ZnH2
_‘I_ II ZnO
_‘I_ _“_ cl-Zn(OH)r
_“_ _I’_ P-Zn(OH)a
_‘I_ _“_ y-Zn(OH)a
_I’_ _“_ 6-Zn(OH)2
_“_ _‘I_ s-Zn(OH)z
amorphous _“_ Zn(OH)a
crystalline III ZnaOs . H20
_“_ II/III Zn305
_I’_ IV ZnOs
_“_ _‘I_ ZnOs Hz0
dissolved II Zn2+
_I’_ _I’_ ZNOH +
_“_ _“_ Zn(OH)s
_“_ _I’_ Zn(OH)s-
_“_ _“_ Zn(OH)42-
_“_ _“_ Zn2(OW-
_I’_ _I’_ Zn2(OH)42-

Mesmer? These complexes are also consistent with thermochemical data as well as the
hydrolysis series of zinc.

Thermochemical data
Published thermochemical data were critically evaluated and data from selected
references were chosen for the preselected solids and aqueous species in the system Zn(cr)-
H*O(l)-Hz(g), Table 3. Auxiliary data (for HzO, OH, etc.) were taken from CODATA.22
Values for Zn(cr), Zn2+ and ZnO(cr) are those from CODATA,22 except for the heat
capacities which were taken from Ref. 23 (temperature functions for the solids) and from
Ref. 24 (standard partial molar heat capacity of Zn2+ at 25°C). The data for E-Zn(OH)z are
from Ref. 25.
The hydrolysis of Zn2+ results in the formation of ZnOH+, Zn(OH)2(aq), Zn(OH)s-
and Zn(OH)42-. Although polynuclear complexes may be formed at high total zinc
concentrations at the lowest temperatures, polynuclear complexes have been neglected in
this work. The values of A@’ at 25°C for the mononuclear hydrolysis complexes were
obtained from the hydrolysis constants recommended in Ref. 21.
The enthalpy data (and equilibrium constants) available for ZnOH+ are contradictory,
because this complex is only present in negligible amounts at all temperatures. The enthalpy
change for the reaction

Zn2+ + Hz0 e ZnOH+ + H+

reported in Ref. 26 has been selected here. This enthalpy of reaction ( + 56 kJ mol- ‘) is in
fair agreement with the stepwise enthalpies of formation of the second, third and fourth
hydrolysis complexes by similar reactions which can be obtained by fitting the equilibrium
110 B. Beverskog and I. Puigdomenech

Table 3. Thermodynamic data at 25°C for the system zinc-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

s” C,O(T)/(J K-’ mol-‘)

Svecies (kJ mol- ‘) (J K-t mol-‘) .+ bx lo3 cx 10-6

Zn(cr) 0 41.63 21.334 11.648 0.054

ZnO(cr) - 320.479 43.65 45.338 7.289 -0.573
E - Zn(OH)z - 555.82 77 74.27
Zn*+ - 147.203 - 109.8 -25.8
Zn(OH)+ - 333.20 -24 10
Zn(OHMaq) - 525.02 42 70
Zn(OH)s - -696.52 40 94
Zn(OH)42- - 860.59 15 -284

+: For aqueous species a corresponds to the standard partial molar heat capacity at 25”C, and the revised
Helgeson-Kirkham-Flowers model has been used to obtain its temperature dependence.

constant data reported in Ref. 27, namely: +44.4, +44.3, and +45.2kJmol-‘,
respectively, and which are adopted here to derive the values of 9’ for Zn(OHMaq),
Zn(OH)s-, and Zn(OH)4.
Standard partial molar heat capacities of Zn(OH)2(aq), Zn(OH)3- and Zn(OH)42-
were obtained from fitting the experimental results of Plyasunov et ~1.~’ constrained to the
equilibrium hydrolysis constants at 25°C selected here from Ref. 21 For ZnOH+, the
standard partial molar heat capacity was obtained from a correlation between the number
of hydroxy ligands and the corresponding A&O, for the reaction:

Zn2+ + nOH_ g Zn(OH)i-”

which were calculated by fitting the data of Ref. 28 as mentioned above.

A critical review of published thermodynamic data has been performed for the solids
and aqueous species described in the previous section. Data is usually available only for a
reference temperature of 25°C in the form of standard molar Gibbs free energy of formation
from the elements (A,G”) and standard molar entropy (So). Equations for the temperature
dependency of the standard molar heat capacity (C,“) are usually available for solid and
gaseous compounds. For aqueous species, the standard partial molar properties are usually
available. Extrapolation of thermodynamic data to other temperatures is performed with
the methodology described elsewhere.29 For aqueous species T-extrapolations have been
based on the electrostatic model of Helgeson et ~1.~~~~and our methodology requires a
value of Cr” at 25°C. The data selected for the calculations performed in this work are
summarised in Table 3.
Calculations to draw the Pourbaix diagrams presented in this work have been performed
for eight temperatures in the interval 25-300°C. Pourbaix diagrams have been calculated in
this work at three concentration levels, 10W5, 10e6 and lo-* molal, at every temperature.
The second is the conventional corrosion limit stipulated by Pourbaix, and the latter is
intended to be used in high purity waters, such as nuclear reactors of the boiling water type.
Revised Pourbaix diagrams for Zn 111

I- --
-- I
Zn*+ i Zn (%z(aq)-
‘3 Zn (OH?
2 OS,_ Zn (OH):
w -- I
---I I‘-,

Zn (cd

Fig. 1. Pourbaix diagram for zinc at 25°C and [Zn(aq)],,, = 10m6molal.

These concentrations are total concentrations, i.e. the sum of all aqueous species containing
zinc at each coordinate point (Es&pH-value).
The parallel sloping dotted lines in the Pourbaix diagrams limit the stability area of
water at atmospheric pressure of gaseous species. The upper line represents the oxygen
equilibrium line (02(g)/H20(1)) and potentials above this line will oxidise water with oxygen
evolution. The lower line represents the hydrogen line (H+/Hz(g)) and potentials below this
line will result in hydrogen evolution.
All values of pH given in this work are values at the specified temperature. The neutral
pH value of pure water changes with the temperature with the ion product of water
(H2W P H+ + OH-, pHneutrai= l/2 p&r). To facilitate reading the Pourbaix diagrams,
the neutral pH value at the temperature of each diagram is given as a vertical dotted line.

The Pourbaix diagrams for zinc at two temperatures (25 and 300°C) with the
concentration lop6 molal are shown in Figs 1 and 2. Zinc does not passivate (forming a
solid compound) in the temperature interval investigated at the concentration of 10e6 M
nor at 10e8 M.
Zinc passivates at lo-’ M with stability of ZnO at pH 8.2-12.1. The predominance for
dissolved zinc species can also be seen in the Pourbaix diagrams, Figs 1 and 2. The diagrams
show that Zn2+ and its hydrolysis products, with the exception of the first one, are stable in
the whole temperature interval investigated. At neutral pH values Zn2+ predominates in the
temperature range 25--150°C while the uncharged complex Zn(OH)z(aq) predominates at

The Pourbaix diagrams for zinc show a very base metal, as the immunity region is
situated far below the hydrogen (H+/HJ line. Its high hydrogen overpotential hinders
112 B. Beverskog and I. Puigdomenech



Zn (OH j,



Fig. 2. Pourbaix diagram for zinc at 300°C and [Zn(aq)ltot = lop6 molal.

kinetically the evolution of hydrogen, and causes zinc to be fairly stable in an aqueous state
despite its base nature. According to our calculations, zinc does not passivate at a
concentration level of 10e6 M as no passive area is formed in the calculated Pourbaix
diagrams, Figs 1 and 2. This result is in contradiction to all earlier published Pourbaix
diagrams for zinc. The reason for this is the uncharged aqueous zinc complex, Zn(OH)z(aq),
which has not been included in the construction of previously reported Pourbaix diagrams.
Exclusion of Zn(OH)z(aq) in our calculation confirms earlier results. This shows the
importance of including all species known to exist in a system, when performing
thermodynamic calculations. Omitting a species that exists or including a species that does
not exist or is unstable in the environment of interest can spoil the calculations and give
misleading information. The uncharged aqueous zinc complex is consistent with all
available experimental data on zinc hydrolysis.*’
The lack of predominance for the first hydrolysis product is in agreement with Refs 11,
14-17 Zubov and Pourbaix published a solubility diagram (concentration vs pH) of zinc
hydroxide, c-Zn(OH)z, where the minimum concentration was just below 10W7. The
ordinate was the sum of the ions Zn*+, HZn02- and Zn022-. However, with the second
hydrolysis step included, the solubility minimum increases above 10m6 M and no precipitate
forms at this concentration level.
Comparison with other reported Pourbaix diagrams for zinc at elevated temperatures is
not meaningful as one study included only three zinc species and the other studies had
sulphur included.
This new information on zinc, here reported for the first time, is it reasonable? Zinc is
known to be a corrosion resistant metal, despite its base nature, which is due to its very high
over-potential for hydrogen evolution and oxygen reduction as well as very low exchange
current densities. The reason for the high corrosion resistance is either high activation
energy for the cathodic reactions on zinc, or inhibition of the surface reactions for zinc
dissolution or a combination of both.
Revised Pourbaix diagrams for Zn 113

The revised Pourbaix diagrams for zinc at 25-300°C at concentrations of 10F6 and
lo-’ molal show that:
1. The uncharged aqueous hydrolysis complex, Zn(OH)*(aq), is included in a Pourbaix
diagram for the first time.
2. Zinc does not passivate at 25°C at 10V6 M concentration of dissolved species, due to
the uncharged complex. This behaviour has not been reported before.
3. Zinc passivates at concentrations > 10p5.’ of dissolved species at 25°C.
4. The oxide and not the hydroxide is the stable passive phase of zinc at 25-300°C.

Acknowledgements-This work has been financed by Toshiba Corp., Isogo Nuclear Engineering Center (Japan). S.-
0. Pettersson is gratefully acknowledged for computer and data handling.


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