The Phase Stability of Cerium Species in Aqueous Systems :

I. E-pH Diagram for the System

Scott A. Hayes, Pu Yu, Thomas J. O'Keefe, Matthew J. O'Keefe and James O. Stoffer

J. Electrochem. Soc. 2002, Volume 149, Issue 12, Pages C623-C630.

doi: 10.1149/1.1516775

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 Journal of The Electrochemical Society, 149 共12兲 C623-C630 共2002兲 C623
0013-4651/2002/149共12兲/C623/8/$7.00 © The Electrochemical Society, Inc.

The Phase Stability of Cerium Species in Aqueous Systems

I. E-pH Diagram for the Ce-HClO4-H2O System
Scott A. Hayes, Pu Yu,*,z Thomas J. O’Keefe,* Matthew J. O’Keefe,
and James O. Stoffer
Graduate Center for Materials Research, University of Missouri-Rolla, Rolla, Missouri 65401, USA

Cerium compounds have been identified as leading candidates to replace hexavalent chrome as conversion coatings on aluminum
alloys to improve corrosion resistance. Cerium also shows promise for use as an inhibiting pigment in paint systems. The cerium
conversion coatings can be deposited using either spontaneous or nonspontaneous electrolytic processes. In both cases the
protective cerium oxide film forms by a precipitation mechanism that is very dependent on electrochemical potential and pH. The
oxidation state and phase of the condensed cerium has been shown to be an important aspect of the corrosion protection properties
provided by the film. Because of the strong influence of the solution chemistry and operating parameters on film performance, a
basic knowledge of the system stability is essential. Toward this end, a revised E-pH diagram was developed for the Ce-H2 O
system. The Ce-H2 O-HClO4 system was chosen as an example system in which hydroxy ions are the only significant complexing
species for the Ce ions. A stability diagram was constructed using more recent thermodynamic data on cerium species not available
for the original diagram published in Pourbaix’s atlas. Significant differences were noted between the previously published
Ce-H2 O diagram and the one presented here. Precipitation tests were carried out to verify the trends indicated in the new diagram.
The importance of the updated E-pH diagram in understanding the formation processes of cerium conversion coatings are
discussed.
© 2002 The Electrochemical Society. 关DOI: 10.1149/1.1516775兴 All rights reserved.

Manuscript submitted February 11, 2002; revised manuscript received May 24, 2002. Available electronically October 18, 2002.

One motivating factor for reexamining the cerium E-pH diagram
is the recent application of cerium films for corrosion protection of
aluminum alloys. There is a desire to decrease or completely remove
the chromium compounds used for conversion coating and paint-
type applications in metal finishing. Regulation of chromium com-
pounds is expected to become more stringent due to toxicity and
carcinogenic effects.1 The use of Ce in conversion coatings is the
subject of several papers and patents and a number of representative
examples can be found in the literature.2-9 Also, to a lesser extent,
there has been some interest in using cerium compounds as a sub-
stitute for chromate in paint and primer-type coatings.2,10
A brief discussion of the cerium coating process on aluminum
alloys, as well as the correlation and use of the Ce E-pH diagram in
conjunction with the precipitation of selected cerium phases, is pre-
sented. In this paper, the term 关X兴 refers to the activity of the species
X. The terms Ce共III兲 and Ce共IV兲 refer to the oxidation states of Ce
present in hydrolyzed or oxide forms, whereas Ce3⫹ and Ce4⫹ refer
to the species that are, at most, only weakly complexed with water
or perchlorate.
The general mechanism of cerium conversion coating deposition
has been described previously.9,11-13 In both the nonelectrolytic and
electrolytic cerium deposition processes, an increase in solution pH
at the cathode interface leads to precipitation of the cerium com-
pounds. In two patented processes, the increase in interfacial pH is
achieved by cathodic polarization of the substrate.3,9 One patent
claims that the final coating is initially deposited as an oxide or
hydroxide with a Ce共IV兲 oxidation state, with the possibility of in-
clusion of some Ce共III兲.3 In this application, a soluble cerium共III兲
salt is used in the electrolyte with an oxidant, such as hydrogen
peroxide, added to assist in forming a final Ce共IV兲 state. Reactions
that would increase pH include
2H2 O ⫹ 2e⫺ → H2 ⫹ 2 OH⫺
2H⫹ ⫹ 2e⫺ → H2
H2 O2 ⫹ 2H⫹ ⫹ 2e⫺ → 2H2 O
H2 O2 ⫹ 2e⫺ → 2 OH⫺
* Electrochemical Society Active Member.
z
E-mail: paulyu@umr.edu
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The reactions for precipitation and film formation are thought to
be
Ce3⫹ ⫹ 3 OH⫺ → Ce共 OH兲 3 关5兴
Ce3⫹ ⫹ OH⫺ ⫹ 1/2H2 O2 → Ce共 OH兲 2⫹
2 关6兴
⫺
2 ⫹ 2 OH → Ce共 OH 兲 4
Ce共 OH兲 2⫹ 关7兴
The conversion coating most likely imparts corrosion resistance
by impeding hydrogen evolution at cathodic sites either by minimiz-
ing the flow of electrons from the substrate or by passivating ca-
thodic sites on the substrate.9 For simple barrier protection, an oxide
or hydroxide with low solubility must be formed.11 Preliminary
evaluations indicate that the phase of cerium deposited and the mor-
phology of the precipitate are important to the corrosion resistance
of the films.
Correlation of film characteristics and properties with cerium
film formation are needed to better understand the influence of depo-
sition parameters, such as pH and cerium species, on corrosion pro-
tection performance. Interest in the thermodynamic stability of vari-
ous cerium species has thus led to a review of recently published
data on cerium species, construction of a revised E-pH diagram
using these data, and some precipitation experiments to verify the
derived E-pH diagram. The E-pH diagram constructed in this study
is significantly different from the one published earlier in Pourbaix’s
atlas 共Fig. 1兲. Of particular practical importance is the need to
clarify the low pH regions where the precipitation of the cerium
compounds seems to occur during processing.
Experimental
To observe the phase transformations of cerium in aqueous solu-
关1兴 tion, titration studies for pH change and cerium hydrolysis were
conducted. The tests were made at ambient temperature 共25 ⫾ 1°C兲
关2兴 using 100 mL of aqueous cerium solution, normally containing 0.01
mol/L of Ce共III兲 or Ce共IV兲. For Ce共IV兲, the solution was made from
关3兴 commercial 0.5 N stock solutions of Ce(ClO4 ) 4 which contained
some free HClO4 . For Ce共III兲, a commercial Ce(ClO4 ) 3 solution
关4兴 共40% w/w兲 was used. Solution pH was monitored continuously.
With continuous solution agitation provided by a magnetic stirrer,
the solution pH was slowly increased by addition of concentrated
共45.3% w/w兲 KOH solution in 10 or 20 ␮L increments using a 25
␮L syringe. As the cerium ions underwent hydrolysis, the pH, solu-
C624 Journal of The Electrochemical Society, 149 共12兲 C623-C630 共2002兲

To resolve reactions involving various Ce共IV兲 species, the Gibbs

energy of formation for each is needed, and the general expression
for Ce4⫹ hydrolysis is
Ki
Ce4⫹ ⫹ iH2 O → Ce共 OH兲 i4⫺i ⫹ iH⫹ 关11兴

where i is the level of hydration with values from 0 to 4.

Using literature values14 for the ⌬G f0 of H2 O, Ce4⫹, and OH⫺ as
well as the K i data,15 the ⌬G f0 values of the hydrolysis species can
be calculated according to the relation
⌬G 0 ⫽ ⫺2.303RT log K i ⫽ ⫺5709 log K i 关12兴

and are listed in Table II.

Using the data in Table II, the following results can be obtained:
when 关 Ce(OH) 3⫹兴 ⫽ 关 Ce4⫹兴 , pH ⫺0.76; when 关 Ce(OH) 2⫹ 2 兴
⫽ 关 Ce(OH) 3⫹兴 , pH 0.72; when 关 Ce(OH) ⫹ 3 兴 ⫽ 关 Ce(OH) 2⫹
2 兴 , pH
1.51; and when 关 Ce(OH) 4 兴 ⫽ 关 Ce(OH) ⫹ 3 兴 , pH 2.67. These results
Figure 1. Pourbaix diagram for cerium 共Pourbaix, 1974兲. are represented as lines B1 through B4 in the constructed E-pH
diagram.
Reactions between Ce(IV)/Ce 3⫹ (pH low to 2.67).—Using the
tion color, and the formation of solid phases were noted when the values in Table II and the general expression for the reactions be-
pH became stable. The experiments were made either open to air or
tween Ce3⫹ and Ce共IV兲
with Ar sparging.
Ce3⫹ ⫹ iH2 O → Ce共 OH兲 i4⫺i ⫹ iH⫹ ⫹ e 关13兴
Diagram Construction
The perchlorate system was chosen because ClO⫺4 has little ten-
For i from 1 to 4, the following four expressions can be obtained and
dency to form complexes with cerium ions, so the cerium behavior calculated
is equivalent to the Ce-H2 O system.
关 Ce共 OH兲 3⫹兴
E ⫽ 1.698 ⫹ 0.05916 log ⫺ 0.05916 pH 关14兴
Reaction between Ce 4⫹/Ce 3⫹.—The basic electrochemical reac- 关 Ce3⫹兴
tion between Ce3⫹ and Ce4⫹ is
关 Ce共 OH兲 2⫹
2 兴
3⫹
→ Ce 4⫹ ⫺
⫹e 关8兴 E ⫽ 1.741 ⫹ 0.05916 log ⫺ 0.1183 pH 关15兴
Ce 关 Ce3⫹兴

Using the updated standard molar Gibbs energy of formation at 关 Ce共 OH兲 ⫹
3兴
E ⫽ 1.830 ⫹ 0.05916 log ⫺ 0.1775 pH 关16兴
298.15 K, ⌬G f0 , of the two ions, the standard potential is14 关 Ce3⫹兴

0 0 关 Ce共 OH兲 4 兴
共 ⌬G f,Ce4⫹ ⫺ ⌬G f,Ce3⫹兲 E ⫽ 1.987 ⫹ 0.05916 log ⫺ 0.2366 pH 关17兴
E0 ⫽ 关 Ce3⫹兴
nF
⫺503,800 ⫹ 672,000 It can also be calculated that when 关 Ce(OH) 3⫹兴 ⫽ 关 Ce3⫹兴 and
⫽ ⫽ 1.743 V 关9兴 pH 0.103, E ⫽ 1.692 V; when 关 Ce(OH) 2⫹ 2 兴 ⫽ 关 Ce 兴 and pH
3⫹
1 ⫻ 96485 ⫹
0.74, E ⫽ 1.653 V; when 关 Ce(OH) 3 兴 ⫽ 关 Ce 兴 and pH 3⫹

RT 关 Ce4⫹兴 1.12, E ⫽ 1.632 V; and when 关 Ce(OH) 4 兴 ⫽ 关 Ce3⫹兴 and pH

E ⫽ 1.743 ⫹ ln 1.68, E ⫽ 1.590 V. All of the calculated potentials are nearly iden-
nF 关 Ce3⫹兴
tical to the values in Table I.
关 Ce4⫹兴
⫽ 1.743 ⫹ 0.05916 log 关10兴 Reactions among Ce(III) species.—Data on the hydrolysis of
关 Ce3⫹兴 Ce3⫹ has also been reported and the stability constants were defined
as
and when 关 Ce4⫹兴 ⫽ 关 Ce3⫹兴 , E ⫽ 1.743 V.
关 Ce共 OH兲 i3⫺i兴
Reactions among Ce(IV) species.—Although the hydrolysis of ␤i ⫽ 关 H⫹兴 i 关18兴
关 Ce3⫹兴
Ce4⫹ is very strong in aqueous solution, Bilal and Muller found that
free Ce4⫹ did exist in highly acidic solutions (⬎6.05 M HClO4 ), Several updated studies provided similar results.16,17 The typical
with a measured constant potential of 1.741 V.15 The same study data are listed in Table III. For the hydrolysis reaction
also found that there were four more distinct potential steps, be-
␤i
lieved to be the stepwise formation of the Ce共IV兲 mono-, di-, tri-,
and tetrahydroxo complexes as shown in Table I. Ce3⫹ ⫹ iH2 O → Ce共 OH兲 i3⫺i ⫹ iH⫹ 关19兴

Table I. Potential and pH experimental data for Ce„IV… species15 „at 298 K, with cerium concentration of 0.005 molÕkg….

Constant potential 共V兲 1.741 1.690 1.651 1.630 1.588 Drift lower
pH at constant potential 共V兲 Lower than ⫺0.7818 0.103 0.735 1.115 1.679 Higher than 1.679
species Ce4⫹ Ce共OH兲3⫹ Ce共OH兲2⫹
2 Ce共OH兲⫹3 Ce共OH兲4 Ce共OH兲4 /CeO2 precipitate
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 Journal of The Electrochemical Society, 149 共12兲 C623-C630 共2002兲 C625

Table II. Thermodynamic data related to Ce„IV… hydrolysis.

⌬G f0 Calculated ⌬G f0
K i values15 共kJ/mol兲14 共kJ/mol兲

log K1 ⫽ 14.76 ⫺ 1 ⫻ 13.996 ⫽ 0.764 (H2 O) ⫽ ⫺237.10 关 Ce共OH兲3⫹兴 ⫽ ⫺745.26

log K2 ⫽ 28.04 ⫺ 2 ⫻ 13.996 ⫽ 0.048 Ce4⫹ ⫽ ⫺503.80 关 Ce共OH兲2⫹2 兴 ⫽ ⫺978.27
log K3 ⫽ 40.53 ⫺ 3 ⫻ 13.996 ⫽ ⫺1.485 (H⫹) ⫽ 0 关 Ce共OH兲⫹3兴 ⫽ ⫺1206.77
log K4 ⫽ 51.86 ⫺ 4 ⫻ 13.996 ⫽ ⫺4.124 (OH⫺) ⫽ ⫺157.20 关 Ce共OH兲4 兴 ⫽ ⫺1428.66

where i is the level of hydration with values from 0 to 3. The Gibbs 关 Ce共 OH兲 4,aq兴
free energy of formation for Ce共III兲 species can then be calculated E ⫽ 1.987 ⫹ 0.05916 log ⫺ 0.2366 pH 关26兴
关 Ce3⫹兴
and the results are also listed in Table III. From these data the
following expressions among Ce共III兲 species can be obtained. When
with unit activity, at pH 2.67, E ⫽ 1.356 V; at pH 8.4, E
关 Ce(OH) 2⫹兴 ⫽ 关 Ce3⫹兴 , pH 8.4; at pH 9.2, 关 Ce(OH) ⫹ 2 兴/
⫽ ⫺0.003 V.
关 Ce(OH) 2⫹兴 ⫽ 1 and at pH 9.6, 关 Ce(OH) 3 兴 / 关 Ce(OH) ⫹ 兴 ⫽ 1.
2
From pH 8.4 to 9.2 where i ⫽ 1
These results are represented as lines C1 through C3 in the con-
structed E-pH diagram. It is also possible to obtain pH 8.8 when 关 Ce共 OH兲 4,aq兴
关 Ce(OH) ⫹2 兴 ⫽ 关 Ce 兴 , and pH 9.1 when 关 Ce(OH) 3 兴 ⫽ 关 Ce 兴 .
3⫹ 3⫹
E ⫽ 1.490 ⫹ 0.05916 log ⫺ 0.1775 pH 关27兴
关 Ce共 OH兲 2⫹兴
The Ce(OH) 3 used in Eq. 19 when i ⫽ 3 is assumed to be a
soluble Ce(OH) 3 ( aq) phase. Since the activity of the precipitate
with unit concentration, at pH 8.4, E ⫽ ⫺0.003 V; at pH 9.2, E
关 Ce(OH) 3 ( precip) 兴 is unity, and 关 Ce(OH) ⫹
2 兴 is less than unity, the
⫽ ⫺0.141 V.
actual pH for precipitation could be higher or lower depending on
the relative activities of these Ce共III兲 species. From pH 9.2 to 9.6 where i ⫽ 2

Reactions between Ce(III)/Ce 0.—Using the values in Table III, 关 Ce共 OH兲 4,aq兴
E ⫽ 0.946 ⫹ 0.05916 log ⫺ 0.1183 pH 关28兴
the expressions between Ce0 and the four Ce共III兲 species can be 关 Ce共 OH兲 ⫹
2兴
obtained. Using a general expression
with unit concentration, at pH 9.2, E ⫽ ⫺0.141 V; at pH 9.6, E
Ce3⫹ ⫹ iH2 O → Ce共 OH兲 i3⫺i ⫹ iH⫹ ⫹ 3e⫺ 关20兴 ⫽ ⫺0.193 V.
When pH is higher than 9.6 where i ⫽ 3
where i is from 0 to 3. For the pH from low values to 8.4 where i
⫽ 0 关 Ce共 OH兲 4,aq兴
E ⫽ 0.377 ⫹ 0.05916 log ⫺ 0.05196 pH 关29兴
关 Ce共 OH兲 3,aq兴
E ⫽ ⫺2.322 ⫹ 0.01972 log关 Ce3⫹兴 关21兴
with unit concentration and at pH 9.6, E ⫽ ⫺0.193 V; at pH 16,
From pH 8.4 to 9.2 where i ⫽ 1 E ⫽ ⫺0.570 V.
The E-pH diagram can then be constructed as shown in Fig. 2
E ⫽ ⫺2.156 ⫹ 0.01972 log关 Ce共 OH兲 2⫹兴 ⫺ 0.01972 pH 关22兴 using the expressions given previously.

From pH 9.2 to 9.6 where i ⫽ 2 Coatings

As described in the introduction, formation of the cerium con-
E ⫽ ⫺1.975 ⫹ 0.01972 log关 Ce共 OH兲 ⫹
2 兴 ⫺ 0.03947 pH 关23兴 version coatings is controlled by a local pH increase that precipitates
Ce compounds at the surface of the metal. The reaction can be
and when pH is above 9.6 where i ⫽ 3 initiated by cathodically polarizing the substrate or by placing it in a
solution where spontaneous dissolution of metal at the local anodes
E ⫽ ⫺1.785 ⫹ 0.01972 log关 Ce共 OH兲 3,aq兴 ⫺ 0.05916 pH will drive reduction reactions, generating OH⫺ and neutralizing H⫹
关24兴 at the cathodic sites.
As an example, using a fairly simple, albeit slow, Ce deposition
Reactions between Ce(IV)/Ce(III) (pH 2.67 and higher).—Using system, a coating was formed on a piece of 7075-T6 Al alloy by
the values in both Table II and Table III and the general expression immersing it for one week in an aqueous 0.01 M Ce(ClO4 ) 3 solu-
tion with some surface activating agents to provide a proper local
Ce共 OH兲 i3⫺i ⫹ 共 4 ⫺ i 兲 H2 O → Ce共 OH兲 4,aq ⫹ 共 4 ⫺ i 兲 H⫹ ⫹ e⫺ pH. A scanning electron microscope 共SEM兲 image 共Fig. 3兲 is shown
关25兴 below and cerium was detected on this substrate using energy dis-
persive spectroscopy.
where i is from 0 to 3, the following expressions can be obtained. The oxidation state of cerium in electrochemically derived ce-
From pH 2.67 to 8.4 where i ⫽ 0 rium oxide coatings for various deposition process parameters was

Table III. Selected thermodynamic data related to Ce„III… species.

⌬G f0 values Calculated ⌬G f0 s
共kJ/mol兲14 ␤ i values17 共kJ/mol兲

(H2 O) ⫽ ⫺237.10 log ␤1 ⫽ ⫺8.41 ⫾ 0.08 关 Ce共OH兲2⫹兴 ⫽ ⫺861.10

(Ce3⫹) ⫽ ⫺672.00 log ␤2 ⫽ ⫺17.60 ⫾ 0.24 关 Ce共OH兲⫹
2 兴 ⫽ ⫺1045.76
(H⫹) ⫽ 0 log ␤3 ⫽ ⫺27.23 ⫾ 1.19 关 Ce共OH兲3 兴 ⫽ ⫺1227.90
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C626 Journal of The Electrochemical Society, 149 共12兲 C623-C630 共2002兲
Figure 2. An updated Pourbaix diagram for cerium in aqueous perchlorate
solution.
determined by analyzing X-ray photoelectron spectroscopy 共XPS兲
data 共Fig. 4兲. Cerium conversion coatings on Al 7075-T6 test panels
that were deposited using different process conditions 共e.g., changes
to pretreatment steps兲 were examined. The characteristic peak for
Ce共IV兲 is at a binding energy of ⬃920 eV, while Ce共III兲 has a
characteristic peak near ⬃907 eV. In almost all of the coatings ana-
lyzed at least some Ce4⫹ was found. Examination of several samples
determined that the majority of coatings contained mainly Ce共IV兲
共process C, Fig. 4兲. However, Ce共III兲 was the predominant species in
one sample 共process A, Fig. 4兲 while a few samples had a distinct
peak at ⬃920 eV but unresolved peaks in the 895-910 eV range,
characteristic of a mixed Ce共III兲/Ce共IV兲 oxidation state 共process B,
Fig. 4兲. It is evident from the XPS data in Fig. 4 that the Ce oxida-
tion state is dependent on the deposition processing conditions.
Precipitation Studies
The major differences between the new and the previous E-pH
diagrams are the pH ranges identified for Ce共IV兲 precipitation and
the potentials for reactions between soluble Ce共III兲 and insoluble
Ce共IV兲 precipitates. Some precipitation tests were conducted to ex-
amine the trends indicated by the new diagram and to attempt to
correlate the changes in stability regions indicated in the new dia-
gram with actual behavior.
Figure 3. SEM image of a cerium coating on 7075-T6 aluminum panel.
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Figure 4. XPS analysis of cerium oxide coatings: 3d signals.
Ce(III) solutions-pH effects.—100 mL of 0.01 mol/L Ce(ClO4 ) 3
solution with an initial pH of about 3.4 was made following previ-
ously described methods. For each titration step, 10 ␮L KOH 共45.3
wt %兲 was added. With the cell open to air, pH stabilization was
slow, so the values were recorded when the solution became stable
共ca. 8 min兲 after each addition of hydroxide. When Ar sparging was
used, pH stabilized much faster. pH values were plotted vs. moles of
KOH added.
The results for Ce(ClO4 ) 3 are shown in Fig. 5. Several important
features were noted in the plots. 共i兲 With the cell exposed to air,
there was a wide buffered region centered at about pH 6 that started
from the initial OH⫺ addition until a stoichiometry of three to one,
hydroxide to cerium, was reached. At this point, the pH rises
abruptly. 共ii兲 With Ar sparging, the buffering occurred at a pH of 8,
which was much higher than in air. After each 10 ␮L KOH addition,
the pH was more stable than when the cell was exposed to air. Also,
when the pH started to rise steeply, the stoichiometry was about 2.5,
implying almost equal concentrations of Ce(OH) ⫹ 2 and Ce(OH) 3 ( aq) .
共iii兲 During the titration, there were no clear pH steps before the
precipitation of Ce(OH) 3 ( precip) and the final pH increase, which
implies that the formation of Ce(OH) 2⫹, Ce(OH) ⫹ 2 , and
Ce(OH) 3 ( aq) could be progressive and continuous. (i v ) Precipitation
occurred when the pH started to rise abruptly. In both Ar and air,
since the rise occurred when the OH⫺ addition was over stoichiom-
etry 2, the implication is that initial cerium共III兲 hydroxide has some
solubility, and precipitation occurred after the solution pH was
higher than about 10
Figure 5. Titration curve of Ce(ClO4 ) 3 solution using concentrated KOH
solution. Slight cloudy appearance was observed from point A1 in Ar atmo-
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 Journal of The Electrochemical Society, 149 共12兲 C623-C630 共2002兲
Figure 6. Titration curves of HClO4 and Ce(ClO4 ) 4 solution using concen-
trated KOH solution.
Ce共 OH兲 3 共 aq兲 → Ce共 OH兲 3 共 precip兲 关30兴
This was later confirmed using more dilute Ce共III兲 solution
共0.001 mol/L兲 with Ar sparging, where the steep pH rise occurred at
a stoichiometry of 3. ( v ) The phases or the structure of the precipi-
tates could change depending on the conditions, such as atmosphere.
With air exposure, the precipitate is yellow, likely containing Ce共IV兲
oxide. But with Ar, the precipitate is an almost colorless, translucent
white gel and probably without Ce共IV兲 oxide. ( v i) The presence of
O2 seems to cause major differences in many aspects of the Ce共III兲
hydrolysis and precipitation processes; apparently Ce共IV兲 was
formed with air exposure. Equation 5 defines the 3:1 stoichiometry
for OH⫺ to Ce3⫹ to give Ce(OH) 3 . Even though some of the Ce共III兲
may be converted to Ce共IV兲, such as in Eq. 31
4Ce共 OH兲 2⫹ ⫹ O2 ⫹ 2H2 O → 4Ce共 OH兲 2⫹
2 关31兴
the conversion neither consumes nor generates extra OH⫺ and there-
fore, the 3:1 ratio is preserved. In Ar, the apparent stoichiometry is
2.5, possibly because the dissolution rate (k ⫺1 ) of Ce(OH) 3 ( aq) is
higher than that when exposed to air
k1
Ce共 OH兲 ⫹ ⫺
2 ⫹ OH  Ce共 OH 兲 3 共 aq兲 关32兴
k ⫺1
therefore, when concentration of Ce(OH) 3 increases 关both
Ce(OH) 3 ( aq) and the gel form Ce(OH) 3 ( precip) ], higher OH⫺ concen-
tration is required to maintain the equilibrium. When O2 is present
the formation of Ce共IV兲 could significantly lower the concentration
of Ce(OH) 3 ( aq) , which favors the reaction in the precipitation direc-
tion for cerium.
Ce(IV) solutions-pH effects.—Similar tests for Ce共IV兲 were per-
formed using 100 mL of 0.01 mol/L Ce(ClO4 ) 4 solution at a starting
pH value of about 0.97. This low value was partly attributed to free
acid in the original stock solution, which was necessary to keep
Ce共IV兲 soluble. To calculate the consumption of OH⫺ solely by
cerium and the initial state of Ce共IV兲, the consumption of OH⫺ by
the free acid had to be considered and estimated.
Titration of the 0.01 mol/L Ce(ClO4 ) 4 containing free HClO4
acid and pH 0.97 solution showed that the total OH⫺ used to neu-
tralize the pH was about 16 共Fig. 6兲 in stoichiometry number 共or 16
units兲 with each number equivalent to 0.001 mol of Ce ions present.
Since the total Ce共IV兲 in the tested solution is 0.001 mol 共one unit兲
and the total ClO⫺ 4 is 0.016 mol, the ionic strength of this solution
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C627
could be 0.22 if all of the cerium is as Ce4⫹, or 0.17 if all the cerium
is as Ce(OH) 2⫹
2 or 0.16 if all of the cerium is present as Ce(OH) 4 .
From experimental observations and E-pH diagram 共Fig. 2兲, it is
reasonable to estimate that the cerium in the starting solution is in
the form of 关 Ce(OH) 3⫹兴 and 关 Ce(OH) 2⫹ 2 兴 with roughly equal con-
centrations 共0.5 unit兲. Thus the ionic strength of this solution is ␮
⫽ 0.180. Using the Debye-Hückel expression18
0.51Z H⫹冑␮
2
⫺log ␥ H⫹ ⫽ 关33兴
1 ⫹ 3.3a H⫹冑␮
⫹
the activity coefficient of H⫹ is calculated to be 0.802, where a H
⫽ 0.9.
Using this number, the starting pH value of 0.97 of the Ce共IV兲
perchlorate solution was equivalent to the H⫹ concentration of 0.134
mol/L, a stoichiometry number of 13.4. Based on the above analysis,
to neutralize Ce共IV兲 in the solution to Ce(OH) 4 and make the solu-
tion pH over 7, one unit of Ce共IV兲 should take about 2.6 unit of
OH⫺, implying that the initial form of Ce共IV兲 was a mixture of
Ce(OH) 3⫹ and Ce(OH) 2⫹ 2 in almost equal amounts.
Another approach is to assume that there is no free acid in the
two 0.01 mol/L Ce共IV兲 solutions, and assume that the activity and
the concentration of H⫹ are the same. Then the pH would probably
be between 7 关without Ce共IV兲 hydrolysis兴 and 1.40 关Ce共IV兲 com-
pletely forming Ce(OH) 4 and generating 0.04 mol/L H⫹]. When the
activity of H⫹ is considered and with the same ionic strength (␮
⫽ 0.18 and ␥ H ⫽ 0.802), the pH is 1.49 for a H⫹ concentration of
0.04 mol/L.
To further confirm the particular pH where the solution has 0.04
mol/L H⫹ with ␮ ⫽ 0.18, a 0.180 mol/L HClO4 (␮ ⫽ 0.180) so-
lution was tested. As shown in Fig. 7, the pH which is 4 units from
neutral was about 1.45. One of the reasons for the slight difference
with the calculated number of 1.49 was probably the accuracy of the
activity coefficient for H⫹ in this relatively concentrated solution.
Data shown in the same figure indicated that further increasing the
ionic strength with the addition of 1.0 mol/L KClO4 (␮ ⫽ 1.18)
caused this pH to decrease to about 0.9 共Fig. 7兲. Examination of
this curve revealed that when KClO4 started to precipitate
(K sp ⫽ 0.042), the ionic strength decreased, resulting in a turn in
the titration curve toward the behavior of lower ionic strength solu-
tion. From these observations, pH 1.45 was considered to be a rea-
sonable value for the 0.01 mol/L Ce(ClO4 ) 4 solution in the hydra-
tion analyses.
Therefore, if the KOH consumption was counted from the very
beginning and from about pH 1.45 in this solution, and using the
theoretical values in Ref. 14, it would be possible that the initial
forms of Ce共IV兲 and the hydrolysis process could be estimated.
The titration curves for Ce(ClO4 ) 4 solutions with either Ar
sparging or air exposure are shown in Fig. 6. The total KOH con-
sumption of the solution is 16 units. When it started from pH 1.45,
about 6.5 units of KOH was used to complete Ce(OH) 4 precipita-
tion and increase the pH to over 7. Therefore, the Ce共IV兲 at pH 1.45
was probably a mixture of Ce(OH) 3⫹ and Ce(OH) 2⫹ in almost
2
equal amounts. The flat, low pH area of the curve that follows is the
neutralization of free acid and the completion of Ce(OH) 2⫹ 2 forma-
tion. The following steep pH rise was the indication of the comple-
tion of both reactions. A buffer region, about 1.5 to 1, 2 units in
width followed where the pH was near 5.5 when the solution was
exposed to air. With Ar sparging, pH slowly increased over the same
region. The last pH rise was clearly the completion of Ce共IV兲 pre-
cipitation. As in the Ce共III兲 systems, the color of the precipitates was
also dependent on the atmosphere. A yellow precipitate was ob-
tained in an air environment, whereas the precipitate was purple
with Ar present.
C628 Journal of The Electrochemical Society, 149 共12兲 C623-C630 共2002兲

Unlike the Ce共III兲 system, the pH buffering region of Ce共IV兲

appeared in the latter part of the titration. By tracking the stoichi-
ometry numbers, the buffered region should be attributable to the
further hydrolysis of the Ce(OH) 2⫹
2 . The reaction could be

⫺ ⫹
2 ⫹ OH → Ce共 OH 兲 3
Ce共 OH兲 2⫹ 关34兴

Since the solution became cloudy 共at the start of precipitation兲 at

the beginning of this region 共note in Fig. 6兲, Ce(OH) 4 is probably
formed. Therefore, the decomposition of Ce(OH) ⫹ 3 was very likely,
because Ce(OH) ⫹ 3 was believed to be unstable and further fast re-
action could be possible. One of the possibilities for decomposition
is

2Ce共 OH兲 ⫹
3 → Ce共 OH 兲 2 ⫹ Ce共 OH 兲 4
2⫹
关35兴

Using the free energies from Table II, a very small positive ⌬G 0
is obtained from Reaction 35 indicating a nonspontaneous reaction,
but this depends on the accuracy of data, activities, and reactivities
of the species involved. Another possibility is that Reaction 34 is
slow, but the following Reaction 36 is much faster
fast
Ce共 OH兲 ⫹ ⫺
3 ⫹ OH ——→ Ce共 OH 兲 4 关36兴
In both cases, the pH could be buffered between Ce(OH) 2⫹ 2 and
Ce(OH) 4 . The slowly increasing pH in Ar implied that Ce(OH) 4
could have some solubility or form a gel-type product. When O2
was present, some phase transformation was observed, such as a
yellow product rather than a purple precipitate. It was also noticed
that the yellow form 共likely CeO2 •xH2 O) separates better from wa-
ter probably because it has lower solubility. This could be favorable
for Reactions 34 or 36 to proceed.
Discussion
Both Ce共III兲 and particularly Ce共IV兲 ions in aqueous solution
have a tendency to hydrolyze and complex. The hydroxides
Ce(OH) 3 and Ce(OH) 4 /CeO2 •2H2 O, although initially soluble to
some degree,15 are normally the major forms precipitated. These
phases could also be in hydrated oxide forms. Furthermore, Ce共III兲
and Ce共IV兲 species could polymerize,16,19 especially at higher ce-
rium concentrations, but additional work is needed in this area. It
should also be noted that the Gibbs energies of formation for cerium
oxides, nonhydrated CeO2 and Ce2 O3 , were not used in the calcu-
lations in this paper, since they are probably not the species formed
in aqueous solutions.
Observations indicated that both Ce共III兲 and Ce共IV兲 could pre-
cipitate as different phases or forms as shown by the color and
appearance of the precipitates in different atmosphere. The presence
of oxygen in solution could have a significant impact on the changes
in phases of the precipitate and the reactions between Ce共III兲 and
Ce共IV兲.
As is often the case, freshly precipitated Ce共IV兲 phases could
vary depending on the specific precipitation conditions. In particular,
the morphology, degree of agglomeration, and surface chemical ac-
tivity may change with experimental methodology.
Comparison of the constructed E-pH diagram to the titration ex-
perimental results shows that the two correlate reasonably well.
However, several differences were also observed.
共i兲 Some of the hydration lines of Ce共IV兲 in Fig. 2 共B1 through
B4兲 appear at lower pH than experimentally observed. For instance,
the B4 line is at pH 2.66, but the titration lines in Fig. 6 show that,
in air, the precipitation is observed at pH 3.5, and the mid value pH
is about 5.5. In argon, these pH values are even higher, although
they are much lower than that in previous E-pH diagrams. One of
the more likely possibilities is that the pH values for B1 through B4
come from solutions containing several moles per liter of ClO⫺ 4 salt.
As shown in Fig. 7, the observed pH would be much lower than for
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Figure 7. Titration curve of HClO4 solution using concentrated KOH solu-
tion. The ionic strength was 0.18.
solutions containing less salt. In other words, the pH values of lines
B1 through B4 may not be fixed values, but depend on the ionic
strength of the solutions. Based on our observations, the free acid in
our precipitation test solution is closer to the minimum amount for
maintaining soluble Ce共IV兲. Therefore, the pH values given in Fig. 6
are closer to the highest possible pH values for the related Ce共IV兲
hydrolysis steps.
共ii兲 As shown in Fig. 5, the pH for Ce共III兲 hydrolysis in air is
lower than 6 after 8 min stabilization and could be even lower with
extended time. This is two scales lower than that predicted in Fig. 2
共C1 through C3兲. The reason for this major difference is probably
because of the shift of equilibrium by the formation of Ce共IV兲 from
Ce共III兲 by oxygen. The hydrolysis of Ce共IV兲 proceeds before Ce共III兲
at a similar pH. For instance, at the solution pH about 4 to 6, Ce3⫹
is a stable soluble form of Ce共III兲, but Ce(OH) 2⫹2 is the only stable
form of Ce共IV兲. The two Reactions 37 and 38
Ce3⫹ ⫹ OH⫺  Ce共 OH兲 2⫹ 关37兴
4Ce3⫹ ⫹ 4 OH⫺ ⫹ O2 ⫹ 2H2 O → 4Ce共 OH兲 2⫹
2 关38兴
compete for hydroxy ions. Although the equilibrium for the revers-
ible Eq. 37 is around pH 8, the irreversible Eq. 38 should be around
pH 4-6. Although Eq. 38 will not change the 3:1 ratio of hydroxy to
cerium as indicated in Eq. 31, it does ‘‘consume’’ hydroxy ions and
lower solution pH to where both Ce3⫹ and Ce(OH) 2⫹ 2 are stable.
When Ce共IV兲 formation was avoided by continuous Ar sparging
before titration 共pH was about 3.4兲, neither Reactions 38 nor 31 are
expected, Reaction 37 and the following Ce共III兲 hydrolysis steps are
the only pH related equilibrium relations, which result in solution
pH values over 8 as shown in Fig. 5.
共iii兲 The effect of oxygen is more significant on Ce共III兲 titration
and less on Ce共IV兲. From previous experience, which will be dis-
cussed in more detail in a subsequent publication, at low pH Ce共IV兲
could oxidize variety of species, including water, and becomes
Ce共III兲, and Ce共III兲 could be oxidized to Ce共IV兲 at higher pH by
other oxidizers including oxygen. The titration results showed that
the Ce共III兲 oxidation by oxygen is a fast reaction, but the reduction
of Ce共IV兲 by water is very slow. A more significant impact of the
presence of oxygen on the Ce共IV兲 hydrolysis is observed on the
Ce(OH) 4 precipitation, indicating a phase change of the precipitate.
It should be mentioned that some expressions plotted in Fig. 2,
such as C3 and B4, were obtained by assuming that the activities of
the species involved are equal. For Ce共III兲, if Ce(OH) 3 ( aq) was used,
 Journal of The Electrochemical Society, 149 共12兲 C623-C630 共2002兲 C629

the line C3 could shift to lower pH when 关 Ce(OH) 3 ( aq) 兴 ⌬G 0 value of Ce共III兲 species ⌬G 0 value of Ce共IV兲 species
⬍ 关 Ce(OH) ⫹ 2 兴 ; but if Ce(OH) 3 ( precip) was used, line C3 could move 共kJ/mol兲 共kJ/mol兲
to higher pH because 关 Ce(OH) 3 ( precip) 兴 ⫽ 1 and 关 Ce(OH) 3 ( precip) 兴 Ce
3⫹
⫺672.00,14 ⫺718.60 20 Ce
4⫹
⫺50.380,14 ⫺510.00 24

⬎ 关 Ce(OH) ⫹ 2 兴 . A similar analog is also valid for Ce共IV兲 for line ⫺678.01, 23
⫺676.00 24
⫺508.00, 26
⫺507.52 27

B4, but since Ce(OH) 4 ( precip) or CeO2 •2H2 O are likely the forms of
⫺677.00,26 ⫺675.72 27
⫺503.80,28 ⫺503.80 29
Ce(OH) 4 , which have unity activity, line B4 would likely shift to a
⫺672.00, 28
⫺672.00 29
⫺505.65 30
higher pH. In solutions where cerium ions may form complexes
with anions other than hydroxy ions, the precipitation pH could be ⫺681.76 30

higher. Ce2 O3 ⫺1896.15ahydr ,1 ⫺1706.20 s 14

CeO2 ⫺916.30 s,20 ⫺1024.60 s 14

Additional thermodynamic data would be useful in further devel- ⫺1706.20 s,24 ⫺1707.93 s 22
⫺1024.60 s,24 ⫺1025.38 s 22

oping the diagrams. Of specific interest are the thermodynamic data

⫺1708.03 s, 27
⫺1706.20 s 28
⫺1025.33 s, 27
⫺1024.60 s 28
for the formation and transition of the precipitates of hydroxides
⫺1707.36 s 30
⫺997.90 s,30 ⫺986.04 pt 21
and/or hydrous and hydrated cerium oxides, the equilibria expres-
3⫹
sions and reactions among precipitates, the identification of any pos- Ce共OH兲3 ⫺1303.86 s, 20,25
⫺1286.40 s 23 Ce共OH兲 ⫺789.94, 20
⫺749.35 27

sible soluble Ce-O species at high pH and pertinent data for possible ⫺1268.59 s,27 ⫺1264.74 s 29
⫺742.27,29 ⫺761.37 30

polymerization reactions. ⫺1286.20 s 30

⫺747.75, 35
⫺743.75 37

⫺1264.82 am, 16
⫺1262.31 am 38
⫺770.58, 36
⫺759.16 38

⫺1227.90 aq, 15
⫺1228.07 aq 35
Conclusions
⫺1228.64 aq,16 ⫺1228.07 aq 38

An updated E-pH diagram for cerium in aqueous HClO4 solution

⫺1261.80 pt 21
was constructed. The major difference noted was that the theoretical ⫹ 2⫹
Ce共OH兲2 ⫺1045.76,21 ⫺1045.76 35 Ce共OH兲2 ⫺1025.92,20 ⫺1020.90 30
pH for Ce共IV兲 precipitation was much lower than indicated in the
original diagram. ⫺1045.76, 38
⫺1050.89 16
⫺980.85, 35
⫺989.41 37

Precipitation tests confirmed that the newly constructed E-pH ⫺989.41 38

diagram seemed reasonable in light of the experimental results. In 2⫹

CeOH ⫺865.25,31 ⫺861.10 15

0.01 mol/L Ce(ClO4 ) 4 solution, the Ce(OH) 4 precipitation starts at ⫺861.73, 33

⫺861.16 34

pH values less than 5. In perchlorate solution, Ce(OH) 2⫹ 2 is a more ⫺861.45, 38

⫺861.73 35

stable ionic form than Ce(OH) 3⫹ and Ce(OH) ⫹ 3 in the Ce共IV兲 hy-
⫺861.73 16
drolysis process. ⫹
The Ce共III兲-Ce共IV兲 system is very sensitive to atmosphere, par- CeO ⫺819.65 31 Ce共OH兲4 ⫺929.27 32

ticularly O2 which proved to have a major impact on the phase CeO共OH兲 ⫺1001.23 aq 31

⫺
formation and solution pH. Different forms of Ce共IV兲 precipitates CeO2 ⫺929.27 31

appeared to be present depending on experimental conditions. a

In Ce(ClO4 ) 3 solution, the initial Ce共III兲 was in the nonhydro-
lyzed form of Ce3⫹. The hydration proceeds to about pH 8 in argon
and less than 6 in air. The three hydrolysis steps are continuous and
relatively fast. Ce共OH兲3 could be soluble and the precipitation oc-
curred when pH is higher than 9.
Overall, the updated E-pH diagrams for cerium and the titration
experiments using both Ce共III兲 and Ce共IV兲 provide further under-
standing for cerium applications such as the deposition of conver-
sion coatings to retard corrosion of aluminum alloys.
Acknowledgments
The authors wish to acknowledge the financial support provided
through the U.S. Air Force under contract F33615-97-D-5009. We
are also grateful for the guidance of program manager Steven
Szaruga of the Materials Directorate of the Air Force Research
Laboratory at Wright-Patterson Air Force Base. The assistance of
John Grant 共WPAFB兲 in obtaining the XPS data is also appreciated.
The Hitachi S4700 SEM used in this work was purchased on
grant DMR 9704288 from the National Science Foundation. The
assistance of the SEM operator, Clarissa Vierrether, is also acknowl-
edged.
The University of Missouri-Rolla assisted in meeting the publication
costs of this article.
Appendix
Some Thermodynamic Data Related to Cerium
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c, crystal; aq, aqueous form; am, amorphous; pt, precipitate; hydr, hydrated form.
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