Electrochimica Acta 83 (2012) 471–477

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Kinetics of oxidation and dissolution of uranium dioxide in aqueous

acid solutions
Coralie Gaulard-Balandret a,b,c,∗ , Nathalie Larabi-Gruet d,∗∗ , Frédéric Miserque e ,
Jean Radwan a , Cécile Ferry a , Annie Chaussé c
a
CEA, DEN, DPC, SECR, Laboratoire de Mesures et Modélisation de la Migration des Radionucléides, F-91191 Gif-sur-Yvette, France
b
ANDRA, Parc de la Croix blanche, 1/7 rue Jean Monnet, 92298 Châtenay-Malabry Cedex, France
c
Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement (CNRS-CEA-Université d’Evry UMR 8587), Université d’Evry Val d’Essonne, 1 rue du Père Jarlan, 91025 Evry
Cedex, France
d
CEA, DEN, DPC, SCCME, Laboratoire d’Etude de la Corrosion Non Aqueuse, F-91191 Gif-sur-Yvette, France
e
CEA, DEN, DPC, SCCME, Laboratoire d’Etude de la Corrosion Aqueuse, F-91191 Gif-sur-Yvette, France

a r t i c l e i n f o a b s t r a c t

Article history: The oxidation and dissolution of UO2 has been studied using electrochemical methods with an UO2
Received 22 December 2011 rotating disc electrode in acidic (pH 3) and non-complexing (trifluoromethanesulfonate: 0.1 mol L−1
Received in revised form 4 April 2012 NaCF3 SO3 ) media. The effect of the experimental parameters such as scan rate (v) and rotation rate
Accepted 4 April 2012
(ω) on the electrochemical signal has been studied. The rotation rate of the electrode does not influ-
Available online 13 June 2012
ence the resulting signal, which indicates that only a charge transfer is involved in the UO2 oxidation
kinetic. However, scan rate variations show different reactions involved in the UO2 oxidation. Linear
Keywords:
sweep voltammetry and cyclic voltammetry coupled to X-ray photoelectron spectroscopy (XPS) and
Uranium dioxide
Oxidation mechanism
inductively coupled plasma mass spectrometry (ICP-MS) measurements suggest two successive elec-
Triflate ions trochemical reactions with an exchange of one electron for each of them and the formation of one
Perchlorate ions intermediate species of U(V).
Rotating disc electrode © 2012 Published by Elsevier Ltd.

1. Introduction corrosion, and especially to well-describe mechanisms occurring

Within the framework of the geological disposal for nuclear
spent fuel, French authorities decided to focus main research fields
onto the long term behavior of the vitrified waste resulting from
the retreatment of spent fuel [1]. Nevertheless, the behavior of the
non-retreated spent fuel directly placed into the geological dis-
posal is still studied as an optional scenario for radioactive waste
disposal performance assessment. Considering the actual disposal
concept, spent fuel conditioning would be maintained by a steel-
container whose sealing performance is guaranteed for a specific
period in the range of 10,000 years. It is then, reasonable to assume
that after this period of time, the groundwater will be in contact
with the spent fuel, as the steel-container would have been already
degraded. This deterioration by the groundwater will lead to UO2
matrix degradation and the release of radionuclides. In such a con-
text, it is necessary to obtain a better understanding of spent fuel
∗ Corresponding author at: CEA, DEN, DPC, SECR, Laboratoire de Mesures et Mod-
élisation de la Migration des Radionucléides, F-91191 Gif-sur-Yvette, France.
Tel.: +33 1 69081260; fax: +33 1 69081586.
∗∗ Corresponding author. Tel.: +33 1 69081260; fax: +33 1 69081586.
E-mail addresses: coralie.gaulard@wanadoo.fr (C. Gaulard-Balandret),
nathalie.gruet@cea.fr (N. Larabi-Gruet).
for UO2 oxidation and dissolution in water-saturated host rock.
Most published studies were conducted under the characteristic
conditions of disposal [2–7]. In such conditions, several parameters
may influence the spent fuel corrosion: intrinsic corrosion rate, pH
values, O2 concentration, solution constituents, temperature and
water radiolysis [8], which lead to obtain a complex electrochem-
ical system to interpret and model. Only a few studies about the
oxidation and dissolution of UO2 were realized at acidic pH val-
ues [2,9,10]. In acidic media, the global reaction UO2 → UO2 2+ + 2e−
predominates and formation of precipitates is avoided. That is the
reason why, the present paper proposed a study of the oxidation
and dissolution of uranium dioxide in deaerated acidic and non-
complexing media. The influence of two different experimental
parameters (scan rate, v and electrode rotation rate, ω) on the elec-
trochemical signal is developed in order to propose a mechanism
for theses electrochemical reactions. Then, these parameters will
be used in further work to develop a robust model for the UO2
oxidation under disposal conditions.
2. Experimental
All electrochemical measurements were performed using an
Autolab pgstat30 potentiostat/galvanostat (Eco Chemie) system

0013-4686/$ – see front matter © 2012 Published by Elsevier Ltd.

http://dx.doi.org/10.1016/j.electacta.2012.04.022
472 C. Gaulard-Balandret et al. / Electrochimica Acta 83 (2012) 471–477
controlled by a computer and using an electrochemical cell con-
ventional at three-electrodes with an UO2 rotating disk electrode
(EDI 101, Hach Lange) as working electrode. The UO2 disc, pro-
vided by CEA of Cadarache (DEN/DEC/SESC/LLCC), (surface area,
S = 0.28 cm2 ) was inserted in a tip (EM-EDI-PE, Hach Lange Speed
Control Unit CTV 101). A platinum wire was used as auxiliary
electrode. In order to avoid possible contaminations of electro-
chemical products formed at the auxiliary electrode, the platinum
wire was isolated from the test solution using a capillary exten-
sion filled with the test solution. An Ag/AgCl wire, isolated from
the test solution using a capillary extension filled with a solution
containing 0.02 mol L−1 NaCl and 0.08 mol L−1 NaCF3 SO3 , was used
as reference electrode. The NaCl/NaCF3 SO3 mixture was used to
fill the reference electrode instead of a pure NaCl solution. The
AgCl deposit requires NaCl, but releases chloride ions, which can
affect the electrochemical signal. In order to minimize this chlo-
ride effect, NaCF3 SO3 is added. In addition, the molar ionic strength
of this NaCl/NaCF3 SO3 mixture is the same as the test solutions
(reference electrode potential value in aqueous solution at 25 ◦ C
relative to SHE is −340 mV versus SHE. This value is determined
from electrochemical system benzoquinone/hydroquinone).
The pH value was measured with a combined glass electrode
(Radiometer pHC3081-8) connected to a pH-meter (Radiometer
pHM 250). The pH glass electrode combined with Ag/AgCl was
calibrated at 25 ◦ C with the NIST solutions at pH 6.87 and pH
4.01. The combined glass electrode was filled of a 0.02 mol L−1
NaCl/0.08 mol L−1 NaCF3 SO3 mixture solution. The pH values were
adjusted with few amount of HCF3 SO3 solution (0.1 mol L−1 ), which
was added using a syringe and the pH variation was always inferior
to 0.05.
All reagents were of analytical grade purity from Sigma Aldrich.
Solutions were prepared using 18 M cm nano-pure water (Milli-
pore), and deaerated with argon (U, Air Liquide). Experiments were
performed under anoxic conditions. Dissolved O2 concentration in
solution was estimated to 1 ppm, i.e. 3.6 × 10−5 mol L−1 using linear
sweep voltammetry on Au rotating disc electrode. This O2 con-
centration is far below the O2 concentrations measured in aerated
media [4,11]. Prepared solutions were maintained to a constant
temperature value of 25 ◦ C with a Thermostat/Cryostat F33-MC
(Julabo) and experiments were conducted in darkness to avoid
disturbances due to the semi-conductor character of the uranium
dioxide.
The UO2 electrode preparation is performed according to the
following three stages:
- a mechanical cleaning of the UO2 electrode, where the pellet is
polished with a 320 grit SiC paper,
- a cathodic cleaning of UO2 electrode where the electrode is
reduced at −1370 mV/SHE then at −880 mV/SHE during five min-
utes. X-ray photoelectron spectroscopy (XPS) experiments show
that these conditions are sufficient to ensure a composition close
to UO2.00 at the electrode surface,
- a potential’s imposition at −90 mV/SHE during 1 h into the solu-
tion. This allows to minimize natural oxidation of UO2 and to be
in a potential range where UO2 is close to stoichiometry. The
three stages ensure reproducibility with always the same com-
position, close to UO2.00 , at the surface before the acquisition of
current–potential curves.
Electrochemical methods used in this study are the cyclic
voltammetry and the linear sweep voltammetry. In the cyclic
voltammogram, the potential is firstly scanned from a relatively
negative potential (Ei = −90 mV/SHE), at which the UO2 pellet is
close to the stoichiometry and the amount of I is close to zero, to
a negative limit (the cathodic limit) and then, the reverse way is
scanned. For each experiment, four scans have been performed. All
curves have been corrected by the IR drop using the current inter-
rupt method. The reproducibility of all electrochemical curves has
been checked by ten similar measurements.
Characterization of the UO2 surface is realized by XPS. XPS spec-
tra were recorded with ESCALAB 220 iXL (ThermoScientific) using
a monochromatized Al-K␣ X-ray source. Scans were performed for
the U-4f region, which consists of the U-4f5/2 and U-4f7/2 peaks
and their satellite peaks, as well as of the C-1s to correct the sur-
face charging (C-1s at 285.0 eV), O-1s and the U-5f valence band
regions.
The U amount in solution is characterized by inductively cou-
pled plasma mass spectrometry (ICP-MS) (810-MS, Varian).
3. Results and discussion
3.1. Thermodynamic data
The oxidation state of UO2 and the redox properties of media
play an important role in the study and the understanding of
the UO2 oxidation/dissolution mechanism. Uranium can be found
under four different oxidation states: +III, +IV, +V and +VI where +IV
and +VI are the most stable oxidation states in aqueous systems.
Fig. 1 shows, in solid lines, Eh-pH diagram of uranium plotted, at
25 ◦ C, zero ionic strength (I = 0) and a total uranium concentration
of 1.7 × 10−7 mol L−1 . This concentration corresponds to the order
of magnitude of uranium in solution at the beginning of experi-
ments. This value has been measured by ICP-MS. Solid phases are
represented in bold and underlined. Moreover, it has been added in
Fig. 1, in gray and in dotted lines, the Eh-pH diagram of uranium at
25 ◦ C and zero ionic strength, and indicating the existence domain
of UO2 + . This Eh-pH diagram is plotted only with aqueous species
because the thermodynamic constants for U(V) solids are difficult
to obtain and unknown. The thermodynamic data used for these
diagrams were selected or calculated from the update of NEA-OECD
[12].
Uranium (VI) species are soluble except for UO3 ·2H2 O(cr),
whose domain of predominance is for 6.3 < pH < 8.7 and for
Eh > 0.25 V/SHE. UO2 2+ is the dominating aqueous U(VI) species for
Eh > 0.2 V/SHE and up to pH 5.3. The other uranium (VI) species are
hydroxides that predominate from pH 5.3. Uranium (IV) is mainly
represented by a solid phase, UO2 (cr), which is the dominating solid
species for Eh < 0.2 V/SHE. At pH > 4.2, secondary phases precipitate
on the UO2 (cr) surface: UO2.25 (cr), ␤-UO2.33 and U3 O8 (cr). UO2 +
exists over a potential range −0.15 V/SHE to 0.1 V/SHE and up to
pH 8.2.
3.2. Choice of medium
Perchloric acid and perchlorate ions are often used as stable
supporting electrolytes in electrochemical studies [3,9,13,14], but
a recent study showed that in the case of metal dissolution, the
reduction of ClO4 − leads to the formation of Cl− plays a substantial
role on the oxidation of the metal [15]. So, Cl− may affect oxidation
rate of the uranium dioxide and this presence should be avoided.
Trifluoromethylsulfonate ions offer a good alternative to perchlo-
rate ions especially when reagents which are potential oxidants
or are solvolytically unstable must be avoided [16]. The sodium
trifluoromethanesulfonate, as sodium perchlorate, is used as inert
supporting electrolyte for electrochemical studies because of its
large range of electroactivity [17,18], its stability to high tempera-
ture and high pressure [19] and its chemical stability. A study was
realized in order to check if the electroactivity range of NaCF3 SO3
is consistent with the study of UO2 . This range was studied on two
inert electrodes, Pt and Au electrodes, at two pH: 3 and 9.2 (pH 3
correspond to the study in acidic non-complexing media, and pH
 C. Gaulard-Balandret et al. / Electrochimica Acta 83 (2012) 471–477
Fig. 1. Eh-pH diagram of uranium ([U]tot = 1.7 × 10−7 mol L−1 , I = 0, T = 25 ◦ C) in bold black lines and existence domain of UO2 + (I = 0, T = 25 ◦ C) in gray and in dotted line.
9.2 correspond to the natural pH of NaCF3 SO3 ), using the j–E curves
(Fig. 2a and b).
Whatever the pH value, the domain of electroactivity on Pt elec-
trode is smaller than that on Au electrode. In addition, at pH 3, a
wave is observed at E = −300 mV/SHE for Pt and at E = −550 mV/SHE
for Au. In contrast, at alkaline pH, no wave is observed. Trémillon
and co-workers have observed this behavior and have attributed
this wave to the reduction of SO3 dissolved [18]. j–E curve obtained
on the UO2 rotating disk electrode in 0.1 mol L−1 NaCF3 SO3 at pH
3 (Fig. 2c) shows that the domain of study of UO2 is over the
potential range of −350 to 800 mV/SHE. The reduction wall, from
−350 mV/SHE, is attributed to the reduction of protons and not to
the reduction of dissolved SO3 from supporting electrolyte. The
increase of the amount of uranium in solution is observed from
550 mV/SHE.
NaCF3 SO3 was chosen as the supporting electrolyte for this
study because it allows to accede at domain of potential that is com-
patible with the electrochemical reactions of uranium. It allows to
avoid the use of sodium perchlorate and the possible formation of
chloride ions, which may affect the corrosion of UO2 .
3.3. Effect of experimental parameters on the electrochemical
curves
The influence of the rotation rate and the scan rate on the
electrochemical signal of the anodic dissolution of UO2 in acidic
solution has been studied. Firstly, it is necessary to bound these
parameters in order to determine the optimal conditions for the
study of the U(VI)/UO2 (s) system. The rotation rate is bounded
between the values 100 and 2100 rotations per minutes (rpm)
to neglect edge effects (ω > 100 rpm) and to avoid turbulent flow
regime according the geometry of the material and the geometry of
the electrochemical cell (ω < 2100 rpm). The scan rate is bounded
between 0.05 and 1 mV/s values. Below the 0.05 mV/s value, the
current is hidden in background and the 1 mV/s value is conven-
tionally used for solid electrodes.
3.3.1. Electrochemical reactions involved in UO2
oxidation/dissolution in acidic non-complexant media
Fig. 3 shows the cyclic voltammograms at pH 3 in 0.1 mol L−1
NaCF3 SO3 , ω = 300 rpm, v = 1 mV/s over a potential range of −750
to 720 mV/SHE. The electrochemical window is located between
−350 and 800 mV/SHE (Fig. 2c). The various peaks of oxidation (A1,
A2 and A3) and reduction (C1) are numbered on Fig. 3.
473
The anodic peak A1, in potential range between −350 and
0 mV/SHE, is attributed to the natural oxidation of UO2 , in pres-
ence of aqueous solution, to the mixed species UIV UV O2 [21]. In
this writing, we have chosen to underline the majority species. This
oxidation was also observed on UO2 by Shoesmith and Casas et al.
[8,22], but not on the SIMFUEL that is considered as stoichiometric
[2,8].
The anodic peak A2, in potential range between 30 and
330 mV/SHE, is attributed to the partial oxidation of U(IV) in the
mixed species UIV UV O2 leading to an enrichment of U(V) in this
species. This mixed species, rich in U(V), has already been observed
by Santos et al. [2]. It is consistent with the data related by Shoe-
smith and Sunder [23] who explained that the oxidative dissolution
occurs in a potential range of 150–200 mV/SHE.
The anodic peak A3, in potential range between 350 and
550 mV/SHE, is due to the oxidation of the U(V) of the mixed species
rich in U(V), UIV UV O2 , to the U(VI) species.
A reduction peak C1, in potential range between 150 and
−100 mV/SHE, is associated with an oxidation peak determined
using j–E curves (Fig. 4).
Fig. 4 shows a series of cyclic voltammograms at pH 3 in
0.1 mol L−1 NaCF3 SO3 , ω = 300 rpm, v = 1 mV/s to different anodic
potential limits (310, 370, 450, 560 and 600 mV/SHE) in order to
determine the reaction associated to the cathodic peak C1.
The reduction peak appears when the anodic limit attained
450 mV/SHE, it increases with the anodic potential limit and
becomes constant when the anodic limit reached 560 mV/SHE. This
confirms that this reduction peak is associated with the oxidation
peak A3 and is characteristic of the reduction of U(VI) to U(V). The
gap between the anodic peak A3 and its associated cathodic peak is
about 300 mV/SHE. In fast systems with the exchange of one elec-
tron at 25 ◦ C and for a monoelectronic reaction, the gap between
the anodic and cathodic peak is about 57 mV/SHE therefore this dis-
crepancy is characteristic of slow system [24]. The reduction peak
of U(V) to U(IV) is not observed in the potential range studied. It
is possible that this reduction occurs after the protons reduction if
electronic exchange is very slow too or if the reverse reaction of
this reaction: U(IV) → U(V) + e− not allows to obtain the same solid
species.
3.3.2. Influence of experimental parameters (v and ω)
A system depends on charge and/or mass transfer. The system
is governed by the charge transfer when, potential range is close to
474 C. Gaulard-Balandret et al. / Electrochimica Acta 83 (2012) 471–477

Fig. 3. Cyclic voltammograms performed on a UO2 rotating disc electrode in

0.1 mol L−1 NaCF3 SO3 at pH 3 and for v = 1 mV/s, ω = 300 rpm and Ei = −90 mV/SHE
(a) between −750 and 800 mV/SHE and (b) expansion of the area between −600 and
700 mV/SHE.

Fig. 4. Cyclic voltammograms performed on a UO2 rotating disc electrode in

0.1 mol L−1 NaCF3 SO3 at pH 3 and for v = 1 mV/s, ω = 300 rpm, Ei = −90 mV/SHE and
different Eanodic limits.

1 mV/s. For further experiments, only the rotation rate of 300 rpm
Fig. 2. Comparison of cyclic voltammograms performed in 0.1 mol L−1 NaCF3 SO3
has been chosen in order to neglect edge effects and to avoid tur-
at ω = 300 rpm and v = 1 mV/s on a rotating Pt disc electrode and a rotating Au disc
electrode at (a) pH 9.2, (b) at pH 3 and (c) on a UO2 rotating disc electrode at pH 3. bulent flow regime. Each of the two curves obtained for 1 mV/s and
0.05 mV/s scan rates present two Tafel’s linear regions dissociated
in the potential range of 200–700 mV/SHE. For higher potential, the
equilibrium and it is governed by the mass transfer when poten- two curves can be represented by a unique third linear region. The
tial range is far from equilibrium. With a rotating disk electrode, two Tafel’s linear regions suggest that oxidation process occurs into
when the system is at the stationary state and is controlled by two electrochemical steps.
mass transfer, a limiting diffusion current, related to the rotation
rate, is observed for high potentials [24]. This is not the case in our
experiments suggesting that the electronic exchange is not con-
trolled by the mass transfer [21]. In order to verify these results,
a study has been conducted on the effect of the rotation rate on
the electrochemical signal. The effect of the scan rate has been also
studied.
Fig. 5 represents the variation of log j as a function of E recorded
at pH 3 in 0.1 mol L−1 NaCF3 SO3 , at two different scan rates (1 mV/s
and 0.05 mV/s) and at three different rotation rates (150, 300 and
1000 rpm).
Two sets of curves are obtained and one can deduce that the
scan rate has an influence on the electrochemical signal in contrast
with the rotation rate which does not affect the electrochemical
signal. This last point suggests that the system is controlled only
Fig. 5. Curves of steady-state current density versus potential for the anodic dis-
by the charge transfer and that the mass transfer is not the limit- solution of UO2 electrode in 0.1 mol L−1 NaCF3 SO3 at pH 3 and for two different v,
ing step between 150 and 1000 rpm and between 0.05 mV/s and Ei = −90 mV/SHE and for three different ω.
 C. Gaulard-Balandret et al. / Electrochimica Acta 83 (2012) 471–477 475

Table 1
Binding energies of the three oxidation states of uranium 4f7/2 and positions of the
corresponding satellite peaks [26–28].

Oxidation state Binding energy (eV) Satellite peak(s) positions

UIV 379.8 ± 0.3 7 ± 0.3

UV 380.9 ± 0.3 8 ± 0.3
UVI 382.2 ± 0.3 3.9 ± 0.3 and 10.2 ± 0.3

The potential range between 200 and 500 mV/SHE, depending

on the scan rate and corresponding to the first Tafel’s linear region.
The potential range between 500 and 700 mV/SHE, depending on
the scan rate and corresponding to the second Tafel’s linear region.
At higher potentials, a deviation from linearity could correspond
to increase of the amount of uranium in solution. It is difficult to
precisely determine an ˛ value (the anodic charge transfer coeffi-
cient) for the second Tafel’s region as the second step is correlated
to the first one. To sum up, the obtained curves shown in Fig. 5 can
be represented by:

- For the scan rate of 0.05 mV/s, the first Tafel’s linear region has
a Tafel slope equal to 263 mV/dec (˛ = 0.23). The second Tafel’s
linear region has a Tafel slope equal to 66 mV/dec (˛ = 0.82).
- For the scan rate of 1 mV/s, the first Tafel’s linear region has a Tafel
slope equal to 327 mV/dec (˛ = 0.27). The second Tafel’s linear
region has a Tafel slope equal to 128 mV/dec (˛ = 0.50).

The ˛ values of the first Tafel’s linear region are close, irrespec-
tive of the scan rate. However, the slope of the second Tafel’s linear
region increases when the scan rate decreases. For further experi-
ments, scan rate of 1 mV/s has been chosen as a good compromise
to observe the two electrochemical steps achieved in a reasonable
experimental time. Also, working with this value allows obtaining
a limit and maximum value of corrosion rate. Besides, according
to the theory, the scan rate (in mV/s) should be below five times
the rotation rate (in rps) in order to obtain a stationary voltam-
mogram [24,25]. The couple (ω = 300 rpm and v = 1 mV/s) satisfies
these conditions.

3.4. Characterization of the surface state of the uranium dioxide

and quantification of the solution in contact with the uranium
dioxide

As observed by electrochemical experiments, the UO2 oxi-

dation/dissolution in acidic non-complexant media involves two
electrochemical reactions. However, electrochemical techniques
are not sufficient to determine whether species are present in solu-
tion or on the UO2 surface as proposed in literature ((UV O2 OH)ads
and (UVI O2 (OH)2 )ads) [2,5,7,9]. For this purpose, it is necessary to
characterize the UO2 pellet surface and the solution in contact with
the UO2 pellet.
Characterization of the UO2 surface has been performed by XPS
after an imposition of different potential during 1 h. These poten-
tials have been chosen from Fig. 3:
• For −200 < E < 30 mV/SHE: potential range between peaks A1 and
A2,
• For 30 < E < 330 mV/SHE: potential range between peaks A2 and
A3,
• For E > 330 mV/SHE: potential range from peak A3.
Fig. 6 shows the deconvolution of the U-4f7/2 peak into contrib-
utions of U(IV), U(V) and U(VI) according to the binding energies
listed in Table 1.
When the potential is imposed at −90 mV/SHE (Fig. 6a), which
correspond to domain of peak A1, the oxidation states +IV and +V
Fig. 6. The deconvolution of the U-4f7/2 peak of XPS spectra obtained at the UO2
surface imposed at different potential.
are present on the UO2 surface. This observation confirms the exist-
ence of a mixed species UIV UV O2 at the beginning of the oxidation
process. When the potential increases, these oxidation states are
still present on the UO2 surface and U(V) contribution increases
while U(IV) contribution decreases. The study proposed by San-
tos et al., at pH 3.5 on SIMFUEL in NaCl 0.1 mol L−1 [2], showed an
enrichment of U(V) with the potential, which is consistent with
our observations. However, they observed three oxidation states at
the surface of the material: +IV, +V and +VI, whatever the potential
value from their XPS experiments. In addition, the binding energies
used in their deconvolution of the U-4f7/2 peak are slightly different
in comparison with the binding energies listed in literature [26–28]
and are variable with the potential. This is not consistent with our
deconvolution of the U-4f7/2 peak that shows only the presence of
U(IV) and U(V) at the material surface.
476 C. Gaulard-Balandret et al. / Electrochimica Acta 83 (2012) 471–477
Fig. 7. Variation of the oxidation state and the logarithm of the uranium concentra-
tion in the solution as a function of the applied potential. The straight line represents
the average initial uranium concentration in solution. The predominance domain of
U(IV), U(V) and U(VI), deducted from the Fig. 3, are noted on the figure.
Fig. 7 shows the evolution of the oxidation state determined
at the surface of UO2 electrode using XPS’s spectra deconvolution
together with the evolution of the logarithm of the uranium con-
centration in the solution measured using ICP-MS as a function of
the imposed potential. We assume in our conditions that uranium
in solution is U(VI) species. Indeed in the solution, disproportiona-
tion of U(V) in U(IV) and U(VI) occurs and at these potentials, and
U(IV) is rapidly oxidized to U(VI) and U(V) is not stable in solution.
In the potential range between −150 and 30 mV/SHE, the oxida-
tion states +IV and +V exist at the surface of the material with a large
predominance of the oxidation state +IV. The amount of uranium in
solution is low and constant. So, the oxidation occurs from mixed
species UIV UV O2 where the proportion of U(IV) is in the majority.
In the potential range between 30 and 330 mV/SHE, the propor-
tion of U(V) at the UO2 surface increases with the potential while
the proportion of U(IV) decreases. However, U(IV) is still major at
the UO2 surface. The amount of uranium in solution is low and in
the same quantity in potential range of −150 and 30 mV/ESH. This
suggests that the UO2 dissolution is low.
In the potential range above 330 mV/SHE, the proportion of U(V)
at the surface of the material increases with the potential and from
600 mV/SHE, U(V) becomes the major species in comparison with
the U(IV) species. The amount of uranium in solution increases with
the increasing potential. The solid is mainly a U(V) species which
dissolves in U(VI).
3.5. Determination of the mechanism of the UO2
oxidation/dissolution in acidic non-complexant media
The oxidation/dissolution of uranium dioxide has been studied
by Nicol and Needes in non-complexing solutions in a pH range of
2–13 using an UO2 disc-gold ring electrode [9]. Current–potential
curves showed two linear regions at low pH values, indicating a suc-
cessive electron-transfer process. The cyclic voltammetry results
suggest the formation of one or more surface intermediate species
and in particular intermediate U(V) species.
A similar mechanism has already been proposed by Shoe-
smith et al. [2,5,7], consisting in an EEC mechanism with
E = Electrochemistry and C = Chemistry. This mechanism can be
described by two successive electron-transfers processes with the
surface intermediate U(V) and U(VI) species and in addition, a third
step corresponding to the dissolution of U(VI) species. Santos et al.
have demonstrated in their study at pH 9.5, on the SIMFUEL, that
the reduction of UO2 + x to UO2 would involve the reduction of U(V)
species and the extraction of an O2− anion from the solid state
surface layer [2]. The mixed species UO2 + x , cited by Santos et al.
correspond to the mixed species UIV UV O2 in our work. At pH 3,
Fig. 8. Mechanism of the oxidation/dissolution of the uranium dioxide in acidic
non-complexing media (a) proposed in this study from our experiments and (b)
proposed by Nicol et al. and later by Shoesmith et al.
the gap of potential between the oxidation peak and the reduction
peak is smaller than at pH 9.5 indicating that the co-ordination to
the oxidized layer surface is lower than the one presents in neu-
tral solutions. This result suggests an intermediate dissolution in
an adsorbed state.
Sunder et al. studied the effect of pH on UO2 corrosion in aerated
sodium perchlorate or sodium sulfate solutions [10]. The difference
between experiments in 0.1 mol L−1 Na2 SO4 at pH 2.9 and the one
at pH 9.7 is a less pronounced oxidation at low pH with a more
reversible associated reduction. For acidic solutions (pH < 5), the
potential range for film growth occurs at more positive values than
for neutral solutions. The oxidative dissolution for the neutral solu-
tions occurs when the surface composition is lower than UO2.33 ,
which is the expected surface composition for the beginning of the
dissolution. The proposed mechanism involves a hydrated U(VI)
layer as intermediate species.
Our recent observations from cyclic voltammetry, XPS and ICP-
MS experiments are in a good agreement with the mechanism
proposed by Nicol and Needes, and later by Shoesmith et al., for
oxidation and dissolution of uranium dioxide in acidic and non-
complexing solutions and presented in Fig. 8b [2,9]. Nevertheless,
in our experimental conditions, the adsorbed surface intermediate
U(VI) species is not present at the UO2 surface. Then, we propose
a slightly different mechanism, presented in Fig. 8a, for the oxida-
tion/dissolution of UO2 in acidic non-complexing media.
This mechanism accounts for two successive electron trans-
fers with a surface intermediate U(V) species. The mixed species
UIV UV O2 , is oxidized to UIV UV O2 OH, where U(IV) and U(V) are the
major uranium species respectively. This mixed species is sug-
gested to be an adsorbed hydroxide species [2,5,9]. U(V) species
is oxidized to U(VI) species which is soluble in solution.
4. Conclusions
This study allowed to obtain a couple of optimum parame-
ters (scan rate (v) and rotation rate (ω)) in order to determine a
mechanism characteristic of the oxidation and dissolution of the
U(VI)/UO2 (s) system. These parameters allowed to obtain a stable
initial surface state of the uranium dioxide, which is important to
exclude all experimental ambiguities, such as solid phase precipita-
tion. This study was performed in non-complexing media, sodium
trifluoromethanesulfonate, acidic media at pH 3 and under anoxic
conditions.
As observed by electrochemical experiments, two electrochem-
ical reactions are involved in the UO2 oxidation/dissolution. Using,
surface and solution characterization, the nature of the species
involved in the electrochemical reactions have been determined
 C. Gaulard-Balandret et al. / Electrochimica Acta 83 (2012) 471–477 477

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