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Electrochemical Studies on Uranium in the Presence

of Organic Acids
a b b b b c
Yoshinori SUZUKI , Takuya NANKAWA , Takuo OZAKI , Toshihiko OHNUKI ,
d c a
Arokiasamy J. FRANCIS , Youichi ENOKIDA & Ichiro YAMAMOTO
a
Department of Materials, Physics, and Energy Engineering , Graduate School of
Engineering, Nagoya University , Furo-cho, Chikusa-ku, Nagoya , 464-8603 , Japan
b
Advanced Science Research Center , Japan Atomic Energy Agency , Tokai, Ibaraki ,
319-1195 , Japan
c
EcoTopia Science Institute, Nagoya University , Furo-cho, Chikusa-ku, Nagoya ,
464-8603 , Japan
d
Environmental Sciences Department, Brookhaven National Laboratory , Upton, New
York , 11973 , USA
e
EcoTopia Science Institute, Nagoya University , Furo-cho, Chikusa-ku, Nagoya ,
464-8603 , Japan
Published online: 05 Jan 2012.

To cite this article: Yoshinori SUZUKI , Takuya NANKAWA , Takuo OZAKI , Toshihiko OHNUKI , Arokiasamy J. FRANCIS ,
Youichi ENOKIDA & Ichiro YAMAMOTO (2007) Electrochemical Studies on Uranium in the Presence of Organic Acids, Journal
of Nuclear Science and Technology, 44:9, 1227-1232

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 Journal of NUCLEAR SCIENCE and TECHNOLOGY, Vol. 44, No. 9, p. 1227–1232 (2007)

ARTICLE

Electrochemical Studies on Uranium in the Presence of Organic Acids

Yoshinori SUZUKI1;2;
, Takuya NANKAWA2 , Takuo OZAKI2 , Toshihiko OHNUKI2;3 ,
Arokiasamy J. FRANCIS4 , Youichi ENOKIDA3 and Ichiro YAMAMOTO1
1
Department of Materials, Physics, and Energy Engineering, Graduate School of Engineering,
Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
2
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Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
3
EcoTopia Science Institute, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
4
Environmental Sciences Department, Brookhaven National Laboratory, Upton, New York 11973, USA
(Received November 24, 2006 and accepted in revised form April 19, 2007)

We examined electrochemical redox reactions of UO2 2þ in perchlorate and organic acid (oxalic, ma-
lonic, succinic, adipic, L-malic, and L-tartaric acids) solutions using cyclic voltammetry to reveal the ef-
fects of complex formation with organic acids on the redox behavior. In the perchlorate and organic acid
solutions, a redox reaction of UO2 2þ /UO2 þ and an oxidation reaction of U(IV) produced by a dispropor-
tionation of UO2 þ were observed. The peak potentials of the UO2 2þ reduction showed a good linear re-
lationship with the stability constants of 1:1 UO2 2þ -organic complexes. In the presence of malonic acid,
the redox potential for UO2 2þ /UO2 þ was constant at pH 1–2 and 5–6 while it decreased with an increase
in pH from 2 to 5. Additionally, it was independent of malonate concentration at 0.1–0.5 M while it de-
creased with an increase in the concentration from 0.005 to 0.1 M. Based on the experimental and the spe-
ciation calculation results, we determined the redox reactions of UO2 2þ -malonate complexes as a function
of pH and malonate concentration. We also determined the redox reactions of UO2 2þ -oxalate complexes
in the same way.
KEYWORDS: uranium organic complex, organic acid, redox reaction, electrochemistry, cyclic vol-
tammetry, stability constant, uranium(V), disproportionation

than that in a non-ligand system. Furthermore,

I. Introduction
It is essential to understand the migration behavior of ac-
tinides (An) in order to assess the safety of their geological
disposal. The actinides, uranium, neptunium, and plutonium
have a number of oxidation states in solution and, in higher
oxidation states of +5 and +6, they form the respective oxy-
genated species, AnOþ and AnO2 2þ . Their chemical proper-
ties depend considerably on their oxidation states.1) For that
reason, it is important to elucidate the redox properties of the
actinides to predict their mobility in the environment.
The electrochemistry of uranium has widely been studied
in aqueous solutions.2–6) UO2 2þ is quasi-reversibly reduced
to UO2 þ at the potential of about 0:138 V (vs. Ag/AgCl)
and further reduced to U4þ at a lower potential in an acidic
solution.6) The UO2 þ species is comparatively stable in only
a narrow pH range between 2 and 4 where the disproportio-
nation of UO2 þ to U4þ and UO2 2þ is quite slow.7,8)
The reduction behavior of UO2 2þ in the presence of inor-
ganic and organic ligands is different from that mentioned
above.3,4,6,9–12) UVI O2 (CO3 )3 4 is quasi-reversibly re-
duced to UV O2 (CO3 )3 5 at 0:85 V (vs. Ag/AgCl) in 1 M
(mol dm3 ) Na2 CO3 solution.6) This potential is much lower


Corresponding author, E-mail: suzuki.yoshinori@jaea.go.jp
ÓAtomic Energy Society of Japan
1227
UV O2 (CO3 )3 5 is stable with respect to disproportionation
in a carbonate solution.
The reduction of UO2 2þ to UO2 þ in the presence of var-
ious organic acids has been studied polarographically.3,9,11,12)
Plock and Miner11) reported that the half-wave potential of
the reduction wave of UO2 2þ in a malonate solution depends
on pH and the malonate concentration. Additionally, the dis-
proportionation rate of UO2 þ increases with an increase in
the malonate concentration at pH 2.5. Kolthoff and Harris3)
reported a similar increasing tendency of the disproportiona-
tion rate with an increase in the oxalate concentration in a
1.89 M HClO4 solution. In a previous study, we investigated
the reduction behavior of UO2 2þ in the presence of citric
acid using column electrodes.13) We found that the reduction
of UO2 2þ in polymeric complexes is more difficult than in
simpler complexes.
In the present study, we investigated the redox behavior of
UO2 2þ in organic acid solutions of oxalic [(COOH)2 ], ma-
lonic (HOOCCH2 COOH), succinic [HOOC(CH2 )2 COOH],
adipic [HOOC(CH2 )4 COOH], L-malic [HOOCCH(OH)-
CH2 COOH], and L-tartaric [HOOCCH(OH)CH(OH)COOH]
acids by cyclic voltammetry to understand the effects of or-
ganic complex formation on the redox behavior in terms of
the stability constants of the complexes. The dicarboxylic
acids were representative of simple chelating ligands that
 1228
would be present in the natural environment. We also deter-
mined details of the electrochemical behavior of UO2 2þ in a
malonate and an oxalate solution. Studies on the redox be-
havior of uranium in an organic solution are helpful to un-
derstand the behavior of neptunium and plutonium because
a complex formation behavior is similar to the same oxida-
tion states among these three actinides.1)
II. Experimental
1. Materials
Samples were prepared by mixing stock solutions of
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UO2 (NO3 )2 , NaClO4 , and an organic acid (oxalic, malonic,
succinic, adipic, L-malic, or L-tartaric acids) to obtain solu-
tions containing 1 mM UO2 (NO3 )2 , 0.1 M NaClO4 , and an
appropriate concentration of the organic acid. All chemicals
used were in the reagent grade (Wako Pure Chemical Indus-
try Ltd., Osaka, Japan). The pH of the samples was adjusted
by adding HClO4 or NaOH.
2. Methods
Cyclic voltammograms were measured under a nitrogen
atmosphere using an ALS/CHI Electrocemical Analyzer
Model 600C (CH Instruments, Inc., Austin, Texas, USA).
A three-electrode system composed of a glassy carbon work-
ing electrode (surface area = 12.56 mm2 ), a Pt counter elec-
trode, and an Ag-AgCl/saturated KCl reference electrode
was utilized. One mol dm3 sodium chloride solution was
used for a salt bridge to connect the sample solution and
the reference electrode. All sample solutions were deoxy-
genated using nitrogen gas for at least 15 minutes prior to
measurements.
III. Results and Discussion
1. Cyclic voltammogram Measurements of UO2 2þ in the
Absence of Organic Acid
Figure 1 shows the cyclic voltammogram of 1 mM
UO2 2þ in an aqueous solution containing 0.1 M HClO4
measured in the potential range from 0:3 to 0.5 V at differ-
ent scan rates (v ¼ 0:025{0:15 V s1 ). Peaks (Pc1 and Pa1 ) of
a redox couple and an anodic peak (Pa2 ) were observed at
around 0:20 (Ec1 ), 0:09 (Ea1 ) and 0.27 V (Ea2 ), respec-
tively. The values of peak separation (
E1 ¼ Ea1  Ec1 ) in-
creased from 0.094 to 0.126 V with an increase in v from
0.025 to 0.150 V s1 . The E1 (¼ ðEa1 þ Ec1 Þ=2) was con-
stant, 0:143  0:002 V, without depending on v. A plot
of the cathodic peak currents of Pc1 (ic1 ) against v1=2 gave
a good linear relationship (data not shown). These results
suggest that the UO2 2þ is reduced to UO2 þ quasi-reversibly.
Mizuguchi et al.6) reported that a quasi-reversible reaction:
UVI O2 2þ þ e $ UV O2 þ ; ð1Þ
was observed at a potential of 0:138 V vs. Ag/AgCl in a
solution containing 0.01 M UO2 2þ , 0.1 M HClO4 , and
0.1 M LiClO4 by cyclic voltammetry with a Pt working elec-
trode. The potential and reversibility of the Pc1 and Pa1 ob-
tained in our study are in good agreement with their results,
so that these peaks are attributable to reaction (1). On the
Y. SUZUKI et al.
Pa1
Pa2
I/A
0.025 V s-1
0.050
0.075
40 A
0.100
0.125
0.150
Pc1
-0.4 -0.2 0 0.2 0.4 0.6
E / V (vs. Ag/AgCl)
Fig. 1 The cyclic voltammogram of 1 mM UO2 2þ in an aqueous
solution containing 0.1 M HClO4 measured in the potential range
from 0:3 to 0.5 V at different scan rates (v ¼ 0:025{0:15 V
s1 ). Initial scan direction: Cathodic.
other hand, Pa2 was not observed in their study. UO2 þ is
known to disproportionate to UO2 2þ and U(IV) species via
the following reactions:14,15)
UV O2 þ þ Hþ $ UV OOH2þ ;
UV O2 þ þ UV OOH2þ $ HOUVI O2 þ þ UIV O2þ ; ð2Þ
UIV O2þ ! stable U(IV) species;
HOUVI O2 þ $ UVI O2 2þ þ OH :
Kihara16) reported that an oxidation wave of U(IV) to U(VI)
was observed at around 0.2 to 0.3 by column electrolysis. So,
we attribute Pa2 to oxidation of U(IV) to U(VI), where U(IV)
was produced by the disproportionation of UO2 þ .
2. Cyclic voltammogram Measurements of UO2 2þ in the
Presence of Organic Acid
Figure 2 shows the cyclic voltammogram of UO2 2þ in an
aqueous solution containing 0.1 M NaClO4 and (a) malonic
or (b) oxalic acids at pH 4.0 measured at a scan rate from
0.010 to 0.15 V s1 . In their presence, peaks of one redox
couple corresponding to UO2 2þ /UO2 þ [(Pmc1 , Pma1 ) and
(Poc1 , Poa1 )] were observed at around 0:42 (Emc1 ), 0:24
(Ema1 ), 0:47 (Eoc1 ), and 0:27 V (Eoa1 ) (Figs. 2a, b). How-
ever, Pma1 and Poa1 were not distinguished at v of 0.010–
0.050 and 0.010–0.025, respectively. This indicates that a
large portion of UO2 þ species produced at Pmc1 or Poc1
may disproportionate to U(VI) and U(IV) species before be-
ing electrochemically oxidized to U(VI) when v is small.
Em1 (¼ ðEmc1 þ Ema1 Þ=2) and Eo1 (¼ ðEoc1 þ Eoa1 Þ=2) were
almost constant at v of 0.075 0:15 V s1 and 0.050–
0.15 V s1 , respectively and were 0:337 V and 0:377 V.
Em1 and Eo1 were much lower than in a non-ligand system.
It is generally known that the redox potential of a metal ion
complexing with inorganic or organic acids differs from that
of an aqueous complex. Thus, the redox potential of UO2 2þ /
UO2 þ was shifted to a negative value by complexing of
JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY
 Electrochemical Studies on Uranium in the Presence of Organic Acids 1229

Psa2
Pma2
(a)
Pma1 (a)

Paa2
I/A

Psc1
(b)
60 A

I/A
0.010 V s-1
0.025 Pmia2
0.050 40 A
Pac1
0.075
0.100
0.125
(c)
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0.150
Pmc1
Pta2
-0.6 -0.4 -0.2 0 0.2 0.4 0.6 Pmic1
E / V (vs. Ag/AgCl)
(d)

(b) Poa1 Ptc1

-1.0 -0.5 0.0 0.5 1.0

E / V (vs. Ag/AgCl)
I/A

Fig. 3 The cyclic voltammogram of 1 mM UO2 2þ in aqueous

solutions containing 0.1 M NaClO4 and 20 mM (a) succinic, (b)
0.010 V s-1 adipic, (c) malic, or (d) tartaric acids at pH 4 and scan rate of
0.025
0.050
0.025 V s1 . Initial scan direction: Cathodic.
0.075
0.100 30 A
0.125
Poc1 0.150 -0.2
Succinic acid
E / V (vs. Ag/AgCl)

-0.6 -0.4 -0.2 0 0.2 0.4 0.6

-0.3
Malonic acid
E / V (vs. Ag/AgCl)
Adipic acid
Fig. 2 The cyclic voltammogram of 1 mM UO2 2þ in aqueous -0.4 Oxalic acid
solutions containing 0.1 M NaClO4 and 20 mM (a) malonic or
(b) oxalic acids at pH 4 at different scan rates (v ¼ 0:010{
0:15 V s1 ). Initial scan direction: Cathodic.
-0.5
Tartaric acid

UO2 2þ with malonic or oxalic acids. In the malonic solution,
an anodic peak was observed at around 0.15 V. We attribute
it to an oxidation reaction of U(IV) species produced by the
disproportionation of U(V) similar to the case in the perchlo-
rate solution.
Figure 3 shows the cyclic voltammogram of UO2 2þ in an
aqueous solution containing 0.1 M NaClO4 and (a) succinic,
(b) adipic, (c) L-malic or (d) L-tartaric acids at pH 4.0 meas-
ured at a scan rate of 0.025 V s1 . In the presence of succin-
ic, adipic, L-malic or L-tartaric acids, a cathodic peak (Psc1 ,
Pac1 , Pmic1 , or Ptc1 ) was observed at around 0:27 (Esc1 ),
0:27 (Eac1 ), 0:51 (Emic1 ) or 0:42 V (Etc1 ), respectively.
These peak potentials were also lower than those in a non-li-
gand system, suggesting that the complex formation of
UO2 2þ occurred with the organic acid. However, an anodic
peak coupled with the cathodic peak was not distinguishable
in their solutions. This result indicates that hardly any oxida-
tion reaction of U(V) occurred on the electrode because of
the fast disproportionation of U(V). An anodic peak Pma2 ,
Psa2 , Paa2 , Pmia2 or Pta2 was observed at around 0.10, 0.15,
Malic acid
-0.6
3 4 5 6 7
log β VI1,1
Fig. 4 The cathodic peak potentials at v of 0.025 V s1 in Fig. 2
and Fig. 3 vs. log VI 1;1 .
0.15, 0.40 or 0.45 V in the respective malonic, succinic,
adipic, L-malic or L-tartaric acid solutions. These peaks
are also thought to be an oxidation reaction of U(IV) pro-
duced by the disproportionation of U(V). We used stability
constants of 1:1 UO2 2þ -organic complexes (VI 1;1 ) as an in-
dicator of stability of the UO2 2þ -organic complexes and ex-
amined the relation between the peak potentials of Pmc1 ,
Poc1 , Psc1 , Pac1 , Pmic1 and Ptc1 and the indicators of the stabil-
ity of the complexes. Figure 4 shows a plot of the peak po-
tentials of the cathodic peak at v of 0.025 V s1 in Fig. 2 and
Fig. 3 vs. VI 1;1 .17) The peak potentials decreased linearly
with an increase in VI 1;1 . These results show that it is more

VOL. 44, NO. 9, SEPTEMBER 2007

 1230
-0.1
E / V (vs. Ag/AgCl)
-0.2
-0.3
E
1
-0.4 E
m1
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E -0.42
o1
-0.5
0 1 2 3 4 5
pH
Fig. 5 The pH dependence of E1 , Em1 and Eox1 .
difficult to reduce UO2 2þ by complexation in the presence of
an organic acid which forms a stronger complex with
UO2 2þ . Essentially, the redox potential of UO2 2þ /UO2 þ in
the presence of organic acid depends on the ratio of the sta-
bility constants of UO2 2þ - and UO2 þ -organic complexes (V
and VI ) and we need to plot the redox potentials against
logðV =VI Þ. However, we can get a good linear relationship
between the peak potentials and log VI 1;1 . The stability con-
stants of UO2 þ complexes are generally considered to be
much smaller than those of UO2 2þ complexes1) and the ef-
fect of formation of UO2 þ complexes on the redox potential
is smaller compared to that of UO2 2þ complexes. This ten-
dency is useful to predict the potential at which UO2 2þ
may be reduced in the presence of an organic acid whose sta-
bility constant is already known.
2þ
3. Effect of pH on the Redox Behavior of UO2
Figure 5 shows pH dependence of E1 in a perchlorate so-
lution, Em1 in a malonate solution and Eo1 in an oxalate solu-
tion at an organic acid concentration of 20 mM. E1 obtained
at pH 0 to 4 was constant (about 0:14 V). In the malonate
solution at pH 1–2, Em1 was almost the same value as E1 ,
suggesting that UO2 2þ did not form complexes with a ma-
lonic acid in this pH range. At pH 2–3 and 3–5, Em1 decreas-
ed with a rise in pH with slopes of 0:134 and 0:061 V/
pH, respectively. The slope of redox potential vs. pH is ex-
pressed theoretically by 0:060m V/pH, where m is the
number of protons involved in the one-electron redox reac-
tion.18) So, those slopes indicate that 2 and 1 protons are in-
volved in the redox reactions at pH ranges of 2–3 and 3–5,
respectively. Em1 was constant above pH 5 (about 0:40
V), suggesting that no protons were involved in the redox re-
action. These results suggest that a different redox reaction
for UO2 2þ proceeded on the electrode for each pH range.
In our previous study, we showed that the reduction poten-
tial of UO2 2þ -citrate complex shifted as the complex species
changed.13) A speciation calculation of the 1 mM UO2 2þ and
20 mM malonate system based on the stability constants re-
Y. SUZUKI et al.
-0.34
Em1
E / V (vs. Ag/AgCl)
-0.36 Eo1
-0.38
-0.40
-2.5 -2 -1.5 -1 -0.5 0
6 log C
Fig. 6 Em1 and Eox1 vs. the logarithm of the organic acid concen-
tration (log C).
ported by Smith and Martell17) showed that the predominant
species of uranyl at pH 1–2, 2–3, and 3–6 are UO2 2þ ,
UO2 Mal0 and UO2 Mal2 2 , respectively (H2 Mal: a malonic
acid). The predominant species of an uncomplexed malonic
acid at pH 2–3, 3–5 and 5–6 are H2 Mal0 , HMal and Mal2 ,
respectively. In consideration of the predominant species of
uranyl and an uncomplexed malonic acid and the m values,
the redox reactions in pH from 2 to 5 are expressed by the
following equations:
UVI O2 Mal0 þ e þ 2Hþ $ UV O2 þ þ H2 Mal0
(pH 2{3); ð3Þ
VI
U O2 Mal2 2  þ V 
þ e þ H $ U O2 Mal þ HMal 
(pH 3{5): ð4Þ
Plock and Miner11) reported the effect of pH on UO2 2þ re-
duction in a 1 M malonate solution by polarography. In their
study, the half-wave potential decreased with an increase in
pH from 1 to 4.8 while Em1 was constant at pH 1 to 2 in our
study. The difference may be caused by the difference of the
malonate concentration. Their work was done at a higher
malonate concentration compared to our study and UO2 2þ
formed a complex with a malonic acid at such a low pH.
In the oxalate solution, Eo1 was constant between pH 4
and 6 (about 0:38 V), suggesting that the predominant
UO2 2þ species does not change and no protons are involved
in the redox reaction of UO2 2þ -oxalate complexes in the pH
range. The speciation calculation of the 1 mM UO2 2þ and
20 mM oxalate system showed that the predominant species
of uranium is UO2 Ox2 2 at the pH range (H2 Ox: an oxalic
acid). Below pH 4, Eo1 could not be determined because
Poa1 was not observed.
4. Effects of the Concentration of Malonic and Oxalic
Acids on the Redox Behavior of UO2 2þ
A plot of Em1 vs. the logarithm of the organic acid concen-
tration (C) at pH 5 is shown in Fig. 6. In the malonate solu-
tion, Em1 decreased proportionately with an increase in log C
JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY
 Electrochemical Studies on Uranium in the Presence of Organic Acids
from 2:3 to 1:0 (C from 0.005 to 0.1 M), suggesting that
a malonate ion coordinating UO2 2þ dissociated as UO2 2þ
was reduced to UO2 þ . In the range from 1:0 to 0:30
(C from 0.1 to 0.5 M), Em1 was constant (about 0:40 V),
suggesting the dissociation of malonate did not occur. So,
the redox reactions attributable to Pmc1 and Pma1 at pH 5
are expressed by the following equations:
UVI O2 Mal2 2 þ e $ UV O2 Mal þ Mal2
(C < 0:1 M); ð5Þ
VI
U O2 Mal2 2  V
þ e $ U O2 Mal2 3
(C > 0:1 M): ð6Þ
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The formal redox potential of Eq. (6) (Ef ) is expressed as the
following equation:18)
Ef ¼ E0 þ RT=F lnðV 1;2 =VI 1;2 Þ; ð7Þ
where E0 , R, T, F, V 1;2 and VI 1;2 are standard redox poten-
tial, gas constant, temperature, the Faraday constant, the sta-
bility constant of 1:2 UV O2 þ -organic complex and the stabil-
ity constant of 1:2 UVI O2 2þ -organic complex, respectively.
LogV 1;2 was estimated as 5:06  0:07 by substituting
Ef ¼ 0:403  0:001 V, E0 ¼ 0:142  0:004 V, T ¼ 298
K and log VI 1;2 ¼ 9:4817) into Eq. (7).
Pma2 was observed at a potential around 0:05 V at the
concentration of 0.005 M (data not shown). It became small-
er with an increase in C and was not observed at C of
0.05 M. These results suggest that the rate of the dispropor-
tionation becomes slower due to the formation of
UV O2 Mal2 3 complex. Kim et al.19) investigated the redox
reactions of [UO2 (DMF)5 ]2þ , UO2 (acac)2 DMF and
UO2 (salen)DMF in DMF solution (DMF=N, N-dimetylfor-
mamide, acac=acetylacetonate, and salen=N, N0 -disalicyli-
dene-ethylenediaminate). They found that U(V) formed
more stable complexes with multidentate ligands such as
acac and salen than those with unidentate ligands such as
DMF. In our study, a similar tendency was obtained in the
aqueous malonate solutions.
A plot of Eo1 vs. the logarithm of C at pH 5 is shown in
Fig. 6. In the presence of an oxalic acid, Eo1 was constant
(about 0:38 V) in the range of log C from 2:3 to 1:0
(C from 0.005 to 0.1 M), indicating that the dissociation of
oxalate from UO2 2þ did not occur (Fig. 6). So, the redox re-
action attributable to Poc1 and Poa1 is suggested as the fol-
lowing equation:
UVI O2 Ox2 2 þ e $ UV O2 Ox2 3 (C > 0:005 M): ð8Þ
LogV 1;2 was estimated to be 6:7  0:1 by substituting
Ef ¼ 0:377  0:004 V, E0 ¼ 0:142  0:004 V, T ¼ 298
K and log VI 1;2 ¼ 10:6417) into Eq. (7).
The logs of the stability constants of UV O2 Mal2 3 and
U O2 Ox2 3 in a 0.1 M NaClO4 solution obtained in the
V
present study were slightly larger than those of
NpV O2 Mal2 3 and NpV O2 Ox2 3 which were determined
by Tochiyama et al.20) using a solvent extraction method
to be 4.22 and 6.15, respectively, in a 1.0 M NaClO4 solu-
tion. A lower ionic strength solution gives larger stability
constants. So, our results are thought to be reasonable in a
0.1 M NaClO4 solution.
VOL. 44, NO. 9, SEPTEMBER 2007
1231
IV. Summary
The redox reactions of UO2 2þ in perchlorate and organic
acid solutions were electrochemically investigated using cy-
clic voltammetry. The quasi-reversible redox reaction of
UO2 2þ /UO2 þ was observed at 0:142 V (vs. Ag/AgCl) in
the perchlorate solution at pH 0–4. The peak for the oxida-
tion reaction of U(IV) species produced by the disproportio-
nation of UO2 þ was observed at around 0.27 V at pH 1.
In the solution containing a malonic or an oxalic acid, a
couple of peaks for UO2 2þ /UO2 þ and an oxidation peak
attributable to U(IV) oxidation to U(VI) were observed.
However, in the solution containing succinic, adipic, L-mal-
ic or L-tartaric acids, only two peaks attributable to the
UO2 2þ reduction to UO2 þ and U(IV) oxidation to U(VI)
were observed and no peak for UO2 þ oxidation was ob-
served because of the fast disproportionation of UO2 þ . The
peak potentials of the UO2 2þ reduction to UO2 þ showed a
good linear relationship with the stability constants of the
1:1 UO2 2þ organic complexes. This tendency would be use-
ful to predict the potential at which UO2 2þ may be reduced
in the presence of an organic acid whose stability constant is
already known.
In the presence of a malonic acid and an oxalic acid, we
found that the redox reaction of UO2 2þ /UO2 þ was related
to the complex species. The reactions were suggested as fol-
lows:
UVI O2 Mal2 2 þ e $ UV O2 Mal þ Mal2
(C < 0:1 M);
VI 2
U O2 Mal2 þ e $ U O2 Mal2 3
 V
(C > 0:1 M); Ef ¼ 0:403 V;
UVI O2 Ox2 2 þ e $ UV O2 Ox2 3
(C > 0:005 M); Ef ¼ 0:377 V:
The stability constants of UV O2 Mal2 3 and UV O2 Ox2 3
were estimated as 5:06  0:07 and 6:7  0:1 V, respectively.
We also found that UV O2 Mal2 3 was comparatively stable to-
wards disproportionation.
Acknowledgements
The Japan Atomic Energy Agency is gratefully acknowl-
edged for its partial financial support to Y. Suzuki as a re-
search fellowship for the Promotion of Science and Young
Scientists. This research was supported in part by a Grant-
in-Aid of the Ministry of Education, Culture, Sports, Science
and Technology to T. Ohnuki and by Environmental Reme-
diation Sciences Program, Office of Biological and Environ-
mental Research Office of Science U.S. Department of
Energy under contract No. DE-AC02-98CH10886 to A. J.
Francis.
References
1) R. J. Silva, H. Nitsche, ‘‘Actinide environmental chemistry,’’
Radiochim. Acta, 70/71, 377 (1995).
2) W. E. Harris, I. M. Koltoff, ‘‘The polarography of uranium. I.
Reduction in moderately acid solutions. Polarographic deter-
 1232
mination of uranium,’’ J. Am. Chem. Soc., 67, 1484 (1945).
3) I. M. Koltoff, W. E. Harris, ‘‘The polarograhy of uranium. II.
Polarography in strongly acid solution,’’ J. Am. Chem. Soc., 12)
68, 1175 (1946).
4) W. E. Harris, I. M. Koltoff, ‘‘The polarography of uranium. III.
Polarography in very weakly acid, neutral or basic solution,’’ 13)
J. Am. Chem. Soc., 69, 446 (1947).
5) L. Sipos, L. J. Jeftic, M. Branica, et al., ‘‘Electrochemical
redox mechanism of uranium in acidic perchlorate solutions,’’ 14)
J. Electroanal. Chem., 32, 35 (1971).
6) K. Mizuguchi, Y. Y. Park, H. Tomiyasu, et al., ‘‘Electrochem- 15)
ical and spectroelectrochemical studies on uranyl carbonato
and aqua complexes,’’ J. Nucl. Sci. Technol., 30, 542 (1993).
Downloaded by [WARSZAWSKI UNIWERSYTET MEDYCZNY- BIBLIOT] at 07:21 24 February 2015
7) K. A. Kraus, F. Nelson, G. L. Johnson, ‘‘Chemistry of aqueous 16)
uranium(V) solutions. I. Preparation and properties. Analogy
between uranium(V), neptunium(V) and plutonium(V),’’
J. Am. Chem. Soc., 71, 2510 (1949).
8) K. A. Kraus, F. Nelson, ‘‘Chemistry of aqueous uranium(V) 17)
solutions. II. Reaction of uranium pentachloride with water.
Thermosynamic stability of UO2 þ . Potential of U(IV)/(V), 18)
U(IV)/(VI) and U(V)/(VI) couples,’’ J. Am. Chem. Soc., 71,
2517 (1949). 19)
9) G. H. Tishkoff, Pharmacology and Toxicology of Uranium
Compounds, McGraw-Hill Book Company, New York (1949).
10) D. Ferri, I. Grenthe, F. Salvatore, ‘‘Studies on metal carbonate
equilibriums. 7. Reduction of the tris(carbonato)dioxouranate
(VI) ion, UO2 (CO3 )3 4 , in carbonate solutions,’’ Inorg. Chem., 20)
22, 3162 (1983).
11) C. E. Plock, F. J. Miner, ‘‘Polarographic behavior of uranium
Y. SUZUKI et al.
(VI) in malonic acid media,’’ Anal. Chim. Acta, 38, 553
(1967).
M. Susic, I. Gal, E. Cuker, ‘‘Polarographic determination of
uranium in ores in ascorbic acid supporting electrolyte,’’ Anal.
Chim. Acta, 11, 586 (1954).
Y. Suzuki, T. Nankawa, T. Yoshida, et al., ‘‘Reduction behav-
ior of uranium in the presence of citric acid,’’ Radiochim. Acta,
94, 579 (2006).
J. Selbin, J. D. Ortego, ‘‘The chemistry of uranium(V),’’ Chem.
Rev., 69, 657 (1969).
H. Imai, ‘‘Reaction rate and electron transfer mechanism in
disproportionation reaction of uranium (V),’’ Bull. Chem.
Soc. Jap., 30, 873 (1957).
S. Kihara, ‘‘Analytical chemical studies on electrode processes
by column coulometry, II. Studies on the electrode processes
of uranium and plutonium in aqueous solutions,’’ Electroanal.
Chem. Interfacial Electrochem., 45, 45 (1973).
R. M. Smith, E. Martell, Critical stability Constants, Vol. 6,
Plenum Press, New York (1989).
L. Meites, Polarographic Techniques, 2nd ed., Wiley, New
York (1965).
S. Y. Kim, H. Tomiyasu, Y. Ikeda, ‘‘Electorocemical studies
on [UO2 (DMF)5 ](ClO4 )2 , UO2 (acac)2 DMF, and
UO2 (salen)DMF (DMF=N, N-dimethylformamide, acac=ace-
tylacetonate, salen=N, N0 -disalicylideneethylenediaminate)
complexes in DMF,’’ J. Nucl. Sci. Technol., 39, 160 (2002).
O. Tochiyama, Y. Inoue, S. Narita, ‘‘Complex formation of
Np(V) with various carboxylates,’’ Radiochim. Acta, 58/59,
129 (1992).
JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY