International Journal of Advanced Research and Publications

ISSN: 2456-9992

Effect Of Uranyl Ions & Hydrazine During The

Oxidation/Reduction Of Ce(iii)/Ce(iv) Ions By
Electrolysis
J. Kavitha, R. Anitha, D. Umamaheshwari
Department of Chemistry,Jay Shriram Group of Institutions,Tiruppur-638 660 ,Tamil Nadu,India

Department of Chemistry,SNS College of Technology,Coimbatore-641 035,Tamil Nadu, India

kavithajchem@gmail.com

Abstract: With a view to determine the influence of uranyl ions on the oxidation of Ce(III) and the effect of Ce(IV) on the reduction of
2
U(VI), electrochemical oxidation/reduction studies were carried out (at a fixed current density of 10 mA/cm ) with 0.05 M pure Ce(III) and
with 0.05 M Ce(III) in the presence of x M U(VI) (x = 0.028, 0.098, 0.246 and 0.411) in 11.5 M nitric acid medium.

Keywords: Uranyl ions, Cerous ions, Concentrations, Uranium, Electrolyser, Oxidation & Reduction

1 INTRODUCTION The anode was isolated from the cathode by means of a

In the reprocessing plant of FBR fuels, use of the redox one end closed, cylindrical and porous porcelain
catalyst Ce(III)/Ce(IV) is envisaged in the dissolution diaphragm tube of height 120 mm, OD 40 mm and 3 mm
cum destruction of the soluble carbon compounds as Ce wall thickness. The surface area of the anode and cathode
is one of the fission products present in the irradiated 2
were 120 and 18 cm respectively. The catholyte was 54
fuel and could be exploited in the electrolyser for the ml of 0.05 M Ce(III) in 11.5 M nitric acid. The current
purpose of dissolution. In order to achieve maximum 2
efficiency in the generation of Ce(IV), the process density was fixed as 10 mA/cm .
parameters such as current density, temperature and
nature and concentration of the mediated electrochemical
catalyst need to be optimized. Further, the influence of
other metallic elements (having high oxidation states) on
the oxidation rate of cerous ions needs to be established. Pt cathode
Feasibility studies are required to get an idea about the
role played by cerous/ceric ions during the Ceramic
electrochemical reduction of uranyl ions for partitioning Diaphragm
applications. The effect of hydrazine as a holding
reductant in destroying the unwanted nitrous acid also Glass beaker
needs to be determined. With these objectives in mind,
electrochemical oxidation/reduction of 0.05 M Ce3+ in
the presence of various concentrations of uranyl ions in
11.5 M nitric acid medium was carried out at a fixed
2 Pt anode
current density (10 mA/cm ). Electro reduction
experiments were also performed with hydrazine with a
view to finding out its optimum concentration required Ce(III) + U(VI)
for the reduction processes in the plant.

2.EXPERIMENTAL PART
2.1 CELL ASSEMBLY
The schematic of the cell assembly is given in Fig. 1. For
the oxidation experiments, 150 ml of 0.05 M Ce(III) and x Fig- 1 Cell arrangement with diaphragm tube
M U(VI) solution in 11.5 M nitric acid was taken in a
glass beaker.Pt-10% If gauze electrodes were employed.
cerous ions were converted to ceric ions and the oxidized
The concentration polarization (arising due to mass ceric ions were reduced to cerous by reversing the
transport) and kinetic polarization or overvoltage polarity.
(restricting the rate of reaction) were minimized by
resorting to proper mixing of the electrolyte and by
conducting experiments below the limiting current density
which value was determined from preliminary
experiments. The experiments were continued until all

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 International Journal of Advanced Research and Publications
ISSN: 2456-9992

3 RESULTS AND DISCUSSION TABLE 2: Reduction experiment with the following

catholyte
TABLE 1 Ce(IV) GENERATION WITH AND WITHOUT
Anolyte: [Ce(III)]: 0.098 M; [H+] = 9.06 M
URANIUM Initial concentration of Ce(III): +
0.05M;[HNO3]: 11.5 M Catholyte: [U(VI)]: 0.098 M; [Ce(III)]: 0.05 M; [H ] =
12.26 M

% of Ce(IV) % of Ce(IV)
Time (h)
[with 0.246 M [without U(VI)]
0
U(VI)] 0
0
M
93.0 95.4
0
U
. 97.3( 99.1
1
5 V
. 98.6 99.3
1 I
0
. 96.9) 99.8
2 ]
5
.

80

60

40

20

U(IV)%

0 0.0 0.5 1.0 1.5 2.0 2.5

Time/h

Fig. 2.Comparison of the oxidation rates of 0.05 M

Ce(III) (pure) and with0.246 M U(VI)

Fig.3. Simultaneous reduction of 0.098 M U(VI) and 0.05

M Ce(IV)

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 International Journal of Advanced Research and Publications
ISSN: 2456-9992

TABLE 3: U(IV) generated without and with [3] G.R. Choppin, H. Bokelund and S. Valkiers, Radiochim.
0.31 M hydrazine Initial [U]: 0.028 or 0.029 M; Acta, 33 (1983) 229.
Initial [Ce3+] = 0.05 M
[4] H. Bokeland, M. Caceci and W. Mullers, Radiochim. Acta,
% of U(IV) % of U(IV) 33 (1983) 115.
Time (h) without with 0.31 M
0 0 0 [5] R.W. Carson, B.W. Bremer, M.L. Mastracci and K.E.
hydrazine hydrazine
0.5 36.7 82 Maggard, US Patent No. 20060144700 (2006).
1.0 51.8 89.1
1.5 59.5 95.7 [6] L.A. Bray, J.L. Ryan and E.J. Wheelwright, Report No. PNL-
5657 (1985).
2.0 73.0 95.7
2.5 82.7 ---
[7] J.L. Ryan, L.A. Bray and A.L. Boldt, US Patent No. 4686019
3.0 90.0 --- (1987).
3.5 95.7 ---
[8] M. Matheswaran, S. Balaji, S.J. Chung and I. Moon, Bull.
Korean Chem. Soc., 2(2007).

[9] S. Balaji, S.J. Chung, T. Ramesh and I. Moon, Chem. Engg.

Jrl., 126 (2007) 51.

[10] T. Raju and C. Ahmed Basha, Portugal. Electrochim. Acta,

23 (2005) 367.

[11] J.-W. Lee, S.J. Chung, S. Balaji, V.V. Kokovkin and

I. Moon, Chemosphere, 68 (2007)1067.

[12] B. Fang, S. Iwasa, Y. Wei, T. Arai and M. Kumagai,

Electrochim. Acta, 47 (2002) 3971.
Fig. 4. Percentage conversion of 0.028 M U(IV) with
[13] A. Paulenova, S.E. Creager, J.D. Narratil and Y. Wei,
(0.31 M) and without hydrazine
J. Power Sources, 109 (2002) 431.
Kumagai,Electrochim. Acta 47 (2002) 3971.
4 CONCLUSION
The rate of oxidation to Ce(IV) and the reduction rate of [14] L. Jelinek, Y. Wei and M. Kumagai, Solvent
Ce(IV) were compared with those results obtained in Extraction & Ion Exchange, 24 (2006) 765.
the subsequent experiments for the
oxidation/reduction of 0.05 M Ce(III) with uranyl ions [15] L. Jelinek, Y. Wei and M. Kumagai, J. Rare Earths,
of concentration 0.028, 0.098, 0.246 mole (representing 24 (2006) 257.
a simulated solution with fuel element)., It was observed
that in all experiments, the kinetics of reduction to be [16] C.S. Kedari, S.S. Pandit and A. Ramanujam, J.
much faster than that of oxidation due to the competing Radioanal. Nucl. Chem., 222 1997) 141.
chemical reduction of ceric ions by the intermediate
nitrous acid produced during electrolysis, the
efficiency of the reduction process was found to be
doubled when the efficiency was compared with that of
the reduction experiment without hydrazine. As the
concentration of U(VI) was very high for 0.05 M
Ce(IV), no improvement could be observed in the
efficiency; nevertheless, hydrazine was found to be
consumed at a faster rate.

5 REFERENCES
[1] J.Y.Ryan and L.A. Bray, "Dissolution of Plutonium Dioxide-
-A Critical Review", Actinide Separations, ACS, Symp.
Series No. 117 (1980) 513.

[2] J.R. Flanary, J.H. Goode, M.S. Bradley, S.W. Ullmann, L.M.
Ferris and G.S. Wall, ReportNo. ORNL – 3660 (1964).

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