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ISSN: 2456-9992
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
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
% 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)%
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).
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).