Appl. h&l. I.wl Vol. 31. No. 4. pp.

358-359, 1986 The etfect of current density on the electrodeposition of

ht. J. Radiur. Appl. Instrum. Parr A uranium has been studied at a constant ammonium oxalate
‘C, Pergamon Press Ltd 1986. Printed in Great Britain. concentration (0.2 M. pH 9.0). and uranyl:oxalate ratio.
0X83-28W86 $3.00 + 0.00
I :95. The concentration of uranium in these solutions was
I .09 mgjmL. It was observed that at a current density of
40 mA/cm’ only 0.2 mg/cm’ of uranium was deposited m
15 min; whereas under otherwise identical conditions but
increased current density (66 mA/cm?). the deposited
Studies on the Electrodeposition of amount was 0.8 mg/cm’.
Now, keeping the other experimental conditions, namely
Uranium on Aluminium
ammonium oxalate concentration. current density and time
constant. the pH of the electrolytic solution was varied. The
N. N. MIRASHI, .I. N. MATHUR, SATYA PRAKASH results are given in Fig. I, which shows a linear increase in
and M. V. RAMANIAH the yields of uranium with increasing pH of the electrolyte.
Radiochemistry Division, Bhabha Atomic Research Centre, As very high yields (99.9%) were obtained at pH 9.0 in a
Trombay, Bombay, 400 085, India short time. investigations at still higher pH were not carried
out. The hydrolysis of many1 ions at such a high pH is
prevented by higher concentration of oxalate ions. The pH
(Receiwd 9 Ma?, 1985: in rrri.rrd fivm 8 Oc~ohrr 1985)
range (S.Cr8.5) used by Wilson and Langer”’ during the
electrodeposition of uranium from 0.2 M ammonium ox-
The electrodeposition method has been used to prepare alate solution agrees very well with the optimum pH of 9.0
thick sources of uranium on aluminium. By applying high observed during the present study. The method described by
current density in the ammonium oxalate solution (0.2 M, Titov”’ requires 5&60 min for electrodeposition of uranium
pH 9.0). containing “‘U, strongly adherent layers of from the heated solution on aluminium discs. which are
uranium (0.8 mg/cm’) are deposited. The electrodeposited subcoated with zinc; while with the conditions optimised
species is found to be U(IV)-oxalate complex. and reported in the present work electrodeposition is com-
plete in only 15 min and does not need prior coating of zinc
on aluminium.
The layer of electrodeposited uranium was observed to
Introduction
have a shining lustre and it was highly adherent to the
Thick and adherent deposits of actinides prepared on surface of the cylinder. The chemical composition of the
aluminium backings are required for nuclear studies and electrodeposited species has been studied and the results are
certain radiochemical techniques such as neutron counting. given below. The electrodeposited layers were scratched
A method of electrodeposition of uranium on aluminium is softly and dissolved in 2.5 M sulfuric acid. The oxidation
described by Wilson and Langer,“’ but they subcoated state of uranium in this sample was investigated by ferrous
aluminium with zinc. The technique of electrodeposition of phenanthroline method. “I Here, to the sample solution (in
uranium on an aluminium disc, reported by Titov,” is sulfuric acid), excess ferric ammonium sulfate and o-
modified in this work to deposit uranium on the inner phenanthroline were added and the reduced ferrous ions
surface of an aluminium cylinder. In the present study zi’U were estimated spectrophotometrically at 520 nm. It was
has been electrodeposited on the inner surface of an alumi- observed that all the uranium present is in +4 oxidation
nium cylinder by applying high current density in ammo- state. During scratching fine aluminium chips get collected
nium oxalateez3’Ll solution at pH 9.0. Also the mechanism along with uranium in the electrodeposited sample. To see
of electrodeposition has been discussed. the effect of aluminium if any. fine aluminium turnings were
added to a uranyl solution in sulfuric acid and the ferrous
Experimental phenanthroline method was carried out to check the pres-
ence of U(IV). It was found that aluminium had no reducing
Aluminium cylinders (1s purity and dimensions: 2 mm
thick, 30 mm id. and 250 mm length) were cleaned by
100 -
mechanical polishing to remove any oxide layers. The
cylinder was plugged at one end with a Teflon plug and
checked for leakage. The required amount of272U (as uranyl
nitrate solution) was added to the known volume of 0.2 M 80 -
ammonium oxalate. The pH of this solution was adjusted to
9.0 and then it was transferred into the cylinder. A platinum
anode rod was centrally positioned in the cylinder through
the top Teflon plug while the aluminium cylinder itself was
used as the cathode. During the electrodeposition, a current
density of 66 mA/cm’ was applied using an a.~. to d.c.
rectifier unit.
The amount of “%I deposited in the cylinder was esti-
mated from the difference in “‘U activity in the solution
before and after electrodeposition. The activity was assayed
using an r-proportional counter.
20 -

Results and Discussion

To establish the best possible deposition conditions, the I I I
electrodeposition of “%) was carried out at different ammo-
OL / ’
6 7 0 9 10
nium oxalate concentrations, at pH 9.0. It was observed that
at ammonium oxalate concentrations higher than 0.2M, the PH
rate of deposition gradually decreased. This decrease is in Fig. 1. Yields of uranium at different pH values of electro-
agreement with the findings of Titov.” lyte solution.

35x
 Technical Note 359

action on uranium during dissolution of the elec- ysis were not successful due to the amorphous nature of the
trodeposited samples. sample.
The formation of tetravalent uranium seems to take place
via the reduction of uranyl ions to the unstable pentavalent
state and its subsequent disproportionation to uranyl ion Conclusion
and U(IV) as reported in the electrolytic reduction of uranyl
solution.+h’ Further the oxalate ions used in the present Milligram amounts of uranium can be deposited on
electrodeposition studies enhance the disproportionation of aluminium using high current density and 0.2 M ammonium
pentavalent uranium by forming U(IV))oxalate complexes. oxalate solution at pH 9.0. Uranium is obtained in the +4
The i.r. spectra of the electrodeposited samples were taken oxidation state and U(C20,h gets deposited.
using a Perkin Elmer 577 grating type i.r. spec-
trophotometer. The presence of oxalate species is shown by Acknon~ledgemetz-The authors thank Dr P. R. Natarajan,
strong bands at 1400 and 1600 cm ’ due to Y, (O-C-O) and Head. Radiochemistry Division, B.A.R.C: for his keen
v, (O-CO) respectively. These bands agree well with the interest in this work.
known bands for oxalate group reported earlier.‘7.K’ The
quantitative estimation of uranium by arsenazo method”’
and of the oxalate group by KMnO, method gave the
References
uranium to oxalate ratio as I:2 in the electrodeposited I. Wilson C. R. and Langer A. Nucleonics 11(S), 48 (1953).
samples. This shows the deposition of U(C,O,), species on 2. Titov V. F. Soaier J. At. Energ. 8, 229 (1961).
the cathode. We conjecture that the main mechanism of the 3. Vyadra F. and Pribil R. Talanra 9, 1009 (1962).
deposition is as follows. The ammonium ions in the vicinity 4. Samartseva A. G. AEC-TR-4497, 400 (1958).
of the cathode get readily discharged leaving a higher 5. Kolthoff I. M. and Harris W. E. J. Am. Chem. Sot. 68,
concentration of oxalate ions near the cathode. Tetravalent 1175 (1946).
uranium ions on reaching the cathode form the 6. Alekperov A. I. and Zhdanov S. I. Russ. J. Inorg. Chem.
U(IV)-oxalate complex and get deposited. The mechanism S(S), 846 (1960).
of this deposition is the same as discussed earlier in the case 7. Fujita J. J. Phys. Chem. 61, 104 (1957).
of deposition of actinide hydroxides.“O.“’ 8. Prasad N. S. K. J. Inorg. Nucl. Chem. 27, 231 I (1965).
Puphal and Olsen”” have suggested the electrodeposition 9. Nemodruk A. A. and Glukhova L. P. Zh. Anal. Khim.
of negatively charged species of Pu)+ and Th4+ from oxalate 18, 93 (1963).
media. Anionic species like U(C,O,)i- are formed at higher 10. Miller H. W. and Brouns R. J. Anal. Chem. 24(3), 536
oxalate concentrations, In the present study as well as that (1952).
of Titov,‘?) with an increase in ammonium oxalate concen- I I. Ramaniah M. V., Singh R. J., Awasthi S. K. and Satya
tration above 0.2 M, the rate of deposition is observed to Prakash, Inf. J. Appl. Rndiar. Isof. 26, 648 (1975).
decrease. Hence deposition of anionic species does not seem 12. Puphal N. W. and Olsen D. R. Anal. Chem. 44(2), 254
likely. (1972).
The formation of any hydroxo species has not been 13. Rajan K. S. and Martell A. E. J. Inorg. NW/. Chem. 29,
considered even at such a high pH (9.0), because the 523 (1967).
uranium to oxalate ratio is very high (1:95) in the electro- 14. Have1 J. Coil. Czechoslot:. Chem. Commun. 134, 3248
lytic solution, and the uranium oxalate complexes are (1969).
known to be highly stable. I”.mIs’ Further attempts to charac- 15. Miyake C. and Nurnberg H. W. J. Inorg. Nucl. Chem.
terise the electrodeposited sample by x-ray diffraction anal- 29, 2411 (1967).