SHORT COMMUNICATION

Journal of Radioanalytical and Nuclear Chemistry, Vol. 246, No. 2 (2000) 433–435

Determination of uranium and plutonium in high active solutions

by extractive spectrophotometry
R. V. Subba Rao,* K. Damodaran, G. Santosh Kumar, T. N. Ravi
Reprocessing Group, Indira Gandhi Centre for Atomic Research, Kalpakkam, 603 102, India

(Received January 3, 2000)

Plutonium and uranium was extracted from nitric acid into trioctyl phosphine oxide in xylene. The TOPO layer was analysed by
spectrophotometry. Thoron was used as the chromogenic agent for plutonium. Pyridyl azoresorcinol was used as chromogenic agent for uranium.
The molar absorption coefficient for uranium and plutonium was found to be 19000 and 19264 liter/mole-cm, respectively. The correlation
coefficient for plutonium and uranium was found to be 0.9994. The relative standard deviation for the determination of plutonium and uranium
was found to be 0.96% and 1.4%, respectively.

Introduction convert all plutonium valancies to Pu(IV). Then uranium

Plutonium and uranium carbides irradiated to
50,000 Mwd/t are dissolved in a nitric acid medium
using the electro oxidative dissolution technique,1 and
the Purex process follows for the recovery of plutonium
and uranium from the above solution. In order to
determine U and Pu concentration in various process
streams to meet the operation requirements of the
reprocessing plant, a simple analytical method, easily
remortisable with reasonable precision and accuracy is
required. Since the samples are highly active, in order to
reduce exposure to plant analytical personnel solvent
extraction using TOPO as the solvent is chosen to
preferentially extract uranium and plutonium from
fission products. Various spectrophotometric methods
are reported for determination of uranium and plutonium
in organic layers in the literature.2–4 These methods are
not suitable for the determination of uranium and
plutonium from the organic layer due to their mutual
interference. A method based on pyridyl azo resorcinol5
is chosen for uranium determination. The determination
of plutonium by thoron as the chromogenic agent6 is
chosen since this method tolerates uranium. Experiments
were carried out and the results obtained are presented
here.
Experimental
A stock solution of uranium and plutonium was
prepared dissolving their respective oxide in nitric acid.
The uranium concentration was standardised by the
DAVIES and GRAY7 method whereas plutonium by a
redox6 titration method. Required concentrations of
uranium and plutonium were prepared by diluting stock
solution with 2M nitric acid. Before the extraction of
plutonium with TOPO, sodium nitrite was added to
* E-mail: prasu@igcar.ernet.in
0236–5731/2000/USD 17.00
© 2000 Akadémiai Kiadó, Budapest
and plutonium were extracted into TOPO (xylene) from
4M nitric acid. Aqueous and organic layers were
separated by centrifuging.
Calibration of uranium
Reagents required for the spetctrophotometric
analysis of uranium were given elsewhere.5 A suitable
aliquot (10–100 µg) was taken in a 10 ml standard flask.
1 ml of triethanol amine buffer, 1 ml of complexing
agent, and 0.4 ml of PAR was added. The volume was
made up to 10 ml with ethyl alcohol, and the absorbance
was measured at 530 nm against a reagent blank.
Calibration of plutonium
A suitable aliquot (8–80 µg) of plutonium was taken
into a 10 ml standard flask and 0.1 ml of conc. HCl and
0.5 ml of 0.1% alcoholic thoron was added, made up to
volume with ethyl alcohol, and the absorbance was
measured at 545 nm against a reagent blank.
Result and discussion
Effect of TOPO concentration
This study indicated that absorbence at 530 nm for
Pu in the 10 ml flask was 0.233±0.008 from 0.025–0.4M
TOPO (xylene), whereas at 0.5M TOPO concentration
the absorbance value was 0.187. Hence 0.1M TOPO
(xylene) was chosen as extractant.
Figures 1 and 2 show the variation of the absorbance
as a function of plutonium and uranium concentration.
Linear regression analysis was carried out for the data
given in the figures. The correlation coefficient for
plutonium and uranium was 0.9994. Hence, the analysis
of plutonium and uranium obeys Beer-Lamberts law,
Akadémiai Kiadó, Budapest
Kluwer Academic Publishers, Dordrecht
 R. V. SUBBA RAO et al.: DETERMINATION OF URANIUM AND PLUTONIUM IN HIGH ACTIVE SOLUTIONS
Fig. 1. Plutonium calibration graph
Table. 1.Intercomparision of the present method and the reported methods
Irradiated Uranium
pellet sample
Present method, DAVIES and GRAY Present method, Alpha-counting,
mg/g
1 1.1
2 1.2
the plutonium or uranium concentration per aliquot as a
function of abosrbance can be given by: Pu or U
concentration (µg) = 125.absorbance.
The molar extinction coefficient for plutonium was
found 19264 liter/mole-cm and for uranium 19000
liter/mole-cm.
Validation with synthetic process solutions
In order to verify the method for analysis of samples
generated during reprocessing of irradiated plutonium
and uranium carbide fuel, different ratios of uranium and
plutonium in nitric acid medium were taken in an
extraction vial, 0.1 ml of 3M sodium nitrite was added
and the acidity was adjusted with 4 N nitric acid to 5 ml.
5 ml of 0.1M TOPO (xylene) was added. Both phases
were mixed using a vortex shaker and the organic phase
was separated. Uranium and plutonium was analysed by
the procedure as given for the calibration graph. The
relative standard deviation for the estimation of uranium
and plutonium was found to be 1.4% and 0.96%,
respectively.
Interference studies were carried out with different
cations that are going to be present along with uranium
and plutonium aqueous solutions. A synthetic solution
containing 0.030 mmoles of chromium or 0.05 mmoles
434
Fig. 2. Uranium calibration graph
Plutonium
method, mg/g mg/g mg/g
1.08 2.8 2.67
– 3.1 3.3
of silver or 0.01 mmoles of iron and plutonium was
prepared. The procedure as given for the validation step
was followed. It was found that bias due to the above
interfering elements is less than 5%.
Application to irradiated fuel samples
An irradiated UC/PuC pellet to 25,000 MWD/t was
dissolved in nitric acid using the EODT method.
Samples were taken and analysed by the procedure given
for the process samples. The results for plutonium were
compared with alpha counting where those for uranium
to the Davies-Gray method. These results are given in
Table 1. Data in table indicated that the results obtained
by the present method and the already known methods
were comparable, indicating the suitability of this
method for analysis of plutonium and uranium in the
high active process solutions.
Conclusions
The present analytical method is simple and can be
easily remotised for hot cell operation. The precision and
accuracy of the method is adequate for the process
control sample analysis.
 R. V. SUBBA RAO et al.: DETERMINATION OF URANIUM AND PLUTONIUM IN HIGH ACTIVE SOLUTIONS

* References

The authors wish to express their sincere thanks to
Shri. R. NATARAJAN, Project Manager, FRFRP and
Shri. M. VENKATARAMAN, Superintendent, Plant Operation,
Reprocessing Group for their encouragement and suggestion during
course of this work.
1. A. PALAMALI et al., Radiochim. Acta, 55 (1991) 25.
2. C. E. CROUTHAMEL et al., Anal. Chem., 24 (1952) 1780.
3. J. H. YOE et al., Anal. Chem., 27 (1953) 1200.
4. K. K. GUPTA et al., Talanta, 40 (1993) 507.
5. E. N. POLLOCK, Anal. Chim. Acta, 88 (1977) 399.
6. Analytical Chemistry of Plutonium, M. S. MILYUKOVA (Ed.),
Chap. 4, p. 126.
7. W. DAVIES, W. GRAY, Talanta, 11 (1964) 1203.

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