Radiochim.
Acta 90, 323–327 (2002)
 by Oldenbourg Wissenschaftsverlag, München
Separation of neptunium and plutonium from acidic medium using
3-phenyl-4-benzoyl-5-isoxazolone
By P. K. Mohapatra, P. B. Ruikar and V. K. Manchanda∗
Radiochemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai 400085, India
(Received October 1, 2001; accepted in revised form January 14, 2002)
Plutonium / Neptunium / Separation / Solvent extraction
Summary. The extraction behaviour of plutonium (IV) and
neptunium (IV) was studied from nitric as well as hydrochlo-
ric acid employing 3-phenyl-4-benzoyl-5-isoxazolone (PBI)
in toluene as the extractant. The forward extraction in hy-
drochloric acid medium was carried out in presence of several
holding oxidants out of which ammonium meta vanadate was
found to give the best results. The stripping behaviour of
Np and Pu was studied employing a variety of reagents out
of which 0.1 M hydroquinione in 1 : 1 HCl was the most
promising. The separation of Np from Pu under simulated
conditions was attempted from hydrochloric acid medium
giving a decontamination factor value of > 104 and ∼ 60%
Pu recovery.
Introduction
Both plutonium and neptunium display a wide range of oxi-
dation states and undergo disproportionation readily in aque-
ous solutions [1]. The oxidising/reducing nature of common
mineral acids further influences the proportion of these oxi-
dation states in acidic solutions. The extraction behaviour of
Pu and Np in the same oxidation state varies only marginally
but it is significantly different when the oxidation states dif-
fer. Development of analytical procedures for their separa-
tion therefore requires the adjustment to different oxidation
states employing common redox reagents.
Due to its low pK a value (1.12), 3-Phenyl-4-benzoyl-
5-isoxazolone (PBI) has been shown as an efficient chelat-
ing extractant for tetravalent actinide ions especially from
strongly acidic as well as complexing media [2, 3]. We
have already developed a method for the recovery of Pu
from Davis–Gray Analytical waste solution which contained
a complex mixture of sulphuric, nitric and phosphoric acids.
In the present work the extraction of both Pu and Np is
carried out from varying concentrations of HCl. The ef-
fect of a variety of oxidising agents such as potassium
bromate, potassium dichromate, sodium nitrite, ammonium
metavanadate and hydrogen peroxide is also investigated.
An attempt has been made in the present work to in-
vestigate the analytical separation of Pu and Np in 1 : 1
*Author for correspondence
(E-mail: acsrcd@magnum.barc.ernet.in).
Brought to you by | New York University Bobst Library Technical Services
Authenticated
Download Date | 5/28/15 3:22 PM
HCl. The aqueous medium chosen in this work is particu-
larly relevant for the separation of the trace concentrations
of 237 Np and 239 Pu formed during the irradiation experi-
ment, viz. 235 U(α, 3n)236 Pu. Aluminium targets used in these
studies are often dissolved in 1 : 1 HCl to facilitate further
radiochemical work on the desired radionuclide 236 Pu [4].
PBI has a distinct advantage over the common β-diketone
TTA in view of its ability to extract Pu(IV) from moderately
strong acidic solutions [5].
Experimental
HPBI was synthesized in this laboratory following a re-
ported method [6]. Pro-analysi grade thenoyltrifluoroace-
tone (TTA) obtained from E. Merck was recrystallised be-
fore use. Hydroquinone was procured from Agfa-Gevaert
(India) and ammonium metavanadate from B.D.H. (Lon-
don). A.R. grade potassium dichromate, potassium bromate,
and sodium nitrite were obtained from Sarabhai Chemicals
(Mumbai) and hydrogen peroxide from Merck (India). Ex-
tra pure grade toluene was obtained from E. Merck and was
used as such. All other reagents used were of A.R. grade.
239
Pu was purified by a reported method [7] and its va-
lency adjustment was done by adding a pinch of sodium
nitrite to the solution in 1 M HNO3 the excess of which was
destroyed by warming the solution under an infrared lamp.
Pu in the tetravalent state was first extracted by 0.5 M TTA
in toluene and subsequently stripped in to 6 M HCl, which
was used as the Pu (IV) stock solution. Similarly, for the
experiments involving HNO3 , the stock solution was made
by the stripping of the Pu (IV) extract into 7 M HNO3 . The
aqueous phase containing the stripped plutonium was con-
tacted twice with toluene so as to remove the dissolved TTA.
Most extraction experiments with Np were carried
out employing 238 Np tracer that was produced by the ir-
radiation of a 237 Np target at a thermal flux density of
1 × 1012 neutrons/sec/cm2 . The irradiated Np target was
dissolved in 1 : 1 HCl and was diluted to give a final acid
concentration of ∼ 1 M. The valency of neptunium was then
adjusted to 4+ using ferrous sulphamate and hydroxylamine
hydrochloride. Np(IV) was then extracted employing 0.5 M
TTA solution in toluene followed by back extraction into
6 M HCl. The aqueous phase containing the stripped nep-
tunium was scrubbed twice with toluene to remove traces
324 P. K. Mohapatra, P. B. Ruikar and V. K. Manchanda

of TTA. The separated aqueous solution was subsequently

used as the Np(IV) stock solution. For experiments involv-
ing HNO3 , the stripping was carried out employing 7 M
HNO3 with subsequent dilution of the aqueous phase. For
a few experiments involving the separation of Np from Pu,
237
Np was used, which was subsequently assayed by alpha-
spectrometry.

Pu
%E
Distribution studies
40
The forward extraction studies involving both Pu and Np
were carried out by equilibrating the aqueous phase con-
taining an adequate concentration of the holding oxidant in
the mineral acid of interest spiked with the respective tracer.
The organic phase contained PBI at the desired concentra-
tion and the volume was usually 0.5 mL. For the backward
extraction as well as stripping studies the activity loaded
organic extract was contacted with the required aqueous
phase. The equilibration was carried out for 1 hour in a ther- Fig. 1. Percent Pu extraction from HCl and HNO3 medium at varying
mostated water bath at 25 ± 0.1 ◦ C. Radiometric assay of the acidity. [PBI] = 0.05 M.
desired aliquots was carried out after the cetrifugation of
the tubes. 239 Pu was measured by liquid scintillation count-
ing and 238 Np by gamma counting employing a well type including partitioning in the presence and absence of hold-
NaI(Tl) detector. ing oxidants. In the studies where no holding oxidant is used,
The distribution ratio of the metal ion (DM ) is defined as the aqueous phase containing the required acid was spiked
the ratio of the organic phase counts per unit time per unit with the tracer whose valency state had been previously ad-
volume to the aqueous phase counts per unit time per unit justed to the +4 state. Near quantitative extraction of Pu is
volume. Percentage metal ion extracted is defined as: observed from 1–5 M HCl, while from HNO3 medium the
same is possible only at acid concentration ≤ 1 M (Fig. 1).
%E = 100DM / (Va /Vo ) + DM , This is explained on the basis of greater complexing power
of nitrate ion as compared to the chloride ion. In the case
where Va and Vo are the aqueous phase and organic phase of Np, only a marginal difference was noticed between
volumes respectively. HNO3 and HCl media (Fig. 2). It is noteworthy that for
both Pu and Np, the %E values decrease sharply beyond
Separation studies 6 M HCl whereas in the HNO3 medium the decrease is less
pronounced.
Known quantities of 233 U (1.8 × 104 Bq), 237 Np (7.4 × It is well known that Pu(IV) is slowly converted to a mix-
103 Bq) and 239 Pu (1.0 × 103 Bq) tracers were mixed in 1 : 1 ture of Pu(III), Pu(IV), Pu(V) and Pu(VI) in HCl medium
HCl solution containing about 20 mg/mL of Al and extrac- due to the disproportionation reactions [8]. Therefore, it is
tion was carried out employing 0.05 M PBI solution. The
organic extract was contacted with an aqueous solution con-
taining 0.1 M hydroquinone in 1 : 1 HCl. Aliquots after the
extraction and stripping as well as from the initial solution
containing the mixture were analysed by alpha-spectrometry
using a silicon surface barrier detector.

Spectrophotometric studies
For the spectrophotometric studies, about 0.5–1 mg/mL of
Np

the metal ion (Np/Pu) was taken in the required aqueous so-
%E

lution. The spectra were recorded using a Beckmann-DU7

spectrophotometer coupled to a glove box facility.

Results and discussion

The present work deals with the extraction behaviour
of Pu(IV) and Np(IV), particularly in hydrochloric acid
medium employing 0.05 M PBI solution. Some data con-
cerning their extraction behaviour from nitric acid medium
is also included for comparison purpose. Distribution stud- Fig. 2. Percent Np extraction from HCl and HNO3 medium at varying
ies were carried out under varying experimental conditions, acidity. [PBI] = 0.05 M.
Brought to you by | New York University Bobst Library Technical Services
Authenticated
Download Date | 5/28/15 3:22 PM
Separation of neptunium and plutonium from acidic medium 325

Table 1. Effect of holding oxidants on plutonium(IV) extraction.

[HCl] = 6 M; [PBI] = 0.05 M.

Holding oxidant Concentration (M) %E Pu

5 × 10−3 86
KBrO3 5 × 10−4 74
5 × 10−5 55

M
5 × 10−3 78 a

%E
K2 Cr2 O7 5 × 10−4 86
5 × 10−5 87

5 × 10−2 < 0.01

NaNO2 5 × 10−3 83
5 × 10−4 87

5 × 10−3 89
NH4 VO3 5 × 10−4 87
5 × 10−5 87

5 × 10−2 84 Fig. 3. Percent Pu and Np extraction from HCl medium at varying

H2 O2 5 × 10−3 90 acidity in presence of 5 × 10−5 M AMV. [PBI] = 0.05 M.
5 × 10−4 44

a: precipitation observed. than that in the case of Pu (Fig. 3). On the other hand, an
opposite trend is observed in the absence of AMV. Table 2
gives the distribution data for both Np and Pu in the ab-
necessary to use a holding oxidant in the aqueous phase. The sence as well as in the presence of AMV (5 × 10−5 M) at
distribution data for Pu(IV), obtained in presence of a var- 6 M HCl. In the absence of AMV, Np(IV) is fairly stable in
iety of holding oxidants are included in Table 1. In these
experiments the HCl concentration is fixed at 6 M and prior
adjustment of the oxidation state is not done to explore the
possible application for the recovery of 236 Pu from irradiated
235
U targets (vide infra).
It is also evident from Table 1 that in the presence of
higher concentration of the K2 Cr2 O7 %E decreases sug-
gesting possible conversion to PuO2 2+ species. In case of
NaNO2 , the %E increases with the decreasing concentration
of the holding oxidant. This is attributed to a) decomposition
of nitrite ion in acidic medium and b) degradation of the
beta-diketone in presence of large concentration of nitrite
ion [9]. Similar behaviour was also observed earlier by us
when PMBP (1-phenyl-3-methyl-4-benzoyl-5-pyrazolone)
was used as the extracatnt for Pu(IV) [5]. Amongst the
holding oxidants employed in the present study ammonium
metavanadate (AMV) gave consistent DPu values in widely
varying concentration ranges (from 5 × 10−3 to 5 × 10−5 M).
Therefore, in all subsequent experiments AMV was em-
ployed as the holding oxidant. Under identical condition
using 5 × 10−5 M AMV as the holding oxidant, Np extrac-
tion is ∼ 9% suggesting that in a single contact a separation
factor (DPu /DNp ) of 92 is achieved. Fig. 4. UV/visible spectra of Pu under varying extraction/stripping
conditions at 1 : 1 HCl; (a) no holding oxidant is used; (b) in presence
It is interesting to note that in presence of AMV the %E of 5 × 10−5 M AMV; (c) the organic phase spectra after equilibration
of Np drops with increasing acidity upto 6 M more sharply with 0.05 M PBI; (d) in presence of 0.1 M hydroquinone.

Table 2. Extraction data for Pu and Np in

the presence and absence of 5 × 10−5 M Experimental DPu %E Pu DNp %E Np S.F. (DPu /DNp )
ammonium metavanadate. [PBI] = 0.05 M. condition
Aqueous phase = 6 M HCl.
5 × 10−5 M AMV a 9.2 90 0.11 9.1 92
no AMV added b 0.38 28 24 96 0.02
no AMV added a 51 98 12 92 4.3

a: valency state adjustment is not done for Pu as well as Np;

b: valency of Pu as well as Np were prior adjusted by TTA extraction to 4+ state.
Brought to you by | New York University Bobst Library Technical Services
Authenticated
Download Date | 5/28/15 3:22 PM
326 P. K. Mohapatra, P. B. Ruikar and V. K. Manchanda

Table 4. Stripping behaviour of neptunium. Extractant: 0.05 M PBI in

toluene.

Strippant % age Pu stripping

6 M HNO3 17
10 M HNO3 > 99
3 M HCl + 0.1 M hydroxyl 2.5
amine hydro chloride
3 M HCl + 0.1 M ammonium oxalate 52
+ 0.1 M oxalic acid
3 M HCl + 0.1 M hydroquinone 2.2
4 M HCl + 0.025 M hydroquinone 2.4
1 : 1 HCl + 0.1 M hydroquinone <1

strippant > 99% Pu and Np are stripped. On the other hand,

Fig. 5. UV/visible spectra of Np under varying extraction/stripping
conditions at 1 : 1 HCl; (a) no holding oxidant is used; (b) in presence
of 5 × 10−5 M AMV; (c) in presence of 0.1 M hydroquinone.
while 0.1 M hydroquinone in 1 : 1 HCl can quantitatively
strip Pu, there is poor stripping of Np (< 1%) under identical
conditions. This is explained on the basis of the larger reduc-
tion potential of the Pu(IV)/Pu(III) couple as compared to
that of the Np(IV)/Np(III) couple:

Pu4+ + e− −→ Pu3+ E ◦ = 0.98 V

HCl medium. However, the same is not true about Pu(IV)
which is slowly reduced to the +3 state. On the other hand, Np4+ + e− −→ Np3+ E ◦ = 0.15 V .
AMV possibly converts Pu(III) back to Pu(IV) and converts
Np(IV) to the poorly extracting Np(V) and Np(VI). This Thus, it is possible to reduce Pu4+ with hydroquinone with-
aspect is verified by UV-Visible spectrophotometry using out effecting similar reduction of Np4+ . Fig. 4d clearly
macro concentrations of Np and Pu (Figs. 4 and 5). It is shows that under the stripping conditions of 0.1 M hydro-
clear from Fig. 4a that under conditions where no hold- quinone and 1 : 1 HCl the predominant species is Pu3+ as
ing oxidant is used, plutonium exists as a mixture of +3, indicated by absoption bands appearing at 550, 610 and
+4, +5 and +6 states. In presence of 5 × 10−5 M AMV,
though changes in the aqueous phase spectrum (Fig. 4b)
was slow, equilibration with 0.05 M PBI indicated near
quantitative extraction of Pu(IV) species due to strong ab-
sorbance at 470 nm (Fig. 4c). On the other hand, Np(IV)
is identified by an intense peak at 723 nm (Fig. 5a) which
is stable in the absence of the holding oxidant. In pres-
ence of 5 × 10−5 M AMV, the spectra changes with the
peak at 617 nm (characteristic of Np(V)) becoming more
intense (Fig. 5b).

Stripping behaviour
Tables 3 and 4 show the stripping behaviour of Pu and Np re-
spectively under various conditions. With 10 M HNO3 as the

Table 3. Stripping behaviour of plutonium. Extractant: 0.05 M PBI in

toluene.

Strippant % age Pu stripping

6 M HNO3 5.5
10 M HNO3 > 99
3 M HCl + 0.1 M hydroxyl 5.1
amine hydro chloride
1 M HNO3 + 0.2 M ammonium oxalate > 95
+ 0.2 M oxalic acid
3 M HCl + 0.1 M hydroquinone 99
4 M HCl + 0.025 M hydroquinone > 99 Fig. 6. Alpha-spectra of the (a) synthetic mixture containing 237 Np +
239
1 : 1 HCl + 0.1 M hydroquinone > 99 Pu; (b) after the extraction step using 0.05 M PBI; (c) after the strip-
ping step using 0.1 M hydroquinone in 1 : 1 HCl.
Brought to you by | New York University Bobst Library Technical Services
Authenticated
Download Date | 5/28/15 3:22 PM
Separation of neptunium and plutonium from acidic medium 327

665 nm. On the other hand, Np4+ is the main species for the Pu at the extraction stage (using 0.05 M PBI as the extrac-
Np stripping system under identical conditions (Fig. 5c). tant and 5 × 10−5 M AMV as the holding oxidant) is 67%
(Fig. 6b) and at the stripping stage (using 0.1 M hydroqui-
237 239 nine in 1 : 1 HCl as the strippant) is > 90% (Fig. 6c). The
Separation of Np from Pu
overall decontamination factor and overall Pu recovery are
Fig. 6 shows the alpha spectra of the synthetic 233 U, 237 Np > 104 and 60% respectively. The overall Pu recovery re-
and 239 Pu mixture (a) before separation; (b) after extraction; ported by Efurd et al. [11] is ∼ 57%. The present method of
and (c) after stripping. The peak at 4.76 MeV is not resolved separation is, therefore a much simpler method and involves
and contains activity due to both 233 U and 237 Np. It is note- only 3 steps compared to more than 40 steps required for the
worthy that the U and Np activity is taken in large excess method reported earlier in the literature [11]. A flow diagram
as compared to Pu to test the efficiency of the separation for the separation method developed in the present study is
method. The synthetic mixture also contains large excess of illustrated in Fig. 7.
Al to simulate the conditions encountered in the samples ob-
tained after irradiating in an accelerator [10]. Recovery of
Conclusions
It can be summarised from the above studies that though
> 90% extraction of Pu can be achieved from 1 : 1 HCl
Irradiated target containing
medium employing 0.05 M PBI and 0.005 M ammonium
the mixture of Pu and Np metavanadate as the holding oxidant, only ∼ 9% Np is ex-
tracted under the same condition. Similarly, though > 99%
Dissolve with Pu stripping is possible employing 0.1 M hydroquinone in
6 M HCl, only < 1% Np stripping is achieved under iden-
1:1 HCl
tical conditions. A simple method for the separation of Np
Solution of Pu + Np from Pu in 1 : 1 HCl is suggested with D.F. > 104 and
recovery ∼ 60%.
1:1 in HCl ; 5x10-5 M AMV
Acknowledgment. The authors are grateful to Dr. S. B. Manohar, Head,
added to it Radiochemistry Division for his keen interest in this work. They also
thank Dr. A. Ramaswamy of Radiochemistry Division for his help dur-
Extraction ing alpha-spectrometric analysis.

with 0.05M
References
PBI in toluene
1. Katz, J. J., Seaborg, G. T., Morss, L. R. (eds.): The Chemistry of
Actinide Elements. Vols. 1 and 2, Second Edition, Chapman and
Hall, New York (1986).
Pu rich organic Np rich aqueous 2. Manchanda, V. K., Mohapatra, P. K.: In: Transuranium Elements:
A Half Century. (Morss, L. R., Fuger, J., eds.) ACS Books, Wash-
phase phase ington DC (1992) Chapt. 33, p. 331.
3. Mohapatra, P. K., Manchanda, V. K.: Radiochim. Acta 61, 69
(1993).
4. Mohapatra, P. K., Manchanda, V. K., Ramaswamy, A.: Nucl. Ra-
Stripping diochem. Symp. Vishakhapattanam, CA-45 (1992).
5. Manchanda, V. K., Mohapatra, P. K.: Sep. Sci. Technol. 29, 1073
with 0.1 M HQ (1994).
6. Korte, F., Storiko, K.: Chem. Ber. 4, 1961 (1956).
7. Mohapatra, P. K.: Ph. D. Thesis. University of Bombay (1993).
in 1:1 HCl
8. Cleveland, J. M.: In: The Chemistry of Plutonium. Gorden and
Breach Science Publishers, New York (1970).
Purified Pu, free from
9. Manchanda, V. K., Mohapatra, P. K.: Results are not published
yet.
Np contamination
10. Ramaswamy, A.: Personal communication.
11. Efurd, D. W., Roensch, F. R., Drake, J., Perrin, R. E.: Radiochim.
Fig. 7. Flow diagram for the suggested separation method. Acta 54, 159 (1991).

Brought to you by | New York University Bobst Library Technical Services

Authenticated
Download Date | 5/28/15 3:22 PM