SHORT COMMUNICATION

Journal of Radioanalytical and Nuclear Chemistry, Vol. 267, No.1 (2006) 233–235

Solvent extraction of lead using a nitrobenzene solution of strontium

dicarbollylcobaltate in the presence of polyethylene glycol PEG 400
E. Makrlík,1 P. Va.ura2
1 Faculty of Applied Sciences, University of West Bohemia, Husova 11, 306 14 Pilsen, Czech Republic
2 Prague Institute of Chemical Technology, Technická 5, 166 28 Prague 6, Czech Republic

(Received January 7, 2005)

From extraction experiments and -activity measurements, the extraction constant corresponding to the equilibrium
Pb2+ (aq)+SrL2+ (nb) PbL2+ (nb)+Sr2+ (aq) taking place in the two-phase water–nitrobenzene system (L = PEG 400; aq = aqueous phase, nb =
nitrobenzene phase) was evaluated as logKex(Pb2+, SrL2+) = 2.0±0.1. Further, the stability constant of the PEG 400 – lead complex in nitrobenzene
saturated with water was calculated for a temperature of 25 °C: log nb(PbL2+) = 12.9±0.1.

Introduction water (about 1 mol/l) of an equal volume, followed by

Dicarbollylcobaltate anion and some of its halogen
derivatives are very useful reagents for the extraction of
alkali metal cations (especially Cs+), and also, in the
presence of polyoxyethylene compounds, for the
extraction of Sr2+ and Ba2+ from aqueous solutions into
an organic high-polar phase, both under latoratory
conditons for purely theoretical or analytical purposes,1
and on the technological scale for the separation of some
high-activity isotopes in the reprocessing of irradiated
nuclear fuel.2–4
The aim of the present work was to determine the
stability constant of the PbL2+ complex species, where L
is PEG 400, in water saturated nitrobenzene.
Experimental
Polyethylene glycol with the mean relative molecular
weight 400 (abbrev. PEG 400) was supplied by Koch-
Light. Cesium dicarbollylcobaltate, Cs DCC, was
synthesized in the Institute of Inorganic Chemistry, ;ež,
Czech Republic, using the method published by
HAWTHORNE et al.5 The radionuclide 85Sr (DuPont,
Belgium) was of standard radiochemical purity.
Nitrobenzene and all other chemicals (analytical grade,
Lachema, Brno, Czech Republic) were used without
further purification.
In order to obtain the solution of HDCC in
nitrobenzene, the solution of CsDCC in this medium
(0.2 mol/l) was twice equilibrated with equal volumes of
15% (v/v) n-propanol in diluted H2SO4 of the
concentration of about 1 mol/l. H2SO4 and n-propanol
were removed from the organic phase by a ten-fold
equilibration with the solution of H2SO4 in distilled
two equilibrations with distilled water. The
concentration of HDCC in the nitrobenzene solution was
determined by neutralization titration (NaOH,
bromocresol green) after a ten-fold dilution with ethanol
or acetone. The equilibration of the nitrobenzene
solution of HDCC with stoichiometric Sr(OH)2, which
was dissolved in the aqueous solution of Sr(NO3)2
(0.2 mol/l), yields the corresponding Sr(DCC)2 solution
in nitrobenzene.
The extraction experiments were carried out in 10 ml
glass test tubes fitted with polyethylene stoppers: 2 ml of
the aqueous solution of Pb(NO3)2 of the concentration in
the range from 1.10–4 to 1.10–3 mol/l and microamounts
of 85Sr were added to 2 ml of the nitrobenzene solution
of PEG 400 and Sr(DCC)2, whose initial concentrations
varied also from 1.10–4 to 1.10–3 mol/l (in all
experiments, the initial concentration of PEG 400 in
nitrobenzene, C in,nb
L , was always equal to the initial
concentration of Sr(DCC)2 in this medium, C in,nbSr(DCC)2).
The test tubes filled with the solutions were shaken for
two hours at a temperature of 25±1 °C using a
laboratory shaker. Under these conditions the
equilibrium in the system under study has been
established already after approximately 15-minute
shaking. Then the phases were separated by
centrifugation (2 minutes, 2,500 rpm). Afterwards, 1 ml
samples were taken from each phase and their
-activities were measured using a well-type NaI(TI)
scintillation detector connected to a single-channel
-analyzer, RFT Strahlungsmessgerät 20 026 (RFT,
Dresden, Germany).
The equilibrium distribution ratio of strontium, DSr,
was determined as a ratio of the measured radioactivities
of the nitrobenzene and aqueous samples.

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 E. MAKRLÍK, P. VALURA: SOLVENT EXTRACTION OF LEAD USING A NITROBENZENE SOLUTION

in,aq
[Pb2+]aq + [PbL2+]nb = CPb(NO (8)
Results and discussion 3 )2
in,nb
[Sr2+]aq + [SrL2+]nb = CSr(DCC) (9)
With regard to the results of previous thepapers,6–8 2

two phase water–Pb(NO3)2–nitrobenzene–Sr(DCC)2 and the measured equilibrium distribution ratio of

extraction system can be described by the following strontium is:
equation:
[SrL2 + ]nb
Pb2+ (aq)+Sr2+ (nb) Pb2+ (nb) + Sr2+ (aq) DSr = (10)
Kex (Pb ,Sr2+)
2+ (1) [Sr 2 + ]aq

with the corresponding exchange extraction constants The combination of previous (5)–(10) relationships
Kex (Pb2+,Sr2+); “aq” and “nb” denote the presence of gives the final expression for the Kex (Pb2+,SrL2+)
the species in the aqueous and nitrobenzene phases, extraction constant:
respectively. For the Kex (Pb2+,Sr2+) constant it can be Kex (Pb2+,SrL2+)=
written as:6
in,nb
1 CSr(DCC)
log Kex (Pb2+,Sr2+) = log K iPb2+–log K iSr2+ (2) = 2
(11)
DSr (1 + DSr )C in,aq in, nb
CSr(DCC)
Pb(NO )
where K iPb2+ and K iSr2+ are the individual extraction 3 2 2

constants for Pb2+ and Sr2+, respectively, in the water- In this study, from the extraction experiments and -
nitrobenzene system.6 Knowing log K iPb2+ = –10.67 and activity measurements (see the Experimental section)
log K iSr2+ = –10.7, inferred from previous results,6,8 the using Relation (11), the following value of the
Kex (Pb2+,Sr2+) extraction constant was simply log Kex (Pb2+,SrL2+) constant was evaluated:
calculated from Eq. (2) as:
log Kex (Pb2+,SrL2+) = 2.0±0.1 (12)
log Kex (Pb2+,Sr2+) = 0.1 (3)
Futhermore, with respect to previous results,10 for
In terms of the previous results,1,9
the two-phase the Kex (Pb2+,Sr2+) and Kex (Pb2+,SrL2+) extraction
water–Pb(NO3)2–nitrobenzene-L (L=PEG 400)– constants defined above, and for the stability constants
Sr(DCC)2 extraction system (see the Experimental of the PbL2+ and SrL2+ complexes in nitrobenzene
section), chosen for the determination of the stability of saturated with water, denoted by nb(PbL2+) and
the PbL2+ complex in water saturated nitrobenzene, can 2+
nb(SrL ), respectively, one gets:
be characterized by the main chemical equation:
log nb(PbL2+) = log nb(SrL2+)+
Pb2+ (aq)+SrL2+ (nb) PbL2+ (nb) + Sr2+ (aq)
+logKex(Pb2+,SrL2+)–logKex(Pb2+,Sr2+) (13)
Kex (Pb2+,SrL2+) (4)
Using the logKex(Pb2+,Sr2+) and logKex(Pb2+,SrL2+)
to which the equilibrium extraction constant is: constants given above, the value log nb(SrL2+) = 11.0
[PbL2 + ]nb [Sr 2 + ]aq (L=PEG 400)9 and applying Eq. (13), we gain the
Kex (Pb2+,SrL2+) = (5) stability constant of the lead – PEG 400 complex in
[Pb 2 + ]aq [SrL2 + ]nb water saturated nitrobenzene at 25 °C:

where “aq” and “nb” refer to the aqueous and log nb(PbL2+) = 12.9±0.1 (14)
nitrobenzene phases, respectively. It is necessary to
In conclusion, it should be noted that the stability
emphasize that the PEG 400 ligand forms, with Pb2+ and
constant of the BaL2+ complex (L=PEG 400) in
Sr2+, the very stable PbL2+ and SrL2+ complexes in the
nitrobenzene saturated with water evaluated in the
nitrobenzene phase.9
water–HClO4–Ba2+ (microamounts)–PEG 400–nitro-
Following the conditions of electroneutrality in the
benzene–HDCC system is log nb(BaL2+) = 12.8.9 It
organic and aqueous phases:
means that the stability constants of the PbL2+ and
in,nb
[PbL2+]nb + [SrL2+]nb = CSr(DCC) (6) BaL2+ complexes in the mentioned medium are
2
comparable.
in,aq
[Pb2+]aq + [Sr2+]aq = C Pb(NO ) (7)
3 2

the mass balances of lead and strontium at equal

volumes of the nitrobenzene and aqueous phases are:

234
 E. MAKRLÍK, P. VALURA: SOLVENT EXTRACTION OF LEAD USING A NITROBENZENE SOLUTION

* 4. J. D. LAW, R. S. HERBST, T. A. TODD, V. N. ROMANOVSKIY,

The present work has been supported by the Czech Ministry of
Education, Youth and Sports, Project No. MSM 4977751303 and
Project No. MSM 6046137307.
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