SOLVENT EXTRACTION AND ION EXCHANGE, 20(2), 227–240 (2002)

EXTRACTION OF ALKALINE EARTHS BY

2,6-DI(5,6-DIPROPYL-1,2,4-TRIAZIN-
3-YL)PYRIDINE

Zdenek Kolarik1,* and Jiřı́ Rais2

1
(Ret.), Fraunhofer-Institut für Chemische Technologie,
76327 Pfinztal, Germany
2
Nuclear Research Institute, 250 68 Řež u Prahy,
Czech Republic

ABSTRACT

The extraction of Ca(II) and, to a lesser extent Sr(II), Ba(II), and

Mg(II) by 2,6-di(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (DPTP)
was studied. The extracted forms were thiocyanates, dicarbolli-
dates, and chlorodicarbollidates. Alcohol modified mixture of
branched alkanes, 1-butanol, and 4-methyl-2-pentanone (MiBK)
were used as diluents. The extractability of the thiocyanates
from < 0.05 M HCl decreases in the element order Ca(II) >
Sr(II)
Mg(II) > Ba(II) and the diluent order MiBK > 1-buta-
nol > modified alkanes > ethyl acetate. Ca(II) thiocyanate is
extracted by DPTP as the complex Ca(SCN)2  3DPTP. The
Ca(II)=Sr(II) separation factor is
270 with the MiBK diluent,

380 with the modified alkane diluent and >500 with the
1-butanol diluent. Ca(II) and Sr(II) chlorodicarbollidates are

*Corresponding author. E-mail: mjl.aquasolv@t-online.de

227

Copyright # 2002 by Marcel Dekker, Inc. www.dekker.com

228 KOLARIK AND RAIS

extracted more effectively than thiocyanates, namely even from

0.5 M solutions of mineral acids. However, the separation effi-
ciency is lower, the Ca(II)=Sr(II) separation factor being 20.
Very efficient is also the extraction of Sr(II) and Ba(II) dicarbol-
lidates in nitrobenzene from 0.1 M NaOH. In this case the
extractability order is Ba(II) > Sr(II) at <0.005 M DPTP and
Sr(II) > Ba(II) at >0.005 M DPTP. The Ba(II)=Sr(II) separation
factor is 9.4 at 0.001 M DPTP, and the Sr(II)=Ba(II) separation
factor is 5.5 at 0.01 M DPTP. Ion-pair formation obviously
proceeds between DPTP and the dicarbollide type extractants.
This makes it in the scope of the work impossible to determine
the composition of the extracted Ca(II)=dicarbollidate=DPTP
species.

INTRODUCTION

2,6-Di(5,6-dialkyl-1,2,4-triazin-3-yl)pyridines,

have been shown to be promising extractants for the separation of Am and Cm

from fission lanthanides (1,2). In this particular case, the extractants exhibit some
considerable advantageous properties. They extract with a good efficiency metal
salts as little lipophilic as nitrates even from acid solutions, exhibiting a high
separation efficiency. For example, with alkyl being propyl, a <0.03 M solution
of the compound in a branched alkane diluent modified with 2-ethyl-1-hexanol
extracts Am(III) nitrate effectively at 1 M HNO3, provided that the total
concentration of nitrate ions is >1 M. It is especially important that the
Am(III)=Eu(III) separation factor is as high as 100–120. It was of interest to
know whether the extractants exhibit unusual extraction efficiency and selectivity
also for pairs or groups of other metals. It also was desirable to know whether the
diluent affects the form of existence of the extractants themselves which, by
the way, appear to exhibit a rather pronounced tendency to self-association (2).
The extraction of alkaline earth metals and Mg(II) by 2,6-di(5,6-dipropyl-1,2,4-
triazin-3-yl)pyridine (DPTP) was studied in this work and the study was
completed by measuring spectra of the extractant.
EXTRACTION OF ALKALINE EARTHS 229

EXPERIMENTAL

Chemicals and Apparatus

Chlorodicarbollide H[(C2B9H8Cl3)2Co] was supplied by Katchem Ltd.,

Czech Republic. Its molecular weight (703) was determined by titration in
ethanol with aqueous 0.1 M NaOH using bromothymol blue as an indicator.
DPTP was synthesized and checked for purity as described in (1,2) in Research
Center Karlsruhe, Institute of Nuclear Waste Management, utilizing the reaction
of 2,6-pyridinedicarboxamidrazone with 4,5-octanedione (3) as the principal
synthesis step. TPH (tetrapropylhydrogène) is a French commercial diluent,
consisting of highly branched alkanes with 1,1,2,2,3,3,4,4-octamethylbutyl as
the essential component. Other chemicals, all of them commercially available
and most of them reagent grade, were used as received. Visible and uv spectra
were recorded on a computer operated spectrometer (Perkin-Elmer Lambda
Series), using glass and quartz cuvettes, respectively. The gamma radioactivity
of 85Sr and 133Ba was measured in discrete energy ranges, using a NaI(Tl)
detector.

Procedure

A fresh DPTP solution and an aqueous phase were equilibrated as

described in (4), using in some cases a magnetic stirrer instead of a mechanical
shaker. Radiochemical work was not licensed in the institute of the first author
and concentrations of metals in the equilibrium phases were in most
experiments determined by titration with 0.001 M disodium ethylenediamine-
tetraacetate. Samples of the organic phase were homogenized with a double to
triple amount of water by adding acetone. Mg(II), Ca(II), and Sr(II) were titrated
after adding 25% ammonia (
0.3 ml per ml sample), taking Eriochrome T as an
indicator. In some cases the metals were determined by ICP or AAS. The
radioactivity measurement was used for the determination of Sr(II) and Ba(II) in
the institute of the second author.

RESULTS AND DISCUSSION

Behavior of the Extractant

Only a short assessment of the behavior was accomplished, rather than a

detailed study of e.g. molecular complex formation. Measurement of absorption
230 KOLARIK AND RAIS

spectra of DPTP was considered an appropriate tool. Fig. 1 shows that the
spectrum exhibits only one intensive, diluent dependent (lmax ¼ 299 nm in
TPH=1-octanol and 287 nm in 1-butanol) band. The asymmetrical form of the
band implies superposition of two peaks. The left one possibly belongs to a H
bonded DPTP=alcohol complex.
The spectrum changes negligibly after 160 min. This is seemingly in
contradiction to observation made in the work with Am(III) and Eu(III) (5). There
the color of DPTP solutions in TPH=2-ethyl-1-hexanol changed within a few
hours from yellow to orange. This change had indeed no influence on the
extraction of Am(III) and Eu(III). It also occurred in this work, in which
1-octanol was taken as a solvent modifier. It seems to be caused by quite
insignificant changes of the spectrum, e.g. by a small increase of the absorbancy
in the region between 320 and 350 nm.
Equilibration of 5.686105 M DPTP in 1-butanol with 0.2 M NH4SCN
has a very small effect on the absorption spectrum of DPTP, slightly enhancing
the absorbancy on the right side of the main peak.
The spectrum of DPTP in TPH=1-octanol (4=1) has the equilibrium form
shown in Fig. 1 only if DPTP is dissolved in a ready mixture of both diluents. If
DPTP is dissolved in 1-octanol and TPH is subsequently added, a transitory
spectrum similar to that in 1-butanol is obtained (see Fig. 2 and compare it with
Fig. 1). Expected conversion of the transitory spectrum to the equilibrium one
proceeds extremely slowly (see Fig. 2), having progressed little even after 8 d. It is
important that the extraction of metal salts was independent of the mode of
dissolution of DPTP.

Figure 1. Influence of the diluent and the solution aging on the absorption spectrum of
5.926105 M DPTP at room temperature.
EXTRACTION OF ALKALINE EARTHS 231

Figure 2. Influence of the mode of dissolving on the absorption spectrum of

5.926105 M DPTP in TPH=1-octanol (4=1) at room temperature.

Extraction of Ca(II), Sr(II), and Mg(II) Thiocyanates

Compared to other metals, alkaline earth elements and Mg(II) are generally
weakly extractable. To investigate their extractability by DPTP, it was desirable to
take the elements in the form of relatively well extractable salts. Data in (6) imply
that thiocyanates should be a suitable form, because in the distribution of Am(III)
and Eu(III) they are more extractable than e.g. nitrates. Also necessary was the
choice of a suitable diluent which had to dissolve effectively DPTP alone as well
as the extracted complexes. THP=1-octanol was used in the first experiments
because it had proved effective in the Am=Eu separation in nitrate systems (1,2).
However, minute amounts of solids formed in the extraction of alkaline earth
thiocyanates. They did not disturb the establishing of the distribution equilibrium
but retarded the phase disengagement. Good dissolving properties were exhibited
by oxygen containing diluents of common classes, and we used them in further
experiments.
Data in Fig. 3 and Fig. 4 corroborate the good extractability of alkaline
earth thiocyanates. Practicable distribution ratios of Ca(II), Sr(II), and Mg(II)
(DCa, DSr, and DMg, respectively) were found even at a pH value as low as pH 1.7.
The extractability of Ba(II) was studied only with the TPH=1-octanol diluent. The
distribution ratio of Ba(II) was <0.12 at 0.2–1.0 M NH4SCN.
The log DM vs. log [SCN] dependencies shown in Fig. 3 are linear, but
their slopes differ from element to element and are <2. As for possible
explanations, different variation of activity coefficients with the thiocyanate
concentration or different thiocyanate complexing of the M2þ ions in the aqueous
232 KOLARIK AND RAIS

Figure 3. Distribution ratios of alkaline earth thiocyanates as functions of the

thiocyanate concentration in the aqueous phase. Initial aqueous phase: 9.36104 M
MgCl2 and CaCl2, 5.36105 M Sr(NO3)2 and BaCl2, and 0.02 M HCl. Initial organic
phase: 0.0234 M DPTP in TPH=1-Octanol (4=1). Room temperature.

Figure 4. Influence of the DPTP concentration on the extraction of Mg(II), Ca(II), and
Sr(II) thiocyanates. Initial aqueous phase: 0.2 M NH4SCN, 0.002 M CaCl2 or 0.02 M
Sr(NO3)2 and 0.02 M HCl. Diluent: TPH=1-Octanol (4=1, full points), MiBK (stars), or
1-butanol (open points). Room temperature.
EXTRACTION OF ALKALINE EARTHS 233

phase is more plausible than the participation of different numbers of thiocyanate

ions in the formation of the extracted complexes.
Dependencies of the distribution ratios on the DPTP concentration are
shown in Fig. 4. With log DM values plotted vs. the logarithm of the initial DPTP
concentration they implied cubic dependencies for Ca(II) and Sr(II). Thus, the
equilibrium concentration of DPTP was calculated from the initial DPTP
concentration by subtracting the threefold organic metal concentration. Within the
limits of the scattering, experimental points for Ca(II) and Sr(II) are then
compatible with straight lines having a slope of 3.0. Extraction of trisolvates of
Ca(II) and Sr(II) thiocyanates is thus plausibly indicated. The distribution ratios
of Mg(II) are low and were measured in a narrow range of the DPTP
concentration, but they apparently are compatible with a straight line with a slope
of 1.
Fig. 4 also gives some information about the effect of the diluent. The
efficiency of the extraction of Ca(II) decreases in the diluent order MiBK > 1-
butanol > TPH=1-octanol > ethyl acetate (not shown in Fig. 4). In the extraction
of Sr(II) the order is MiBK > 1-butanol  TPH=1-octanol.
The extractability decreases in the common order Ca(II) > Sr(II) > Ba(II).
The Ca(II)=Sr(II) separation factor is rather high, being aCa=Sr ¼ DCa=DSr
380
with the TPH=1-octanol diluent. It can be estimated as aCa=Sr
270 with the
MiBK diluent and roughly estimated as aCa=Sr
1000 with the 1-butanol diluent.
Such separation factors are noticeably higher than those attained e.g. with
acidic organophosphates, which belong to the few compounds effectively
extracting alkaline earth elements. For example, octyl chloromethylphosphonate
yields aCa=Sr ¼ 51, di[p-(1,1,3,3-tetramethylbutyl)phenyl]phosphoric acid yields
aCa=Sr ¼ 56, and octyl phenylphosphonate yields aCa=Sr ¼ 220 (all in xylene
diluent and with 1 M (H,Na)Cl as the aqueous phase) (7).
The log DCa vs. log [Hþ ] dependency is shown in Fig. 5 to be a curve
approaching a slope of 2 at low DCa(II) values. However, the dependency was in
fact not measured at a constant concentration of free DPTP, because the fraction
of DPTP bound in the extracted complex was not negligible. Knowing that a
trisolvate was the extracted Ca(II) species, it was possible to recalculate the DCa(II)
values for the initial DPTP concentration. It is shown in Fig. 5 that after this
correction the experimental points are well compatible with a straight line having
the expected slope 2. Thus, the extracted complex can be written as
Ca(SCN)2  3DPTP.
It should be pointed out that DPTP extracts Ca(II) as thiocyanate with an
unusually high effectiveness. Comparison of data from Fig. 5 with those from (7)
shows that di[p-(1,1,3,3-tetramethylbutyl)phenyl]phosphoric acid, which belongs
to the most effective extractants for Ca(II) known up to date, would at the same
concentration give distribution ratios lower by a factor of more than 100. Ca
indeed is not a metal of value and no demand can be expected to recover it by
234 KOLARIK AND RAIS

Figure 5. Influence of the hydrogen ion concentration on the extraction of Ca(II)

thiocyanate. Initial aqueous phase: 0.002 M CaCl2, 0.2 M NH4SCN, and variable HCl.
Initial organic phase: 0.00515 M DPTP in 1-butanol. Room temperature.

solvent extraction. However, it might be of interest to separate Ca(II) impurities

from value elements.

Extraction of Ca(II) and Sr(II) Chlorodicarbollidates

from Acid Solutions

Alkaline earth dicarbollidates can be expected to be still more extractable

than thiocyanates. The polyhedral Co(III)-dicarbolide anion, [p-(3)-1,2-
B9C2H11]2Co (8), and still better its chloro derivative (9) extract Sr(II) in the
presence of a commercially available polyethylene glycol as a synergist. Sr(II) is
extracted from acid solutions, but only using a nitro compound (most frequently
nitrobenzene or nitromethane) as a diluent. It is shown below that with DTPT as a
synergist the alkaline earth elements can be extracted using common diluents
other than nitro compounds. It also is shown that the effectiveness of the Ca(II)
chlorodicarbollidate extraction is unusually high even at rather high acid
concentrations and low DPTP concentrations.
It is seen in Fig. 6 that the distribution ratios of Ca(II) and Sr(II) are
irregular functions of the concentration of chlorodicarbollide in the acid form
(HClDC). The maximum DM values are reached at initial [HClDC]=[DPTP]
concentration ratios of 1.1 for Ca(II) and 0.7 for Sr(II).
The variable dependency can most plausibly be explained by ion-pair
formation between DTPT and HClDC. This of course makes simple calculations
EXTRACTION OF ALKALINE EARTHS 235

Figure 6. Influence of the chlorodicarbollide concentration on the extraction of Ca(II)

and Sr(II) chlorodicarbollidates. Initial aqueous phase: 0.002 M CaCl2 or 0.0022 M SrCl2,
and 0.15 M HCl. Initial organic phase: 0.00884 M DPTP and variable HClDC in butyl
acetate. Room temperature.

of the concentrations of really free HClDC and DPTP impossible, and it impedes
the slope analysis. It is insufficient to consider for the slope analysis solely the
fraction of HClDC bound to Ca(II) and Sr(II) and to calculate formally ‘‘free’’
concentrations of HClDC. To demonstrate, we calculated the ‘‘free’’ concentra-
tion of HClDC, plausibly assuming that two anions of HClDC are needed to
neutralize the charge of the Ca2þ and Sr2þ ions, and used this value as the
independent variable in Fig. 6. It is not surprising that the steepness of the
ascending part of the dependencies does not correspond to the expected slope 2.
Instead, the slopes 0.5 and 1 are approached at low ‘‘free’’ HClDC concentrations
with Ca(II) and Sr(II), respectively.
The log DCa vs. log [Hþ ] dependency shown in Fig. 7 is steeper as
expected. The upper curve has a slope of 3.15, and the middle curve can be
described as tending to a slope of 3 rather than 2. Again it has to be referred to the
credible ion-pair formation between HClDC and DPTP, which most probably is
responsible for it.
Figure 7 also illustrates the diluent effect, showing that the extraction of
Ca(II) is much less effective with the extractants dissolved in MiBK than in ethyl
acetate. For this reason ethyl acetate, or its less aqueous soluble analogue butyl
acetate, was used in further work. Such diluents as 2-ethyl-1-hexanol, 1-butanol
and TPH=2-ethyl-1-hexanol (4=1) are inapplicable due to solubility problems. An
attempt to dissolve both HClDC and DPTP in them results in the formation of a
yellow precipitate, which most probably is a DPTP salt of HClDC.
236 KOLARIK AND RAIS

Figure 7. Influence of the hydrogen ion concentration on the extraction of Ca(II)

chlorodicarbollidates. Initial aqueous phase: 0.002 M CaCl2 and variable HCl. Initial
organic phase: 0.0122 M HClDC þ 0.0116 M DPTP (1), 0.0119 M HClDC þ 0.0086 M
DPTP (2), and 0.0116 M HClDC þ 0.099 M DPTP (3). Room temperature.

The distribution ratios of both Ca(II) and Sr(II) increase rather steeply with
the DPTP concentration in ethyl acetate, approaching slopes of 5 and 4,
respectively (see Fig. 8). Again due to the impossibility of calculating simply the
concentration of really free DPTP, the steepness of the curves gives no direct
information about the solvation numbers of the extracted complexes.
It was of interest to check the behavior of DPTP in one of the nitro diluents,
which have almost exclusively been used in the work on dicarbollides. Fig. 8
shows the extraction of Sr(II) chlorodicarbollide by DPTP in o-nitrophenyl octyl
ether, and compares it with that by DPTP in butyl acetate. With the nitro diluent,
even HClDC alone gives for Sr(II) a measurable distribution coefficient, while a
very low value is to be expected with the butyl acetate diluent. On the other side,
synergistic increase of the Sr(II) extraction by DPTP in the nitro diluent is
minimal. There is even a suppression of the Sr(II) extraction at high DPTP
concentrations, ascribable to binding of HClDC and DTPT in molecular
complexes.
It is to be noticed in Fig. 6 to Fig. 8 that the synergistic combination
HClDC=DPTP extracts Ca(II) and Sr(II) with an unusually high efficiency. So a
distribution ratio of 1 is attained with
0.01 M HClDC þ
0.01 M DTPT in an
alkyl acetate diluent at a HCl concentration as high as
0.5 M. Figure 6 and Fig.
8 show that the Ca(II)=Sr(II) separation efficiency is indeed lower than in the
extraction of thiocyanates. A separation factor of aCa=Sr
20 can be attained at a
suitable concentration ratio of the extractants, e.g., as indicated in Fig. 6, at
0.009 M DPTP and 0.016–0.020 M HClDC.
EXTRACTION OF ALKALINE EARTHS 237

Figure 8. Influence of the DPTP concentration on the extraction of Ca(II) and Sr(II)
chlorodicarbollidates. Initial aqueous phase: 0.002 M CaCl2 or 0.0022 M SrCl2 and 0.15 M
HCl (solid points), and trace Sr(II) þ 0.2 M HNO3 (open points). Butyl acetate (AcOBu) or
o-nitrophenyl octyl ether (NPOE) diluents. Room temperature.

Extraction of Sr(II) and Ba(II) Dicarbollidates from an

Alkaline Solution

Some attention was paid to the extractability of alkaline earths from an

NaOH solution. Due to some omission in coordination of the experimental work,
sodium dicarbollidate and the dicarbollide ‘‘correlative’’ diluent nitrobenzene were
used. Clearly, this makes the results less comparable with those described above.
We also are aware of the limited acceptability of the nitrobenzene diluent in solvent
extraction. However, the results represent a completion of the data on the extraction
from acid solutions and so we choose to include these results in this paper.
First, at high pH values the dicarbollide extractants are converted to Na
salts in the organic phase. This makes formation of hydrogen bonded molecular
complexes or ion-pairs between DPTP and a dicarbollide highly improbable. We
took such specific interactions as an explanation for the irregular form of the log
DCa or log DSr vs. log [HClDC] dependencies shown in the extraction from acid
solutions (see Fig. 6).
Fig. 9 shows that the dependency of the distribution ratio of Sr(II) on the
sodium dicarbollidate (NaDC) concentration exhibits a maximum, i.e. it is similar
to the dependencies shown in Fig. 6. This implies possible ion-pair formation
even between NaDC, or its anion, and DPTP. As to the nature of the ion-
pairs, potential existence of an Naþ bridge between the anion of NaDC and a
nitrogen atom of DPTP can be mentioned but it is pure speculation. The
238 KOLARIK AND RAIS

Figure 9. Influence of the Na dicarbollidate concentration on the extraction of trace

Sr(II) as dicarbollidate from 0.1 M NaOH. Equilibrium organic phase: 0.01 M
DPTP þ variable NaDC in nitrobenzene. Room temperature.

Figure 10. Influence of the DPTP concentration on the extraction of trace Sr(II) or
Ba(II) as dicarbollidates from 0.1 M NaOH. Equilibrium organic phase: 0.01 M
NaDC þ variable DPTP in nitrobenzene. Room temperature.

bad reproducibility of the data in Fig. 9 can be ascribed to the very steep character
of the log DSr vs. log [DPTP] dependency at >0.003 M DPTP (see Fig. 10).
The DSr values may thus be so sensitive to small changes of the DPTP
concentrations that even common inaccuracies in pipetting deteriorate the
reproducibility of them.
EXTRACTION OF ALKALINE EARTHS 239

Second, log DSr or log DBa vs. log [DPTP] dependencies shown in Fig. 10
clearly demonstrate that DPTP can cause a very strong synergistic effect in the
extraction by NaDC from 0.1 M NaOH. In contrast, there is practically no
synergistic effect in the extraction by HClDC in a nitro diluent from 0.2 M HNO3
(see the lower curve in Fig. 8).
The extremely steep part of the log DSr vs. log [DPTP] dependency is in
Fig. 10 interpreted by a full line as approaching a slope of 5, but approach to a
slope of 6 would be a plausible interpretation as well. The log DBa vs. log [DPTP]
dependency is in Fig. 10 interpreted to approach a slope of 4. The Sr(II)=Ba(II)
separation factor is moderate, namely 5.5 at 0.01 M DTPT. The less common
reverse extractability order, Ba(II) > Sr(II), is found only at low DPTP concen-
trations, i.e. in the region of low DSr and DBa values. The Ba(II)=Sr(II) separation
factor is 9.4 at 0.001 M DPTP.

CONCLUSIONS

0.005–0.02 M DPTP extracts Ca(II) thiocyanate from moderately acid

solutions (0.05 M HCl), yielding a noticeable selectivity over Sr(II)
(aCa=Sr ¼
270 to
1000). The efficiency of the extraction decreases in the
diluent order MiBK > 1-butanol > TPH=1-octanol (4=1) > ethyl acetate. The
extraction of Ca(II) chlorodicarbollidate by 0.004–0.02 M DPTP at 0.003–
0.04 M HClDC is effective at still higher acid concentrations (0.5 M HCl), but it
is less selective with regard to Sr(II) (aCa=Sr ¼
20). In this case the extraction
efficiency decreases in the diluent order ethyl or butyl acetate > MiBK. Sr(II)
dicarbollidate is extractable from 0.15–0.2 M Hþ by 0.01 M DPTP in butyl
acetate but not in o-nitrophenyl octyl ether. A very high extraction effectiveness is
achieved with a similar diluent, namely nitrobenzene, in the extraction of Sr(II) and
Ba(II) dicarbollidates by 0.003–0.01 M DPTP at 0.01 M NaDC from 0.1 M NaOH.

ACKNOWLEDGMENT

The work of one of us (J. R.) was supported by the Czech grant
104=01=0142 of Czech Grant Agency.

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240 KOLARIK AND RAIS

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Received June 23, 2001