Accepted Manuscript

N,N-diethyl-N,N-
diphenyl-1,10-phenanthroline-2,9-dicarboxamide as an
extraordinarily effective extraction agent for trivalent europium
and americium

Emanuel Makrlk, Petr Vaura, Pavel Seluck, Vasily Babain,

Mikhail Alyapyshev, Dmitriy Dar'in

PII: S0167-7322(16)33732-1
DOI: doi: 10.1016/j.molliq.2017.04.032
Reference: MOLLIQ 7185
To appear in: Journal of Molecular Liquids
Received date: 22 November 2016
Revised date: 6 April 2017
Accepted date: 11 April 2017

Please cite this article as: Emanuel Makrlk, Petr Vaura, Pavel Seluck, Vasily Babain,
Mikhail Alyapyshev, Dmitriy Dar'in , N,N-diethyl-N,N-
diphenyl-1,10-phenanthroline-2,9-dicarboxamide as an extraordinarily effective
extraction agent for trivalent europium and americium. The address for the corresponding
author was captured as affiliation for all authors. Please check if appropriate.
Molliq(2017), doi: 10.1016/j.molliq.2017.04.032

This is a PDF file of an unedited manuscript that has been accepted for publication. As
a service to our customers we are providing this early version of the manuscript. The
manuscript will undergo copyediting, typesetting, and review of the resulting proof before
it is published in its final form. Please note that during the production process errors may
be discovered which could affect the content, and all legal disclaimers that apply to the
journal pertain.
 ACCEPTED MANUSCRIPT

Short Communication

N,N-Diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-
dicarboxamide as an extraordinarily effective extraction agent
for trivalent europium and americium
Emanuel Makrlk a*, Petr Vaura b, Pavel Seluck c, Vasily Babain d,e,
Mikhail Alyapyshev e,f, Dmitriy Dar'in g

PT
a
Faculty of Environmental Sciences, Czech University of Life Sciences, Prague,
Czech Republic
b
Department of Analytical Chemistry, University of Chemistry and Technology, Prague,

RI
Czech Republic
c
Nuclear Research Institute, e, Czech Republic

SC
d
ThreeArc Mining Ltd., Moscow, Russia
e
ITMO University, St. Petersburg, Russia
f
Polymetal International, St. Petersburg, Russia
NU
g
Institute of Chemistry, St. Petersburg State University, St. Petersburg, Russia

________________________________________________________________________________________________________________
MA

ABSTRACT
___________________________________________________________________________

Solvent extraction of microamounts of Eu3+ and Am3+ from water into nitrobenzene by means
of a mixture of hydrogen dicarbollylcobaltate (H+B-) and N,N-diethyl-N,N-diphenyl-1,10-
D

phenanthroline-2,9-dicarboxamide (L) was studied. The equilibrium data were explained

E

assuming that the species HL+, H 2 L2 , HL2 , ML32 , and ML33 (M3+ = Eu3+, Am3+; L = N,N-
PT

diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide) are extracted into the organic

phase. Extraction and stability constants of the cationic complex species in nitrobenzene
saturated with water were determined and discussed. From the experimental results it is
evident that this very efficient N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-
CE

dicarboxamide receptor for the Eu3+ and Am3+ cations could be considered as a potential
extraction agent for nuclear waste treatment.
___________________________________________________________________________
AC

Keywords:
Solvent extraction
Europium and americium
N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide
Extraction and stability constants
Waternitrobenzene system

______________________________
*
Corresponding author.
E-mail address: makrlik@centrum.cz (E. Makrlk).
 ACCEPTED MANUSCRIPT

1. Introduction
Dicarboxylic acid diamides are a subject of active research as potential extractants of
actinides (in particular of minor actinides) from radioactive wastes. Important information
concerning substituted malonic diamides has been reported [1,2]. Lately, interest has shifted
to the properties of tetraalkyl-diglycolamides [3-6], with emphasis on tetraoctyl-
diglycolamide (TODGA), suggested as an extractant of Pu(IV), Np(IV), Am(III), and Cm(III)
in solutions with hydrocarbon diluents [3-5]. The ability of TODGA to extract many other

PT
metals has been discussed [6,7] and the very high extractive capacity of this agent was shown
to allow its application as a solid extractant [8]. Complexation of trivalent lanthanides and

RI
actinides with several novel diglycolamide-functionalized calixarenes has been studied
recently [9-11]. Besides, some of these functionalized calixarenes have been applied for the

SC
isolation of carrier-free 90Y from 90Sr [12].
The dicarbollylcobaltate anion [13] and some of its halogen derivatives have been
NU
employed often for the solvent extraction of various metal cations (e. g., Cs+, Sr2+, Ba2+, Eu3+,
and Am3+) from aqueous solutions into a polar organic phase, both under laboratory
MA

conditions for theoretical or analytical purposes [14-18], and on the technological scale for the
separation of some high-activity isotopes in the reprocessing of spent nuclear fuel and acidic
radioactive waste [19,20]. Furthermore, a process involving chlorinated cobalt dicarbollide,
D

polyethylene glycol, and diphenyl-N,N-dibutylcarbamoylmethyl phosphine oxide, also called

E

UNEX, has been suggested for the simultaneous recovery of cesium, strontium, lanthanides,
PT

and actinides from highly acidic media into phenyltrifluoromethyl sulfone (abbrev. FS-13)
[19,20]. It is necessary to emphasize that the FS-13 diluent was developed for the UNEX
CE

process as an alternative organic diluent to the highly polar nitrobenzene. Finally, FS-13 has
the advantage of low viscosity and good solubility of metal solvates as well as the UNEX
extractants [20]. However, in Russia, nitrobenzene derivatives (e.g., 3-nitro--
AC

trifluorotoluene, also denoted by F-3) have been successfully utilized as diluents for cobalt
dicarbollide processes [19].
Recently, diamides of 1,10-phenanthroline-2,9-dicarboxylic acid have been proposed as
selective extractants for trivalent americium and curium. The mixture of N,N,NN-tetraoctyl-
1,10-phenanthroline-2,9-dicarboxamide and Br-cosan effectively extracts americium with a
separation factor (SFAm/Eu) over 40 [21]. High SFAm/Eu values (up to 51) have been also
demonstrated for metal extraction by 1,10-phenanthroline-2,9-dicarboxamides from
perchloric media [22].

2
 ACCEPTED MANUSCRIPT

In the present work, the solvent extraction of microamounts of trivalent europium and
americium into nitrobenzene by using hydrogen dicarbollylcobaltate (H+B-) [13] and N,N-
diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide (abbrev. L; see Fig. 1) was
investigated. In this context we must add that the solvent extraction of these trivalent cations
into nitrobenzene by means of the mentioned electroneutral N,N-diethyl-N,N-diphenyl-1,10-
phenanthroline-2,9-dicarboxamide ligand (L) only is nearly negligible; therefore, the mixture
of H+B- and L was employed. Moreover, we intended to find the composition of the species in
the organic phase of the waternitrobenzene extraction system and to determine the

PT
corresponding equilibrium constants.

RI
2. Experimental section

SC
2.1. Chemicals
N,N-Diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide (abbrev. L; see
NU
Fig. 1) was supplied by St. Petersburg State University, Russia, and it was employed as
received. Cesium dicarbollylcobaltate, Cs+B-, was synthesized by the method published by
MA

Hawthorne et al. [23]. Other chemicals used (Lachema, Brno, Czech Republic) were of
reagent grade purity. A nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B-) [13]
was prepared from Cs+B- by the procedure described elsewhere [24]. The carrier-free
D

radionuclides 152,154Eu3+ and 241Am3+ were obtained from Polatom, Poland; their radionuclidic
E

purities were 99.9%.

PT

2.2. Extraction
The extraction experiments in the twophase systems waterHNO3152,154Eu3+ (ca. 20 kBq)
CE

nitrobenzene L (N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide)
H+B- and waterHNO3241Am3+ (ca. 20 kBq) nitrobenzene L (N,N-diethyl-N,N-
AC

diphenyl-1,10-phenanthroline-2,9-dicarboxamide) H+B- were performed in 10 mL

polypropylene test-tubes with polypropylene stoppers, using 2 mL of each phase. The test-
tubes filled with the solutions were shaken for 2 h at 25 1 oC, using a laboratory shaker.
However, under these conditions, the equilibria in the systems under study were established
after approximately 1 h of shaking. Then the phases were separated by centrifugation. Finally,
1 mL samples were taken from each phase and their -activities were measured by means of a
well-type NaI(Tl) scintillation detector (its efficiency is about 50%) connected to a -analyzer
Triathler (Hidex, Turku, Finland).

3
 ACCEPTED MANUSCRIPT

The equilibrium distribution ratios of europium and americium, D, were determined as the
152,154
ratios of the corresponding measured radioactivities of Eu3+ and 241
Am3+ in the
nitrobenzene and aqueous samples.

3. Results and discussion

The dependences of the logarithm of the europium and americium distribution ratios
(log D) on the logarithm of the numerical value of the total (analytical) concentration of the

PT
N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide ligand in the initial
nitrobenzene phase, log c(L), are presented in Figs. 2 and 3, as well as in Tables 1 and 2,

RI
respectively. The initial concentrations of hydrogen dicarbollylcobaltate (H+B-) in the organic
phase, cB = 0.0025 and 0.005 mol/L, as well as the initial concentration of HNO3 in the

SC
aqueous phase, c(HNO3) = 0.05 mol/L, are always related to the volume of one phase. The
occurrence of the characteristic maxima on these dependences can be explained qualitatively
NU
in terms of the competition between the charged trivalent complexes ML3n,org (M3+ = Eu3+,

Am3+) and the protonized ligand L (i.e., HL+, H 2 L2 , and HL2 ; in detail, see the text below)
MA

during the balancing of the dicarbollylcobaltate electrostatic charge in the organic phase,
similarly as in our previous work [25].
With regard to the results of our previous papers [13,16-18,26], the considered water
D

HNO3M3+ (microamounts; M3+ = Eu3+, Am3+)nitrobenzene N,N-diethyl-N,N-diphenyl-

E

1,10-phenanthroline-2,9-dicarboxamide (L) H B systems can be described by the set of

PT

reactions:
CE

Laq Lorg (1)

Horg Lorg HLorg (2)
AC

2H org L org H 2 L2org (3)

H org 2L org HL2,org (4)

M 3aq 3H org

M3org
3H aq (5)

M 3aq nLorg 3H org

ML3n,org 3H aq

(6)

to which the following equilibrium constants correspond:

4
 ACCEPTED MANUSCRIPT

[L org ]
KD (7)
[L aq ]

[HLorg ]
(HLorg )
(8)
[H org ][L org ]

[HL22,org ]
(H 2 L )
2
org
(9)
[H org ]2 [L org ]

PT
[HL2,org ]
(HL
2,org )
(10)
[H org ][Lorg ]2

RI
3

[M 3org ][H aq ]
Kex (M 3org ) (11)
[M 3aq ][H org

SC
]3

[ML3n,org ][H aq
3
]
Kex (ML3n,org ) (12)
NU
[M 3aq ][L org ]n [H org

]3
MA

The subscripts aq and org denote the aqueous and organic phases, respectively. At this
point we must add that Eq. (5) characterizes the investigated two-phase systems for [Lorg] 0.
A subroutine UBBE, based on the relations given above, the mass balance of the N,N-
D

diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide (L) ligand and the

E

electroneutrality conditions in both phases of the system under consideration, was

PT

formulated [27,28] and introduced into a more general least-squares minimizing program
LETAGROP [29] used for determination of the best values of the extraction constants
CE

Kex (ML3n,org ) (M3+ = Eu3+, Am3+; L = N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-

dicarboxamide). The minimum of the sum of errors in log D, i.e., the minimum of the
AC

expression

U = (log Dcalc log Dexp)2 (13)

was sought.
The values log KD = 2.3 (see Table 5, footnote a), log (HLorg ) 9.5 (Table 5, footnote

b), log (H 2 L2org

) 11.3 (Table 5, footnote b), log (HL2,org ) 12.9 (Table 5, footnote b),

log K ex (Eu 3org ) 1.3 (inferred from Ref. [31]), and log Kex (Am3org ) 1.5 (inferred from Ref.

5
 ACCEPTED MANUSCRIPT

[31]) were used for the respective calculations. The results are listed in Tables 3 and 4. From
these tables it is evident that the extraction data can be best explained assuming the complexes
ML32 and ML33 (M3+ = Eu3+, Am3+; L = N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-

2,9-dicarboxamide) to be extracted into the nitrobenzene phase.

Knowing the values log K ex (Eu 3org ) 1.3 and log Kex (Am3org ) 1.5 , which were inferred

from Ref. [31], as well as the extraction constants log K ex (EuL32,org ) 25.28 ,

log Kex (EuL33,org ) 33.76 , log Kex (AmL32,org ) 26.81 , and log Kex (AmL33,org ) 35.38

PT
(Tables 5 and 6), the stability constants of the complexes ML32 and ML33 (M3+ = Eu3+,

RI
Am3+; L = N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide) in the
nitrobenzene phase defined as

(ML 3
)
[ML32,org ]
SC
NU
2,org
(14)
[M 3org ][L org ]2

3
[ML33,org ]
(ML ) (15)
MA

3,org
[M 3org ][L org ]3

can be calculated employing the following simple relations:

E D

log (ML32,org ) log Kex (ML32,org ) log K ex (M 3org

) (16)
PT

log (ML33,org ) log Kex (ML33,org ) log Kex (M 3org

) (17)
CE

The respective equilibrium constants are summarized in Tables 5 and 6. It should be noted
AC

that the stability constants of the cationic complex species ML32 and ML33 (M3+ = Eu3+,
Am3+; L = N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide) in water-
saturated nitrobenzene are log (EuL32,org ) 23.98 , log (AmL32,org ) 25.31 ,

log (EuL33,org ) 32.46 , and log (AmL33,org ) 33.98 , as given in Tables 5 and 6. This means

that in the mentioned nitrobenzene medium, the stability constants of the complexes
AmL32,org and AmL33, org are somewhat higher than those of the corresponding cationic species

EuL32,org and EuL33,org .

6
 ACCEPTED MANUSCRIPT

Moreover, Fig. 4 presents the contributions of the species H org , HLorg , H 2 L2org

, and HL2,org

to the total proton concentration in the equilibrium nitrobenzene phase, whereas Figs. 4 and 5
show the contributions of the cations M 3org , ML32,org , and ML33,org (M3+ = Eu3+, Am3+; L =

N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide) to the total trivalent

metal cation concentrations in the corresponding equilibrium organic phase. From Figs. 4, 5,
and 6 it follows that the species HL2,org , EuL33,org , and AmL33,org are present in significant

concentrations only at relatively high amounts of the N,N-diethyl-N,N-diphenyl-1,10-

PT
phenanthroline-2,9-dicarboxamide (L) ligand in the systems under consideration. On the other

hand, the contributions of the cations H 2 L2org , Eu 3org , and Am3org are very small, as also

RI
follows from Figs. 4, 5, and 6.

SC
Finally, Table 7 summarizes the stability constants of the complex species ML32 and

ML33 (M3+ = Eu3+, Am3+) with two electroneutral ligands L (L = N,N-diethyl-N,N-diphenyl-

NU
1,10-phenanthroline-2,9-dicarboxamide, bis(diphenylphosphino)methane dioxide (DPPMDO)
see Fig. 7) in water-saturated nitrobenzene. From the data reviewed in this table it is
MA

apparent that in the considered nitrobenzene medium, the stabilities of the complexes ML32,org

and ML33,org (M3+ = Eu3+, Am3+) containing the N,N-diethyl-N,N-diphenyl-1,10-

D

phenanthroline-2,9-dicarboxamide ligand are essentially higher than those of the respective

E

cationic complexes ML32,org and ML33,org (M3+ = Eu3+, Am3+) with the ligand DPPMDO. It
PT

means that complexation ability towards Eu3+ and Am3+ of the N,N-diethyl-N,N-diphenyl-
1,10-phenanthroline-2,9-dicarboxamide ligand under study is also substantially higher than
CE

that of the DPPMDO ligand.

In conclusion, we must state that the separation factors SFAm/Eu , reached in the studied
AC

twophase waternitrobenzene extraction system, defined by means of the corresponding

equilibrium distribution ratios, D(Am3+) / D (Eu3+), are very high, in the range from 29 to 71.
This fact follows from the results presented in Figs. 2 and 3 or in Tables 1 and 2, respectively.

4. Conclusions
In the present work, the solvent extraction of trivalent europium and americium from
acidic aqueous solutions into nitrobenzene was investigated by means of a mixture of
hydrogen dicarbollylcobaltate (H+B-) and N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-

7
 ACCEPTED MANUSCRIPT

2,9-dicarboxamide (L). It was proven that the cationic species HL+, H 2 L2 , HL2 , ML32 , and

ML33 (M3+ = Eu3+, Am3+; L = N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-

dicarboxamide) are extracted into the organic phase of the waternitrobenzene system. It was
found that in nitrobenzene saturated with water, the stability constants of the complexes
AmL32,org and AmL33, org are somewhat higher than those of the corresponding cationic species

EuL32,org and EuL33, org . Furthermore, the reached separation factors SFAm/Eu in this twophase

PT
system are in the range of 29-71. Finally, it was evidenced experimentally that the N,N-
diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide ligand can be considered in the

RI
nitrobenzene medium as an extraordinarily strong receptor for the Eu3+ and Am3+ cations. On
the basis of the previous facts it is obvious that this investigated electroneutral ligand L could

SC
be also considered as a potential extraction agent for nuclear waste treatment.
NU
Acknowledgements
This work was supported by the Grant Agency of Faculty of Environmental Sciences,
MA

Czech University of Life Sciences, Prague, Project No.: 42900/1312/3114 entitled

Environmental Aspects of Sustainable Development of Society, by the Czech Ministry of
Education, Youth, and Sports, Project MSMT No.: 20/2015, and finally, by the Government
D

of Russian Federation, Grant No.: 074-U01.

E
PT
CE
AC

8
 ACCEPTED MANUSCRIPT

References

[1] C. Cuillerdier, C. Musikas, P. Hoel, L. Nigond, X. Vitart, Separ. Sci. Technol. 26 (1991)
1229-1244.

[2] V. K. Manchanda, P. N. Pathak, Separ. Pur. Technol. 35 (2004) 85-103.

[3] Y. Sasaki, G. R. Choppin, Anal. Sci. 12 (1996) 225-230.

[4] Y. Sasaki, Y. Sugo, S. Suzuki, S. Tachimori, Solvent Extr. Ion Exch. 19 (2001) 91-103.

PT
[5] Y. Sasaki, S. Tachimori, Solvent Extr. Ion Exch. 20 (2002) 21-34.

[6] Y. Sasaki, Y. Sugo, S. Suzuki, T. Kimura, Anal. Chim. Acta 543 (2005) 31-37.

RI
[7] S. A. Ansari, P. N. Pathak, V. K. Manchanda, M. Husain, A. K. Prasad, V. S. Parmar,

SC
Solvent Extr. Ion Exch. 23 (2005) 463-479.

[8] E. P. Horwitz, D. R. McAlister, A. H. Bond, R. E. Barrans, Jr., Solvent Extr. Ion Exch. 23
NU
(2005) 319-344.

[9] M. Iqbal, P. K. Mohapatra, S. A. Ansari, J. Huskens, W. Verboom, Tetrahedron 68

MA

(2012) 7840-7847.

[10] P. K. Mohapatra, M. Iqbal, D. R. Raut, W. Verboom, J. Huskens, S. V. Godbole, Dalton

Trans. 41 (2012) 360-363.
D

[11] D. R. Raut, P. K. Mohapatra, S. A. Ansari, S. V. Godbole, M. Iqbal, D. Manna, T. K.

E

Ghanty, J. Huskens, W. Verboom, RSC Advances 3 (2013) 9296-9303.

PT

[12] P. K. Mohapatra, D. R. Raut, M. Iqbal, J. Huskens, W. Verboom, Appl. Radiat. Isot. 85

CE

(2014) 133-138.

[13] E. Makrlk, P. Vaura, Talanta 32 (1985) 423-429.

AC

[14] E. Makrlk, P. Vaura, P. Seluck, J. Solut. Chem. 38 (2009) 1129-1138.

[15] E. Makrlk, P. Vaura, P. Seluck, J. Solut. Chem. 39 (2010) 692-700.

[16] E. Makrlk, P. Vaura, P. Seluck, V. A. Babain, I. V. Smirnov, Acta Chim. Slov. 56

(2009) 718-722.

[17] E. Makrlk, P. Vaura, Z. Sedlkov, J. Radioanal. Nucl. Chem. 283 (2010) 157-161.

[18] E. Makrlk, Z. Spchal, P. Vaura, P. Seluck, J. Radioanal. Nucl. Chem. 295 (2013)
2135-2140.

9
 ACCEPTED MANUSCRIPT

[19] V. N. Romanovskiy, I.V. Smirnov, V. A. Babain, T. A. Todd, R. S. Herbst, J. D. Law, K.

N. Brewer, Solvent Extr. Ion Exch. 19 (2001) 1-21.

[20] J. D. Law, R. S. Herbst, T. A. Todd, V. N. Romanovskiy, V. A. Babain, V. M.

Esimantovskiy, I. V. Smirnov, B. N. Zaitsev, Solvent Extr. Ion Exch. 19 (2001) 23-36.

[21] M. Galletta, S. Scaravaggi, E. Macerata, A. Famulari, A. Mele, W. Panzeri, F. Sansone,

A. Casnati, M. Mariani, Dalton Trans. 42 (2013) 16930-16938.

[22] D. Manna, S. Mula, A. Bhattacharyya, S. Chattopadhyay, T. K. Ghanty, Dalton Trans. 44

PT
(2015) 1332-1340.

RI
[23] M. F. Hawthorne, D. C. Young, T. D. Andrews, D. V. Howe, R.L. Pilling, A. D. Pitts, M.
Reintjes, L. F. Warren, P. A. Wegner, J. Am. Chem. Soc. 90 (1968) 879-896.

SC
[24] E. Makrlk, Collect. Czech. Chem. Commun. 57 (1992) 289-295.

[25] P. Vaura, J. Rais, P. Seluck, M. Kyr, Collect. Czech. Chem. Commun. 44 (1979) 157-
NU
166.

[26] E. Makrlk, P. Vaura, Z. Spchal, P. Seluck, J. Radioanal. Nucl. Chem. 298 (2013) 243-
MA

248.

[27] P. Vaura, E. Makrlk, J. Rais, M. Kyr, Collect. Czech. Chem. Commun. 47 (1982)
D

1444-1464.
E

[28] P. Vaura, E. Makrlk, Collect. Czech. Chem. Commun. 58 (1993) 1324-1336.

PT

[29] L. G. Silln, B. Warnqvist, Arkiv Kemi 31 (1969) 315-339.

[30] J. Rais, E. ebestov, P. Seluck, M. Kyr, J. Inorg. Nucl. Chem. 38 (1976) 1742-1744.
CE

[31] J.Rais, S. Tachimori, Separ. Sci. Technol. 29 (1994) 1347-1365.

AC

10
 ACCEPTED MANUSCRIPT

PT
RI
SC
NU
Fig. 1. Structural formula of N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-2,9-
dicarboxamide (abbrev. L).
MA
E D
PT
CE
AC

11
 ACCEPTED MANUSCRIPT

Table 1
Logarithm of the europium distribution ratio (log D) as a function of logarithm of the
numerical value of the analytical concentration of the N,N-diethyl-N,N-diphenyl-1,10-
phenanthroline-2,9-dicarboxamide ligand in the initial nitrobenzene phase (log c( L)); the
values of log c(L) and log D are given for all experimental points.
_______________________________________________________________________

c(HNO3) = 0.05 mol/L, cB = 0.0025 mol/L

-4.301, -1.045; -4.046, -0.719; -3.796, -0.288; -3.553, 0.133; -3.301, 0.582;
-3.046, 1.036; -2.796, 1.397; -2.553, 1.122; -2.301, -0.049

PT
c(HNO3) = 0.05 mol/L, cB = 0.005 mol/L

RI
-4.301, -0.633; -4.046, -0.170; -3.796, 0.125; -3.553, 0.573; -3.301, 1.061;
-3.046, 1.562; -2.796, 1.974; -2.553, 2.342; -2.301, 2.313

SC
_______________________________________________________________________
NU
MA
E D
PT
CE
AC

12
 ACCEPTED MANUSCRIPT

Table 2
Logarithm of the americium distribution ratio (log D) as a function of logarithm of the
numerical value of the analytical concentration of the N,N-diethyl-N,N-diphenyl-1,10-
phenanthroline-2,9-dicarboxamide ligand in the initial nitrobenzene phase (log c( L)); the
values of log c(L) and log D are given for all experimental points.

________________________________________________________________________

c(HNO3) = 0.05 mol/L, cB = 0.0025 mol/L

-4.301, 0.615; -4.046, 1.152; -3.796, 1.551; -3.553, 2.063; -3.301, 2.451;

PT
-3.046, 3.012; -2.796 3.210; -2.553, 2.451; -2.301 1.320

c(HNO3) = 0.05 mol/L, cB = 0.005 mol/L

RI
-4.301, 0.841; -4.046, 1.295; -3.796, 1.805; -3.553, 2.321; -3.301, 2.737;

SC
-3.046, 3.316; -2.796, 3.561; -2.553, 4.073; -2.301, 3.633
________________________________________________________________________
NU
MA
E D
PT
CE
AC

13
 ACCEPTED MANUSCRIPT

Table 3
Comparison of various models of europium extraction from aqueous solution of HNO3 by
nitrobenzene solution of H+B- in the presence of N,N-diethyl-N,N-diphenyl-1,10-
phenanthroline-2,9-dicarboxamide (L).

Europium complexes
in the organic phase log K ex a Ub
EuL32 25.81 (26.37) 46.00
EuL33 35.05 (35.47) 12.27

PT
EuL32 , EuL33 25.280.12, 33.760.24 0.03

RI
a
The values of the extraction constants are given for each complex. The reliability interval
of the constants is given as 3(K), where (K) is the standard deviation of the constant

SC
K [29]. These values are given in the logarithmic scale using the approximate expression
log K {log [K+1.5(K)] log [K1.5(K)]}. For (K) 0.2 K, the previous expression is
not valid and then only the upper limit is given in the parentheses in the form of
NU
log K (log [K + 3(K)]) [29].
b
The error-square sum U = (log Dcalc log Dexp) 2.
MA
E D
PT
CE
AC

14
 ACCEPTED MANUSCRIPT

Table 4
Comparison of various models of americium extraction from aqueous solution of HNO3 by
nitrobenzene solution of H+B- in the presence of N,N-diethyl-N,N-diphenyl-1,10-
phenanthroline-2,9-dicarboxamide (L).

Americium complexes
in the organic phase log K ex a Ub
AmL32 26.85 (27.35) 7.44
3 37.35 (37.79) 3.56

PT
AmL 3

AmL32 , AmL33 26.810.15, 35.38(35.76) 0.02

RI
a
See Table 3, footnote a.

SC
b
See Table 3, footnote b.
NU
MA
E D
PT
CE
AC

15
 ACCEPTED MANUSCRIPT

Table 5
Equilibrium constants in the waterHNO3Eu3+(microamounts)nitrobenzene N,N-diethyl-
N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide (L) H B system.

Equilibrium log K
Laq Lorg 2.3 a

Horg Lorg HLorg 9.5 b

2H org
L org H 2 L2org 11.3 b

Horg 2Lorg HL2,org 12.9 b

PT
Eu 3aq 3H org

Eu 3org
3H aq 1.3 c
Eu 3aq 2L org 3H org

EuL32,org 3H aq
25.28

RI
Eu 3aq 3Lorg 3H org

EuL33,org 3H aq
33.76

Eu 3org 2L org EuL32,org 23.98

SC

Eu 3org 3L org EuL33,org 32.46

a
Determined by the method of the concentration dependent distribution [30].
NU
b
Determined by the method described in Ref. [25].
c
Inferred from Ref. [31].
MA
E D
PT
CE
AC

16
 ACCEPTED MANUSCRIPT

Table 6
Equilibrium constants in the waterHNO3Am3+(microamounts)nitrobenzene N,N-diethyl-
N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide (L) H+B- system.

Equilibrium log K
Laq Lorg 2.3 a

Horg Lorg HLorg 9.5 b

2H org
L org H 2 L2org 11.3 b

Horg 2Lorg HL2,org 12.9 b

PT
Am3aq 3H org

Am3org
3H aq 1.5 c
Am3aq 2L org 3H org

AmL32,org 3H aq
26.81
Am3aq 3Lorg 3H org

AmL33,org 3H aq

RI
35.38

Am3org 2Lorg AmL32,org 25.31

SC

Am3org 3Lorg AmL33,org 33.88

a
Determined by the method of the concentration dependent distribution [30].
NU
b
Determined by the method described in Ref. [25].
c
Inferred from Ref. [31].
MA
E D
PT
CE
AC

17
 ACCEPTED MANUSCRIPT

Table 7

Stability constants of the complexes ML32 and ML33 (M3+ = Eu3+, Am3+; L = N,N-diethyl-
N,N-diphenyl-1,10-phenanthroline-2,9-dicarboxamide, bis(diphenylphosphino)methane
dioxide (DPPMDO) see Fig. 7) in nitrobenzene saturated with water at 25 C.

Quantity L

PT
DPPMDO a N,N-diethyl-N,N-diphenyl-1,10-
phenanthroline-2,9-dicarboxamide b

RI
log (EuL32,org ) 17.76 23.98

SC
log ( EuL33,org ) 24.59 32.46
NU
log ( AmL32,org ) 17.73 25.31

log ( AmL33,org ) 24.72 33.88

MA
D

a
Ref. [18].
b
E

This work.
PT
CE
AC

18
 ACCEPTED MANUSCRIPT

PT
RI
SC
NU
MA
E D
PT

Fig.2. Log D as a function of log c(L), where L = N,N-diethyl-N,N-diphenyl-1,10-

phenanthroline-2,9-dicarboxamide, for the system water HNO3
3+
Eu (microamounts)nitrobenzene N,N-diethyl-N,N-diphenyl-1,10-phenanthroline-
CE

2,9-dicarboxamide (L)H+B-; 1 c(HNO3) = 0.05 mol/L, cB = 0.0025 mol/L; 2 c(HNO3)

= 0.05 mol/L, cB = 0.005 mol/L. The curves were calculated using the constants given
in Table 5.
AC

19
 ACCEPTED MANUSCRIPT

PT
RI
SC
NU
MA
D

Fig.3. Log D as a function of log c(L), where L = N,N-diethyl-N,N-diphenyl-1,10-

water HNO3
E

phenanthroline-2,9-dicarboxamide, for the system

Am3+(microamounts)nitrobenzene N,N-diethyl-N,N-diphenyl-1,10-
PT

phenanthroline-2,9-dicarboxamide (L)H+B-; 1 c(HNO3) = 0.05 mol/L,

cB = 0.0025 mol/L; 2 c(HNO3) = 0.05 mol/L, cB = 0.005 mol/L. The curves were
calculated using the constants given in Table 6.
CE
AC

20
 ACCEPTED MANUSCRIPT

PT
RI
SC
NU
MA

Fig. 4. Distribution diagram of proton in the equilibrium nitrobenzene phase of the water
HNO3Eu3+(microamounts)nitrobenzene N,N-diethyl-N,N-diphenyl-1,10-
D

phenanthroline-2,9-dicarboxamide (L) H+B extraction system in the forms of H ,

-
E

HL , H 2 L2 , and HL2 ; c(HNO3) = 0.05 mol/L, cB = 0.0025 mol/L.

1 (H ) [Horg

]/c(H )org , 2 (HL ) [HLorg ]/c(H )org ,
PT

3 (H 2 L2 ) 2 [H 2 L2org

]/c(H ) org , 4 (HL2 ) [HL2,org ]/c(H )org , where
c(H ) org [H org

] [HLorg ] 2 [H 2 L2org

] [HL2,org ].
CE

The distribution curves were calculated using the constants given in Table 5.
AC

21
 ACCEPTED MANUSCRIPT

PT
RI
SC
NU
MA

Fig. 5. Distribution diagram of europium in the equilibrium nitrobenzene phase of the water
HNO3Eu3+(microamounts)nitrobenzene N,N-diethyl-N,N-diphenyl-1,10-
D

phenanthroline-2,9-dicarboxamide (L) H B extraction system in the forms of Eu 3 ,

E

EuL32 , and EuL33 ; c(HNO3) = 0.05 mol/L, cB = 0.0025 mol/L.

1 (Eu 3 ) [Eu 3org

]/c(Eu 3 ) org , 2 (EuL32 ) [EuL32,org ]/c(Eu 3 )org ,
PT

3 (EuL33 ) [EuL33,org ]/c(Eu 3 )org , where c(Eu 3 )org [Eu 3org

] [EuL32,org ] [EuL33,org ] .
The distribution curves were calculated using the constants given in Table 5.
CE
AC

22
 ACCEPTED MANUSCRIPT

PT
RI
SC
NU
MA

Fig. 6. Distribution diagram of americium in the equilibrium nitrobenzene phase of the water
D

HNO3Am3+(microamounts)nitrobenzene N,N-diethyl-N,N-diphenyl-1,10-
phenanthroline-2,9-dicarboxamide (L)H+B- extraction system in the forms of Am 3 ,
E

AmL32 , and AmL33 ; c(HNO3) = 0.05 mol/L, cB = 0.0025 mol/L.

PT

1 (Am3 ) [Am3org

]/c(Am3 ) org , 2 (AmL32 ) [AmL32,org ]/c(Am3 ) org ,
3 (AmL33 ) [AmL33,org ]/c(Am3 )org ,
CE

where c(Am3 )org [Am3org

] [AmL32,org ] [AmL33,org ] .
The distribution curves were calculated using the constants given in Table 6.
AC

23
 ACCEPTED MANUSCRIPT

O O
P P

PT
RI
SC
Fig. 7. Structural formula of bis(diphenylphosphino)methane dioxide (abbrev. DPPMDO).
NU
MA
E D
PT
CE
AC

24
 ACCEPTED MANUSCRIPT

HIGHLIGHTS

Solvent extraction of trivalent europium and americium from water into nitrobenzene was
investigated.
Extraction and stability constants of the proven complexes were determined and discussed.
Separation factors of the pair Am(III)/Eu(III) in the studied water-nitrobenzene system are
in the range of 29 - 71.

PT
RI
SC
NU
MA
E D
PT
CE
AC

25
 ACCEPTED MANUSCRIPT

GRAPHICAL ABSTRACT

PT
RI
SC
NU
MA
DE
PT
CE
AC

26