J Radioanal Nucl Chem (2012) 292:1093–1098
DOI 10.1007/s10967-011-1568-y
Extraction of europium by sodium oleate/pentanol/heptane/NaCl
microemulsion system
W. Wang • Y. Z. Yang • H. Zhao • Q. W. Guo •
W. J. Lu • Y. M. Lu
Received: 15 November 2011 / Published online: 10 December 2011
Ó Akadémiai Kiadó, Budapest, Hungary 2011
Abstract The extraction of europium to a W/O micro-
emulsion with an anionic surfactant was studied. In the
sodium oleate (NaOL)/pentanol/heptane/NaCl system, the
influence of aqueous-microemulsion ratio, concentration of
NaOL, extraction temperature, concentration of cosurfac-
tant, pH and salting-out agent on the extraction yield were
investigated. Europium was probably extracted into the
microemulsion phase in the form of Eu(OL)2Cl, and the
extraction yield (E%) was above 99% when R = 8. The
enthalpy and entropy of Eu(III) extraction were calculated
to be -12.18 kJ/mol and -61.41 J/(mol K), respectively.
The back-extraction is conducted by hydrochloric acid
(0.8 mol/L), which provided better back-extraction yields
(95.15%).
Keywords Microemulsion  Eu(III)  Extraction 
Back-extraction  Sodium oleate
List of symbols
w Mass fraction of each component in the total mass
of microemulsion phase
E% Extraction yield
D The distribution ratio of Eu(III)
a Aqueous phase
o Oil phase
W. Wang  Y. Z. Yang (&)  Q. W. Guo  W. J. Lu  Y. M. Lu
Key Laboratory of Special Functional Aggregated Materials of
Education Ministry, School of Chemistry and Chemical
Engineering, Shandong University, Jinan 250100, China
e-mail: yzhyang@sdu.edu.cn
H. Zhao
National Engineering Technology Research Center for Colloidal
Materials, Shandong University, Jinan 250100, China
Introduction
The demand for rare earth metals has been increasing in
recent years because of their unique physical and chemical
properties as the new constituents of electronic, optical and
magnetic devices [1]. Europium is one of the rarest rare
earth metals and widely used in phosphor powder, laserable
materials, shielding materials and nuclear energy industry.
Therefore, the research of europium’s separation and
concentration has been greatly encouraged.
Conventional solvent extraction is one of the most
effective methods. There are many extractants have been
used in solvent extraction systems for the extraction of
europium(III), for instance, calixarene derivatives [2, 3],
amide derivatives [4], organic phosphinic extractant [5–7]
and [bis(di-iso-propyltriazinyl)pyridine] (DiPTP) [8].
Europium(III) was also extracted by cloud point extraction
method using di(2-ethylhexyl)phosphoric acid and Triton
X-100 [9]. Furthermore, europium(III) had been extracted
from aqueous solution by using room-temperature ionic
liquid and supercritical carbon dioxide in conjunction [10].
But these methods are all limited in terms of their low
extraction yield and high costs.
There are four types of microemulsion systems called
Winsor I, Winsor II, Winsor III and Winsor IV. Generally
speaking, only the Winsor II microemulsion, which is oil
continuous, can be used to separate materials from aqueous
phase. Water-in-oil microemulsion, which contains an
anionic surfactant and an electrically neutral organic ligand
(extractant), was introduced as a new medium for effective
metal extraction and separation from an aqueous solution
of high ionic strength [11]. Microemulsions are optically
isotropic, transparent, thermodynamically stable colloid
mixtures of two immiscible solvents stabilized by an
adsorbed surfactant film at the liquid–liquid interface
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1094
[12, 13]. Microemulsion extraction systems used as sepa-
ration media have excellent properties such as the nano-
meter-sized spherical bicontinuous structure, the rapid
coalescence and reseparation dynamics of structure and the
enhanced solubilization capacity [14]. The attraction
between the head group of surfactant and metal ions is the
driving force of extraction process. The microemulsion
systems applied in metallic cations extraction have great
advantages over the conventional solvent extraction and
other new techniques. Compared with conventional solvent
extraction, the microemulsion, combining the forward
extraction and the backward extraction, not only simplified
the operating process but also reduced the cost and
enhanced extraction yield. Various types of metallic ions
can be extracted by this type of microemulsion [15–17].
The extraction of Eu(III) from aqueous HNO3 solution into
a water-in-oil (W/O) microemulsion occurring in hexane
was studied [18]. In this research, Aerosol OT (AOT-) was
used as an anionic surfactant, and a bulky diamide (DA),
N,N0 -dioctyl-N,N0 -dimethyl-2-(30 -oxapentadecyl)propane-
1,3-diamide, was employed as an electrically neutral
extractant. However, the research about extracting Eu(III)
by microemulsion was limited. In order to facilitate large-
scale industrial applications of microemulsion separation
processes, knowledge of the optical conditions and the
thermodynamic constants associated with the distribution
of Eu(III) between immiscible media is necessary.
The purpose of the present work is to investigate the
possibility of europium ions removal from aqueous solu-
tions by Winsor II systems with extractant NaOL. Various
factors, including contact time, aqueous-microemulsion
ratio (R), and concentration of NaOL, extraction tempera-
ture, concentration and sort of alcohol, pH of the feed
aqueous and salting-out agent on the extraction yield of
europium were studied. The extraction of Eu(III) indicates
that the stoichiometry of the extracted species probably
was Eu(OL)2Cl. Using the sodium oleate microemulsion, it
was found that over 99% of the total Eu(III) could be
extracted and the back-extraction yield could be reached to
95.15% when using HCl (0.8 mol/L) as stripping.
Experimental
Apparatus
UV-754 spectrophotometer (Shanghai Precision & Scien-
tific Instrument Co., Ltd); Vibrator (Yancheng Science
Instrument Factory, Jiangsu Province), with a vibration
frequency of 275 ± 5 min-1 and a temperature controlling
precision of ±1 K; DDS-307 type digital electric conduc-
tivity meter (Shanghai Precision & Scientific Instrument
123
W. Wang et al.
Co., Ltd) were used. Centrifuger (TDL 80-2B, Shanghai
Anting Science Instrument Factory).
Reagents
Sodium oleate, europium oxide, sodium chloride, hydro-
chloric acid, sodium hydroxide, sulfuric acid, potassium
chloride was purchased from Sinopbarm Chemical Reagent
Co., Ltd. Octanol, heptane, hexanol, pentanol was pur-
chased from Tianjin Damao Reagent Factory. Arsenazo III
was purchased from Beijing Changping Shanying Chemi-
cal Plant. Magnesium chloride was purchased from Tianjin
Kaitong Chemical Reagent Co., Ltd. All of these chemicals
were of analytical reagent grade and were used without
further purification.
All aqueous solutions were prepared using distilled
water.
Methods
In the following studies, unless indicated specially, the
temperature was generally maintained at 298 ± 1 K. The
initial aqueous solution, containing europium (6.5 mmol),
was prepared by adding Eu2O3 to HCl solution. The pH
of the aqueous solution was adjusted to 2.9 with 1 mol/L
HCl or 1 mol/L NaOH. The organic phase was prepared
via injecting NaOL, NaCl solution and pentanol in hep-
tane. In the present study, sodium oleate is used as a
typical anionic surfactant and pentanol is used as
cosurfactant.
The dissolubility of sodium oleate is very poor in the
mixture and the initial appearance is turbidity. To solve
this, sodium chloride solution (1 mol/L) was substituted for
water to be added into the mixture until it was clarified.
The procedure of metal extraction into microemulsion
system is, in principle, the same as for ordinary solvent
extraction experiment. All extractions were carried out in
10 mL centrifuge tube. The feed phase consisted of Eu3?,
HCl, and NaCl, was first placed in the bottom of the cen-
trifuge tube and the microemulsion, mentioned before, was
added on the top of the feed phase. Prior to being kept
under rest for phase separation (microemulsion and aque-
ous phase) the mixture was shaken for 10 min. After
extraction, the europium concentration in aqueous solution
was measured by spectrophotometry at 660 nm and the
europium concentration in organic solution was calculated
by mass balance. The extraction yield (E%) of euro-
pium(III) is:
m0  mt
E% ¼  100% ð1Þ
m0
where m0 and mt are the total amount of europium (III) ions
in the feed solutions at t = 0 and t = t, respectively.
Extraction of europium 1095

The extraction process is shown in Fig. 1.

Results and discussion

Effect of contact time

The influence of contact time of microemulsion and feed

solution on the europium extraction yield was measured so
as to establish the optimum time required to attain equi-
librium. The vibration time was varied from 1 to 15 min. It
is found in Fig. 2 that the extraction percentage of Eu(III)
can reach up to 99% within 3 min and the extraction
equilibrium is achieved rapidly within 5 min. Thus, 10 min Fig. 2 Effect of contact time on the extraction yield of Eu(III);
could be chosen as an appropriate time in the posterior w (NaOL) = 8%, w (pentanol) = 32%, R = 8
experimentation.

Effect of aqueous-microemulsion ratio (R)

The effect of the volume ratio of aqueous to microemulsion

(R) on the europium extraction yield (E%) was investigated
(Fig. 3).
Figure 3 shows that, the extraction yield (E%) decreases
slowly with the increase of R from 2 to 8, and decreases
drastically when R increases from 9 to 12. Considering the
extractability and treatment capacity, R = 8 is the most
suitable condition for europium extraction. But the euro-
pium extraction yield was close to 100% under that con-
dition. Because of this, R = 10 was chosen to discuss other
impact factors in the posterior experimentation. Fig. 3 Effect of aqueous-microemulsion ratio on the extraction yield
of Eu(III); w (NaOL) = 8%, w (pentanol) = 32%
Effect of sodium oleate concentration
extraction and improve the extractability, increased, with
The effect of sodium oleate concentration on the distribu- the concentration of NaOL increasing.
tion ratio of Eu(III) is shown in Fig. 4. The amount of The extraction reaction between Eu(III) and NaOL
microemulsion produced, which could accelerate the microemulsion could be hypothesized as below:

Fig. 1 Extraction mechanism

based on the sodium oleate
microemulsion system

123
1096 W. Wang et al.

Fig. 5 The natural logarithm of the distribution ratio (D) as a

Fig. 4 The logarithm of the distribution ratio (D) as a function function of 1,000/T; w (NaOL) = 8%, w (pentanol) = 32%, R = 10
of the logarithm of surfactant concentration; w (NaOL) = 8%,
w (pentanol) = 32%, R = 10
Table1 Thermodynamic parameters for Eu3? extraction by sodium
oleate at various temperatures
 þ
Eu3þ
ðaÞ þð3nÞClðaÞ þnNaOLðoÞ
Eu(OL)n Clð3nÞðoÞ þnNaðaÞ T/K K DGh (kJ/mol) TDSh (kJ/mol) DHh (kJ/mol)
ð2Þ 288.15 0.10304 5.4448 -17.6248
The equilibrium constant is: 293.15 0.08954 5.8816 -18.0616
303.15 0.07643 6.4812 -18.6612 -12.18
½EuðOLÞn Clð3nÞ ðoÞ ½Naþ nðaÞ 313.15 0.06714 7.0325 -19.2125
K¼ ð3nÞ
ð3Þ
½Eu3þ ðaÞ ½Cl ðaÞ ½NaOLnðoÞ 318.15 0.06216 7.3486 -19.5286

And the distribution ratio is:

The lgK values for Eu(III) in sodium oleate micro-
½EuðOLÞn Clð3nÞ ðoÞ emulsion can be calculated as per the extraction data and
D¼ ¼ K½Naþ n  3n n
ðaÞ ½Cl ðaÞ ½NaOLðoÞ the Eq. 5.
½Eu3þ ðaÞ
By plotting the natural logarithm of the equilibrium
ð4Þ
constant (K) as a function of 1,000/T, a straight line is
lg D ¼ lg K  n lg½Naþ ðaÞ þ n lg½NaOLðoÞ obtained, with the intercept of -7.3854 and slope of
ð5Þ 1.4652, shown in Fig. 5.
þ ð3  nÞ lg½Cl ðaÞ
Using the Van’t Hoff equation:
It can be seen that the slope of lgD versus lg[NaOL](o) is DH h DSh
1.99, closing to 2. So the extraction reaction can be written ln K ¼  þ ð7Þ
RT R
as:
and Gibbs function:
 þ
Eu3þ
ðaÞ + ClðaÞ + 2NaOLðoÞ
Eu(OL)2 ClðoÞ + 2NaðaÞ ð6Þ
DGh ¼ RT ln K ¼ DH h  TDSh ð8Þ
It indicates that europium is probably extracted into the
microemulsion phase in the form of Eu(OL)2Cl, coinciding The values calculated for the thermodynamic parameters of
with the ion exchange mechanism reported in the publi- Eu(III) extraction are listed in Table 1.
cation [19]. The enthalpy and the entropy change of this reaction are
-12.18 kJ/mol and -61.41 J/(molK), respectively, which
Effect of temperature indicating that this is an exothermic reaction.

In the series of research, the effect of various temperatures
on the europium extraction yield (E%) was investigated. The
results, which are shown in Fig. 5, indicate that europium
extraction yield (E%) decreased with the temperature
increasing. The extraction processes are driven by enthalpy
and it favors the partition of metal ions at lower temperature
[20].
Effect of alcohol concentration
The effect of alcohol concentration of microemulsion on the
europium extraction yield (E%) was investigated with three
alcohols, including pentanol, hexanol and octanol (Fig. 6).
The three extraction yield (E%) all increased with the
increase of alcohol concentration first and then decreased.

123
Extraction of europium 1097

Fig. 6 Effect of alcohol concentration on the extraction yield of Fig. 7 Effect of pH of the feed solution on the extraction yield of
Eu(III); w (NaOL) = 8%, R = 10 Eu(III); w (NaOL) = 8%, w (pentanol) = 32%, R = 8

The extraction yield (E%) order using different alcohols is:

E% (hexanol) [ E% (octanol) [ E% (pentanol).
The amphiphilic nature, short hydrophobic chain and
terminal hydroxyl group of 1-pentanol, make it to interact
with surfactant monolayers at the interface, affect the
packing of the interface, and in turn influence the curvature
of the interface and interfacial energy. The amphiphilic
nature of low molecular cosurfactants also can distribute
between the aqueous and oil phase, altering the chemical
composition and the relative ratio of hydro/lipophilicity.
These two properties render short chain alcohols useful for
the preparation of microemulsion [21]. Emulsion breaking
always occurs in process of europium extraction when long
chain alcohols are used as cosurfactant of the microemul-
sion. Wherefore, pentanol was chosen as cosurfactant. Fig. 8 Effect of salt concentration on the extraction yield of Eu(III);
w (NaOL) = 8%, w (pentanol) = 32%, R = 10
Effect of pH
As hydration, inorganic salt attracts part of free water
The europium extraction yield (E%) as the function of pH molecules leading a high concentration of europium per the
of the feed solution was analysed (Fig. 7). The extraction Salt-Effect Theory. At the same time, the critical micelle
yield is very low when pH is lower than 1.5, then the concentration (cmc) of ionic surfactant decreases, while the
extraction yield increases sharply till the pH of 4 and keeps aggregation number of reverse micelles increases. There-
a certain value from 4 to 7. Oleic acid, which leads to fore, the europium extraction yield can be improved by
decreasing the amounts of the surfactant and the extractant, adding salt. On the other hand, the K? or Mg2? in the
is generated in the aqueous solution when pH is low. And aqueous phase has competitive adsorption with Eu(III).
Eu(OH)3 is produced in the solution, while pH C 7. Based These two actions competed with each other, which lead to
on this feature, a higher extraction field value is got while the experimental phenomena.
4 2 pH 2 7.
Back-extraction
Effect of salt concentration
Back-extraction process consists of europium recovery by
The effect of cation concentration on the europium adding an acid to the microemulsion concentrated in
extraction yield (E%) were investigated. The tendency of europium. In the back-extraction stage, different concen-
the curve descends first, then raises, and descends finally, trations of hydrochloric acid and sulfuric acid were
which is shown in Fig. 8. Each curve has a maximum of investigated. Compared with sulfuric acid, hydrochloric
E% and a minimum of E%. The maximum of E% by acid gets higher back-extraction yield at the same con-
adding MgCl2 is higher than that by adding KCl. centration. The obtained result is that hydrochloric acid

123
1098
(0.8 mol/L) provided better back-extraction yields (95.15%
within 10 min).
Conclusion
Important conclusions could be drawn from this work, all
related to the europium extraction process using NaOL
microemulsion. The extraction of europium by winsor II
microemulsion was very efficient and the extraction yield
(E%) could be higher than 99%.
Various factors which impact the europium extraction
yield (E%) had been investigated in this paper. The W/O
microemulsion was maintaining higher extractability in a
considerable pH range (4–7). The enthalpy and entropy of
Eu(III) extraction into microemulsion were calculated to be
-12.18 kJ/mol and -61.41 J/(mol K). Equilibrium inves-
tigation on the extraction of Eu(III) by sodium oleate
indicated that the extracted species was probably to be
Eu(OL)2Cl. The hydrochloric acid (0.8 mol/L) was the
proper back-extraction agent through back-extraction pro-
cess and the high back-extraction yield (95.15%) is
obtained. The results presented in the paper show a
hydrometallurgical method for the efficient and economical
recovery of europium.
Acknowledgment The authors acknowledge financial support for
this work from The National Natural Science Foundation of China
(No. 20876089), The National Natural Science Foundation of China
(No. 21076115), Natural Science Foundation of Shandong province
(Grant No. Y2007B05), and Key Technologies R&D Programme of
China (NO. 2007BAD87B05).
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