Proc. Indian Acad. Sci. (Chem. Sci.), Vol. 110, No. 2, April 1998, pp. 83-88.

© Printed in India:

Studies on the solvent extraction of trivalent lanthanides

with hexafluoroacetylacetone (HFAA) and
tri-n-octylphosphineoxide (TOPO)

K S R M U R T H Y , R J K R U P A D A M and Y A N J A N E Y U L U *
Centre for Environment, Institute of Post Graduate Studies and Research,
Jawaharlal Nehru Technological University, Hyderabad 28, India
MS received 22 September 1997; revised 2 December 1997
Abstract. Trivalent lanthanides can be synergistically extracted from aqueous
solution as mixed ligand complexes with HFAA and TOPO with the general
formula, Ln (HFAA)3"2TOPO. The optimum conditions for extraction like equilib-
ration time, pH, effect of solvent, metal ion concentration, and reagent concentra-
tion were established. The solvent extraction by mixed ligand system can be used for
the preparation of volatile gas chromatographable lanthanide complexes.
Keywords. Synergic extraction; mixed ligand complexes; trivalent lanthanides.

1. Introduction

Solvent extraction enables quantitative separation of metal chelates into organic

phase 1,2. Hexafluoroacetylacetone, CF 3 - C ( = O ) - C H 2 - C ( = O ) - C F 3 , (HFAA), forms
hydrated chelates with rare earths, which are poorly extractable 3. Neutral donors like
T O P O , TBP, DBSO etc. are known to act as synergistic agents and enhance percentage
extraction of metal chelates 4. To develop a best solvent extraction system for the
preparation of gas cl'tromatographable volatile complexes of lanthanides using HFAA
and T O P O , the authors made systematic and detailed studies and these results
are presented in this paper. The optimum conditions were established for achieving
effective separation of complex group of rare earth elements considering entire
rare earths into two groups. The first group consists of lighter elements (La, Ce, Pr, Nd,
Sm and Eu) while the second group consists of the remaining rare earths (Gd, Tm, Dy,
Ho, Er and Lu).

2. Experimental
2.1 Reagents
The lanthanide oxides (M/s Indian Rare Earths Ltd, 99"9% purity) were dissolved in
0"01 M hydrochloric acid and standardised by titrating with E D T A using xylenol
orange as an indicator 5
0.1 M solution of hexafluoroacetylacetone (M/s Fluka, Switzerland)and tri-n-
octylphosphine oxide (M/s E-Merck) were prepared using cyclohexane as a diluent.

* For correspondence
83
84 K S R Murthy, R J Krupadam and Y Anjaneyulu

2.2 Solvent extraction procedure

5 ml of the 0-01 M lanthanide ion solution was placed in a separating funnel and the
acidity was adjusted to 0.01 M HC1 and the total volume made up to 10ml. 10ml
portions of cyclohexane with 0-1 M HFAA and 0-1 M T O P O were added to the
separating funnel, stoppered and shaken for 15 min. The phase separation was achieved
by centrifugation and percent extraction was determined by titration of aqueous phase
with EDTA using xylenol orange as an indicator.

3. Results and discussion

Detailed experimental studies of solvent extractions were carried out on typical

lanthanides, neodymium (representative of tighter lanthanides) and dysprosium (repre-
sentative of heavier lanthanides) for establishing optimum conditions for extraction.

3.1 Effect of equilibration time and acidity/pH

A 10-minute equilibration time was found to be enough quantitatively to extract all the
lanthanides. Quantitative extraction can be achieved from 0.001-0-04 M hydrochloric
acid or nitric acid for all lanthanides with fixed concentration of HFAA and T O P O
whereas with sulphuric acid and perchloric acid, the extraction was not quantitative
and non-reproducible results were observed, particularly in high acid medium. Studies
on the dependence of percentage extraction on pH indicated that quantitative extrac-
tion of lanthanide ions could be achieved from pH 2 to 7.

3.2 Effect of solvent

Of the organic solvents such as cyclohexane, hexane, benzene, carbon tetrachloride,
chloroform and methylisobutylketone, tested cyclohexane was found to be the best
solvent for the quantitative extraction of lanthanides. The distribution coefficients of
lanthanide complexes of H F A A - T O P O system at pH 2"0 into different non-polar
solvents were found to be in the same order of the solubilities of these solvents in water
(table 1). With more polar solvents like hexone or chloroform, low percentage

Table 1. Correlation of metal distribution coefficient with water solubility of

diluent
Aqueous phase: 5"0ml of 0-01 M Ln(III) solution; acidity 0"01 M hydrochloric acid.
Total volume made up to 10.0ml
Organic phase: 10-0ml of cyclohexane with 0.1 M HFAA and 0-1 M TOPO

Distribution coefficient of
Ln-HFAA-TOPO system Water solubility of
pure
Diluent Nd Dy diluent (g/l)

Cyclohexane 1"0 × 10 3 0-97 X 10 3 0-04

Hexane 0.90 x 103 0.92 X 10 3 0-07
Carbontetrachloride 8'85 x 102 8'76 x 102 0-12
Benzene 6.51 x 102 6.48 x 102 0-54
Chloroform 5.5 x 102 5.45 x 102 1-30
Hexone 5.0 x 102 5.0 x 102 16-0
 Studies on the solvent extraction of trivalent lanthanides 85

0- Dysprosium

l x- Neodymium

N
III

00000.~ 0006 i r~O ~ t r m N ~ . _ _ ~

G(~5 ~ (:K)I9 QOI5 0.0130010 0.007 0 0 0 3 ~ 0 0 0
~- TOPO Coneent ralrion

Figure 1. Synergistic effecton the extraction of lanthanides due to HFAA/TOPO

mixtures. O Dysprosium; X Neodymium.

extraction of lanthanide-HFAA-TOPO system was observed which may be due to the

greater dipole-dipole interaction between polar solvents and HFAA-TOPO reagent
system than with non-polar solvents like cyclohexane.

3.3 Effect of reagent concentration

Extraction studies were performed using varying concentrations of HFAA and TOPO
in cyclohexane from 0-01 M hydrochloric acid containing lanthanide ion solutions.
Very high synergic effect in the extraction was observed (figure 1) which was evident
from the large increase in percentage extraction of the mixed ligand complexes HFAA
and TOPO system when compared to the individual ligands.

3.4 Nature of extraction species

To obtain information on the possible species being extracted into the cyclohexane
phase, the three variables in the system l-H+], HFAA and TOPO were examined,
keeping two constant at a time. As expected from trivalent metal-HFAA system, it was
found that on keeping H + and TOPO concentration constant, while varying the
HFAA concentration, a log/log plot of partition coefficients of lanthanide ions against
HFAA concentration gave a straight line of slope 3. A similar log/log plot varying only
86 K S R Murthy, R J Krupadam and Y Anjaneyulu

H + concentration gave a line of slope 3. O n keeping both H ÷ and H F A A concentra-

tion constant, variation of T O P O concentration gave a line of slope 2.
Based on the above data, the formation of the mixed-ligand complex can be
represented by the following reaction

[Ln 3 + ] + 3 [ H H F A A ] + 2 [ T O P O I ~ [ L n ( H F A A ) 3 . 2 T O P O I + [H +].
(i)
When the initial concentration of the H F A A was kept in-constant excess, and the
concentration of H ÷ was maintained at a low level (0.01 M), the equilibrium was shifted
to the right and the amount of T O P O becomes the limiting quantity in the extraction.
Maximum percent extraction will therefore occur when the stoichiometric amount of
T O P O at 2 was added.

3.5 Effect of ionic size on the extraction of trivalent lanthanide ions

To understand the influence of ionic size of the metal ion on its extraction with
H F A A - T O P O system the percentage extraction of all the trivalent lanthanide ions
along with scandium and yttrium ions with fixed limited concentrations of H F A A
(3 times) and T O P O (2 times) was studied (table 2 and figure 2). F r o m these data the
following observations can be made.
• Extraction of the rare earths reaches a m a x i m u m at Eu or Sm, which lie near the
middle of the lanthanide series
• the extraction of scandium is higher than that of all the rare earth ions, although it
exceeds that of Eu and Sm by only a small amount
• the extraction of yttrium is similar to that of erbium and thulium in all cases.
The above features can be explained in terms of the known chemistry of the trivalent
rare earth metal ions. The complexes formed by all the rare earth metals tend to be
largely ionic in nature. Owing to the p o o r mutual shielding of the 4f electrons, each

Table 2. Extraction of rare earth ions as HFAA-TOPO

mixed ligand complexes

Element Ionic radius ( / ~ ) %Extraction

Sc 0.68 99-9
Y 0.88 80.0
La 1.061 75-0
Ce 1.034 87-0
Pr 1'013 98"0
Nd 0"998 98-0
Sm 0"964 99-0
Eu 0"950 98"0
Gd 0'938 98-0
Tb 0-923 98-0
Dy 0-908 95-0
Ho 0'894 95.0
Er 0"881 81-0
Tm 0"869 82.0
Yb 0"858 76.0
Lu 0"848 74-0
 Studies on the solvent extraction of trivalent lanthanides 87

100

/
90

/
80 LJ

7O
Sc Y La Ce Pr Nd Sm Eu Gd Tb Oy Ho Er Tm Yb Lu
Element

Figure 2. Extraction of rare earths as HFAA-TOPO mixed ligand complexes.

successive electron experiences a gradual increase in effective nuclear charge, with the
result that 4f shell (and hence the ionic radius) decreases markedly in size through the
series from lanthanum (0, 106 nm) to lutecium (0, 085 nm). Since the electrostatic interaction
between the cation and the ligand should be proportional to the reciprocal of the cationic
radius, the stabilities of ionic complexes would be expected to increase through the series
from trivalent lanthanum to lutecium which may result in increase in percentage extraction
with decreasing ionic radius. Such an increase is often observed only for the lighter
lanthanides. Once the cationic radius diminishes to a limiting size to that of Eu or Sm the
steric factors become significant such that any decrease in the radius cannot accommodate
the three HFAA molecules and two TOPO molecules. Thus, the heavier of lanthanides do
become too small in their ionic radius to accommodate all the HFAA and TOPO ligands
with a consequent reduction in the stability of the complexes which may be due to decrease
in the coordination number of lanthanide ion or increase in significance of steric factors, or
both 6. It can be seen that maximum extraction is achieved for dysprosium, europium,
gadolinium and neodymium with fixed limited concentration of HFAA (3 times) and
TOPO (2 times) when compared to other lanthanides.

4. Conclusions

It was observed that by solvent extraction, mixed ligand complexes of lanthanides,

Ln(HFAA)3 2. TOPO can be efficiently separated from interfering with major matrix
88 K S R Murthy, R J Krupadam and Y Anjaneyulu

elements and the pure solid volatile mixed complexes can be rapidly prepared by
evaporating the extractant and recrystallisation. Further, the extact of the mixed ligand
complex oflanthanides can be directly fed into gas chromatograph for the separation of
individual lanthanides and their estimation.

Acknowledgements
The authors gratefully acknowledge the financial support given by the Department of
Atomic Energy, Government of India, New Delhi for executing this work.

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