Separation and Purification Technology 57 (2007) 294–303

Separations and recovery of indium and gallium using

bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272)
Bina Gupta ∗ , Niti Mudhar, Indu Singh
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667, Uttranchal, India
Received 10 October 2006; received in revised form 6 April 2007; accepted 6 April 2007

Abstract
The extraction of indium(III) and gallium(III) along with the associated metal ions from hydrochloric acid medium by bis(2,4,4-
trimethylpentyl)phosphinic acid (Cyanex 272) has been studied. The extraction profiles of indium(III) and gallium(III) have been investigated
as a function of type and molarity of the acid, nature of organic diluent and concentration of the metal ion and the extractant. The extracting species
have been identified as In(OH)R2 , Ga(OH)R2 and H+ GaCl4 ·2R. It has been possible to strip In(III) and Ga(III) from the organic phase by appropriate
molarity of HCl. Conditions for a number of binary and ternary separations of analytical interest have been optimized. The developed conditions
have been extended to recover pure In(III) from sphalerite and galena and Ga(III) from bottom ash and electronic waste. Loading capacity of the
extractant was evaluated and the results reveal that Cyanex 272 can hold indium(III) up to one-fifteenth and gallium(III) up to one-twentieth of its
molar concentration. The hydrolytic stability and regeneration capacity of the extractant has been assessed.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Gallium; Indium; Cyanex 272; Solvent extraction separation; Recovery

1. Introduction [10] reported an enhancement in the extraction of In(III) when

Indium and gallium have emerged as important strategic
metals as they are vital for the electronic industry. There are
no primary sources of indium and gallium. Indium is gene-
rally found in low concentrations in some sulfide ores of zinc,
copper and lead, from which it is obtained as a by-product. Gal-
lium is mostly associated with aluminum, zinc, and germanium.
Both metals are extensively used in the manufacture of semi-
conductor devices. Since the use of these metals is likely to
increase in the near future, sincere efforts are being made to reco-
ver these metals from leaner sources, namely ores and wastes.
In view of the complexity of materials to be processed and
the purity of metals desired, solvent extraction offers an effec-
tive technology to recover the metals. A variety of extractants,
such as carboxylic acids [1,2], high molecular weight amines,
HMWA [3–5] and oximes [6–9] have been studied. Oximes
generally require addition of modifiers and long equilibration
time whereas carboxylic acids and HMWA suffer from limita-
tions like extractant loss and emulsion formation. Khan et al.
∗ Corresponding author. Tel.: +91 1332 285326; fax: +91 1332 273560.
E-mail address: bvgcyfcy@iitr.ernet.in (B. Gupta).
a mixture of 8-quinolinol and 3,5-dichlorophenol was used.
Alkylphosphorus compounds like bis(2-ethylhexyl)phosphinic
acid [11], di-(2-ethylhexyl)phosphoric acid [12–14], tributyl-
phosphate [15,16], trioctylphosphine oxide [17,18], bis(2,4,4-
trimethylpentyl)dithiophosphinic acid (Cyanex 301) [19] and
trialkylphosphine oxide (Cyanex 923) [20,21] have also been
used as extractants for In(III) and Ga(III). Among these, the
alkylphosphine derivatives are reported to be better extractants
as compared to the other organophosphorus compounds like
tributylphosphate (TBP) and di-(2-ethylhexyl-phosphoric acid)
(DEHPA) because of their low aqueous miscibility and resis-
tance to hydrolysis.
The present study focuses on the use of Cyanex 272 for
the extraction and recovery of In(III) and Ga(III). Cyanex 272,
i.e., bis(2,4,4-trimethylpentyl)phosphinic acid, is a liquid even
at low temperature and has low aqueous solubility, good recy-
cling capacity and miscibility with the commonly used diluents.
The paper embodies distribution studies on In(III) and Ga(III)
along with some commonly associated metal ions. The effect
of various aqueous-phase and organic-phase variables on the
extraction of In(III) and Ga(III) has been investigated. The
extracting species have been identified. Procedures were deve-
loped to recover In(III) from sphalerite and galena and Ga(III)

1383-5866/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2007.04.011
 B. Gupta et al. / Separation and Purification Technology 57 (2007) 294–303 295

from bottom ash and semiconductor waste. The loading capacity

of the extractant has been determined. The hydrolytic stability
and regeneration power of the extractant were assessed.

2. Experimental

2.1. Reagents and materials

Cyanex 272 (Av. Mol. Wt. 290) was obtained from Cytec
Inc., Canada and used without purification. Indium sulfate and
gallium sulfate were AR/GR reagents from Sigma Aldrich.
All other chemicals were AR/GR grade reagents from Thomas
Baker/E. Merck (India). The metal ion solutions were prepared
by dissolving their salts in a minimum amount of appropriate
acid and making up the solution to a known volume with double
distilled water. The metal ion solutions were standardized by the
usual complexometric titrations. The sphalerite and galena were
originally from Rajasthan (India) and obtained from Department
of Earth Sciences, IIT Roorkee, India. Bottom ash sample was
obtained from a local municipal solid waste incinerator (MSWI), Fig. 1. Effect of concentration of different mineral acids on the extraction of
In(III) and Ga(III) using Cyanex 272, [metal ion] = 1.0 × 10−3 mol L−1 , [Cyanex
Belgium and light emitting diodes (LED) waste was procured 272] = 0.5 mol L−1 , [HCl, HNO3 , H2 SO4 ] = 1 × 10−2 to 5.0 mol L−1 .
from the local market of Roorkee, India. In(III)114+114m radioi-
sotope was purchased from Board of Radiation and Isotope
extraction of Ga(III) from H2 SO4 medium was poor in the inves-
Technology, Bhabha Atomic Research Centre, Mumbai (India).
tigated range of acid molarity. In the case of HNO3 medium,
around 60% extraction was achieved at 1 × 10−2 mol L−1 HNO3
2.2. Methodology
followed by a continuous decrease. Detailed studies for In(III)
and Ga(III) were carried out only using HCl medium.
For the distribution studies equal volumes (10 mL) of the
aqueous phase (metal ion solution in appropriate mineral acid)
and organic phase (Cyanex 272 solution in appropriate diluent) 3.2. Effect of equilibration time
were shaken for 5 min to ensure complete equilibration. The two
phases were separated and a suitable aliquot of the aqueous phase The equilibration time was varied from 30 s to 30 min. For
was assayed for the metal ion concentration by ICP-AES (Induc- both In(III) and Ga(III) the equilibrium was attained in about
tively Coupled Plasma-Atomic Emission Spectrometry) or AAS 30 min. In all further studies the two phases were equilibrated
(Atomic Absorption Spectrophotometry). In the case of In(III) for 5 min to ensure complete equilibration.
distribution studies were carried out using its isotope In114+114m .
The activity of the aqueous and organic phases was determined 3.3. Effect of nature of diluent
using a NaI (Tl) scintillation counter. All the values reported are
an average of a minimum of three observations. Other experi- Diluents of varying nature and dielectric constants like
mental conditions are mentioned along with the corresponding toluene, n-hexane, benzene, xylene, nitrobenzene, chloroform
data. and kerosene (bp 160–200 ◦ C) were investigated for the
extraction of In(III) and Ga(III) at 0.1 and 1 × 10−2 mol L−1
3. Results and discussion HCl, respectively, using 0.5 mol L−1 Cyanex 272 solution
(Table 1). No correlation between percent extraction and die-
3.1. Extraction behavior of Ga(III) and In(III) lectric constant was observed for In(III) and Ga(III). For further
studies toluene was used as the diluent. However, kerosene can
The partition studies for In(III) and Ga(III) were carried out replace these diluents for commercial purposes.
from the three mineral acids, namely hydrochloric, nitric and sul-
furic acid, using a 0.5 mol L−1 solution of Cyanex 272 (Fig. 1). 3.4. Effect of temperature
The acid molarity was varied from 1 × 10−2 to 5 mol L−1 acid.
The extraction of In(III) was quantitative in all the three acids The effect of temperature (10–70 ◦ C) on the distribu-
up to 0.1 mol L−1 acid and thereafter it decreased, except in tion of Ga(III) and In(III) was observed at 1 × 10−2 and
the case of HCl where a slight increase was observed beyond 5 × 10−2 mol L−1 HCl, respectively, using 0.2 mol L−1 toluene
1 mol L−1 HCl. The extraction of Ga(III) was quantitative at solution of Cyanex 272. An increase in extraction with increa-
1 × 10−2 mol L−1 HCl but started decreasing thereafter, attai- sing temperature was observed, indicating the process to be
ning a minimum value at 0.1 mol L−1 HCl. It again increased endothermic. Plots between 1000/T and log K (Fig. 2) gave
and attained a quantitative value (∼95%) at 5 mol L−1 HCl. The straight lines with negative slope values of 2.6 Ga(III) and
296 B. Gupta et al. / Separation and Purification Technology 57 (2007) 294–303

Fig. 3. Effect of concentration of Cyanex 272 on the extraction of In(III)

Fig. 2. Effect of temperature on the extraction of In(III) and Ga(III)
[metal ion] = 1 × 10−3 mol L−1 , [Cyanex 272] = 0.2 mol L−1 , [HCl] = (a)
1 × 10−2 mol L−1 and (b) 5 × 10−2 mol L−1 .
3.4 In(III). The values of H as calculated using the Van’t
Hoff equation, −ln K =H/R.1/T, were found to be 50 and
65 kJ mol−1 for Ga(III) and In(III), respectively.
3.5. Effect of Cyanex 272 concentration
To investigate the effect of the concentration of Cyanex 272
on the partition of In(III) and Ga(III), its concentration was
varied from 1 × 10−2 to 0.5 mol L−1 keeping the hydrochloric
acid constant. For In(III) the studies were carried out only at
5 × 10−2 mol L−1 HCl because at higher acidity In(III) shows
poor or negligible extraction. In the case of Ga(III) studies were
carried out at two acid molarities, i.e. 1 × 10−2 and 5.0 mol L−1
HCl because Ga(III) is extracted both at low and high HCl mola-
rities. The results, illustrated in Fig. 3, indicate an increase in
the distribution of the metal ions with increasing concentration
of the extractant. For both the metal ions log–log plots between
concentration of Cyanex 272 and distribution ratio give straight
lines with slope values around two. This indicates the involve-
ment of two molecules of Cyanex 272 in the formation of the
extracting species.
and Ga(III) from hydrochloric acid [metal ion] = 1 × 10−3 mol L−1 , [HCl] = (a)
5 × 10−2 mol L−1 , (b) 1 × 10−2 mol L−1 and (c) 5 mol L−1 .
3.6. Effect of equilibrium pH on the extraction of In(III)
and Ga(III)
In order to ascertain the composition of the extracting species
the effect of equilibrium pH on the distribution of In(III) and
Ga(III) was studied in the pH range 1–3. For both the metal ions
plots between equilibrium pH and log D gave straight lines with
slope values around two (Fig. 4). This indicates the liberation of
two H+ ions per metal atom in the formation of the extracting
species. Based on the results of above slope analysis data, the
extracting In(III) and Ga(III) species in the pH range 1–3 are
proposed as M(OH)R2 or MXR2 (M = In/Ga, HR = Cyanex 272,
X = anion).
3.7. Effect of Cl− ion concentration
Experiments were conducted to investigate the effect of Cl−
concentration on the distribution of In(III) and Ga(III), at a fixed

Table 1
Effect of the nature of diluents on the percent extraction of In(III) and Ga(III)
Diluent Dielectric constant Percent extraction

In(III) Ga(III)

n-Hexane 2.0 99 95
Kerosene (160–200 ◦ C) 2.0 99 96
Xylene 2.2 98 89
Benzene 2.2 92 85
Toluene 2.4 99 91
Chloroform 4.8 65 Hydrolyse
Nitrobenzene 35.7 68 87

Conditions: [metal ion] = 1 × 10−3 mol L−1 ; [HCl] = 0.1 mol L−1 (In(III)); Fig. 4. Effect of equilibrium pH on the extraction of In(III) and Ga(III) [metal
1 × 10−2 mol L−1 (Ga(III)); [Cyanex 272] = 0.5 mol L−1 . ion] = 1 × 10−3 mol L−1 , [Cyanex 272] = 0.2 mol L−1 .
 B. Gupta et al. / Separation and Purification Technology 57 (2007) 294–303 297

Fig. 5. Effect of Cl− concentration on the extraction of Ga(III) [metal

ion] = 1 × 10−3 mol L−1 , [Cyanex 272] = 0.5 mol L−1 , [HNO3 ] = 5 mol L−1 ,
[Cl− ] = 1–5 mol L−1 .
molarity of HNO3 . For In(III) the effect was investigated only at
1 × 10−2 mol L−1 HNO3 and no change in distribution ratio with
increasing Cl− concentration (1 × 10−2 to 0.1 mol L−1 ) was
observed, thus indicating that Cl− does not contribute towards
the formation of the extracting species. In the case of Ga(III) the
effect of Cl− concentration was observed at two acid molarities.
Results revealed that at 1 × 10−2 mol L−1 HNO3 the distribu-
tion of Ga(III) is not affected by increasing Cl− concentration
(1 × 10−2 to 0.1 mol L−1 ). However, at 5 mol L−1 HNO3 the dis-
tribution of Ga(III) increases with increasing Cl− concentration
(1–5 mol L−1 ) and the log–log plot between Cl− and D gave a
straight line with a slope value around four, thus indicating the
involvement of four Cl− ions in the formation of the extracting
species (Fig. 5).
3.8. Equilibrium treatment
Based on the results of slope analysis the extracting species
for In(III) and Ga(III) are In(OH)R2 , Ga(OH) R2 (at low acidity)
and H+ GaCl4 − ·2HR (at high acidity). The following extraction
equilibria can be proposed
In(OH)aq 2+ + H2 R2org ⇔ In(OH)R2org + 2Haq +
(at low acidity)
Ga(OH)aq 2+ + H2 R2org ⇔ Ga(OH)R2org + 2Haq +
(at low acidity)
GaCl4aq − + H2 R2org ⇔ H+ GaCl4 − ·2HRorg (at high acidity)
Cyanex 272 is presumed to exist as a dimer in the orga-
nic phase [22–25]. The results indicate that Cyanex 272 acts
as cation exchanger at low acidity and as a solvating mole-
cule at high acidity. The action of Cyanex 272 both as cation
exchanger and solvating molecule is documented [26] in litera-
ture.
Fig. 6. Effect of concentration of metal ion on the extraction of In(III) and Ga(III)
from hydrochloric acid using 272 [HCl] = 1 × 10−2 mol L−1 (Ga(III)) and
5 × 10−2 mol L−1 (In(III)), [Cyanex 272] = 0.5 mol L−1 (Ga(III)), 0.3 mol L−1
(In(III)), [metal ion] = 10−4 to 5 × 10−2 mol L−1 .
3.9. Effect of metal ion concentration
In order to check the loading capacity of Cyanex 272 for
Ga(III) and In(III) the metal ion concentration was varied
from 1 × 10−4 to 5 × 10−2 mol L−1 keeping the acid molarity
constant at 1 × 10−2 and 5 × 10−2 mol L−1 HCl, respectively,
and the results are shown in Fig. 6. A straight line is obser-
ved up to around 2.2 × 10−2 mol L−1 of Ga(III)organic and
2 × 10−2 mol L−1 of In(III)organic , indicating that the extracting
species remain the same in this concentration range. Beyond
this concentration range loading of the extractant is complete.
The results reveal that the extractant can hold In(III) up to around
one-fifteenth and Ga(III) up to around one-twentieth of its molar
concentration.
3.10. Stripping reagents
Various stripping reagents were tested to strip In(III) and
Ga(III) from the loaded organic phase. The results of stripping
studies at aqueous/organic = 1 are reported in Table 2. Solu-
tions of 1 mol L−1 HCl, 3 mol L−1 HNO3 , 3 mol L−1 H2 SO4 and
0.1 mol L−1 oxalic acid were found effective for the stripping
of In(III) whereas, 0.1–1 mol L−1 HCl and 0.1 mol L−1 oxalic
acid were found effective for Ga(III). In all further studies three
volumes of 1 mol L−1 HCl and two volumes of 0.1 mol L−1 HCl
were used to strip In(III) and Ga(III), respectively.
3.11. Hydrolytic stability and recycling capacity
The stability and recycling capacity of an extractant needs to
be evaluated to assess its utility as an extractant for commercial
purposes. The aforesaid characteristics of Cyanex 272 have been
investigated for In(III) and Ga(III) in terms of change in percent
extraction.
298 B. Gupta et al. / Separation and Purification Technology 57 (2007) 294–303

Table 2
Effect of various stripping reagents on the stripping of In(III) and Ga(III)
Strippant used Stripping Stripping
of In(III) of Ga(III)

0.1 mol L−1 HCl 1 96

0.5 mol L−1 HCl 85 89
1 mol L−1 HCl 94 87
3 mol L−1 HNO3 83 85
3 mol L−1 H2 SO4 93 85
0.1 mol L−1 oxalic acid 39 93
0.1 mol L−1 citric acid 0 86
0.1 mol L−1 tartaric acid 1 81
0.1 mol L−1 EDTA 1 8
3% H2 O2 2 0

Organic:aqueous = 1:1.

The stability of the extractant towards prolonged contact with

HCl was checked by keeping its toluene solution in contact
with 5 mol L−1 HCl and the extraction of the metal ions was
observed every 5 days. No significant decrease in the percent
Fig. 7. Effect of concentration of hydrochloric acid on the extraction of asso-
extraction was observed even after a contact period of 50 ciated metal ions using Cyanex 272 [metal ion] = 1.0 × 10−3 mol L−1 , [Cyanex
days. 272] = 0.5 mol L−1 [HCl] = 1.0 × 10−2 to 5 mol L−1 .
The regeneration capacity of the extractant was assessed by
carrying out successive extraction and stripping cycles for In(III)
and Ga(III). The organic phase after stripping was regenerated 3.14. Binary separations
by washing with water until the washings were neutral. The reco-
very of the metal ion (In(III)/Ga(III)) in each step was calculated 3.14.1. In(III)
from the amount of the metal extracted in the organic phase in The extraction behaviour of Fe(III) is quite similar to
that particular cycle. Results revealed practically insignificant that of In(III) therefore for the In(III)–Fe(III) separation,
change in the percent extraction/stripping of In(III)/Ga(III) up Fe(III) was first reduced to Fe(II) using 5 × 10−2 mol L−1
to 10 cycles studied. ascorbic acid followed by the extraction of In(III) at
0.1 mol L−1 HCl. This results in quantitative extraction of
In(III) leaving Fe(II) in the raffinate. In(III) is separated
3.12. Extraction behaviour of associated metal ions
from Ge(IV)/Ti(IV)/Ga(III)/Tl(III)/Al(III)/Pb(II)/Cd(II)/Zn(II)/
Cu(II)/Mn(II) by extracting the former at 0.1 mol L−1 HCl using
The extraction behavior of associated metal ions, namely
0.5 mol L−1 Cyanex 272. In all of the above cases In(III) was
Ti(IV), Ge(IV), Tl(III), Fe(III), Al(III), Pb(II), Cd(II), Zn(II),
recovered from the organic phase by washing the organic phase
Cu(II), Fe(II) and Mn(II), from HCl medium is shown in
with three volumes of 1 mol L−1 HCl.
Figs. 7 and 8.
Fe(III) exhibited an extraction pattern almost similar to that
of In(III) showing a minimum at 3 mol L−1 HCl. The extrac-
tion of Ti(IV) and Tl(III) was poor at low acidity but attained
a quantitative value at high acidity. The extraction of Ge(IV),
Al(III) and Zn(II) was poor (≤20%) in the investigated range of
acid molarity. The extraction of Fe(II) was negligible at lower
acidity but increased to around 20% at 5 mol L−1 HCl. Pb(II),
Cd(II), Cu(II) and Mn(II) showed negligible (<5%) extraction
in the investigated range of acid molarity.

3.13. Separations

The partition data obtained for the metal ions provide condi-
tions for the separation of In(III) and Ga(III) from each other
and from the associated metal ions. A number of binary and ter-
nary separations of analytical importance involving In(III) and
Ga(III) were carried out. The results indicating the conditions Fig. 8. Effect of concentration of hydrochloric acid on the extraction of asso-
for the separations and the percentage recovery of the metal ions ciated metal ions using Cyanex 272 [metal ion] = 1.0 × 10−3 mol L−1 , [Cyanex
are tabulated in Tables 3–5. 272] = 0.5 mol L−1 [HCl] = 1.0 × 10−2 to 5 mol L−1 .
 B. Gupta et al. / Separation and Purification Technology 57 (2007) 294–303 299

Table 3
Binary separations of In(III) (1.0 × 10−3 mol L−1 ) using 0.5 mol L−1 Cyanex 272
Metal ions Molar ratio Acid molarity Metal ion remaining in Metal ion transferred into Recovery of metal ion from
(mol L−1 ) the aqueous phase (%) the organic phase (%) the organic phase (%)a

In(III):Fe(II) 1:10 0.1 99 ± 1.0, Fe 99 ± 1.1, In 97 ± 1.0, In

10:1 99 ± 1.0, Fe 99 ± 1.2, In 96 ± 1.2, In
In(III):Ge(IV) 1:10 0.1 98 ± 1.2, Ge 99 ± 1.0, In 95 ± 1.0, In
10:1 98 ± 1.0, Ge 98 ± 1.5, In 95 ± 1.0, In
In(III):Ti(IV) 1:10 0.1 98 ± 1.0, Ti 99 ± 1.8, In 96 ± 1.1, In
10:1 98 ± 1.2, Ti 98 ± 1.5, In 95 ± 1.0, In
In(III):Ga(III) 1:10 0.1 97 ± 1.5, Ga 99 ± 1.5, In 96 ± 1.0, In
10:1 98 ± 1.0, Ga 98 ± 1.2, In 97 ± 1.2, In
In(III):Tl(III) 1:10 0.1 98 ± 1.2, Tl 98 ± 1.1, In 96 ± 1.0, In
10:1 97 ± 1.5, Tl 97 ± 1.1, In 96 ± 1.0, In
In(III):Al(III) 1:10 0.1 98 ± 1.1, Al 97 ± 1.5, In 95 ± 1.5, In
10:1 99 ± 1.0, Al 98 ± 1.5, In 95 ± 1.2, In
In(III):Cd(II) 1:10 0.1 99 ± 1.0, Cd 99 ± 1.1, In 96 ± 1.2, In
10:1 99 ± 1.0, Cd 99 ± 1.2, In 96 ± 1.1, In
In(III):Zn(II) 1:10 0.1 99 ± 1.0, Zn 98 ± 1.2, In 95 ± 1.2, In
10:1 99 ± 1.0, Zn 99 ± 1.1, In 96 ± 1.0, In
In(III):Cu(II) 1:10 0.1 99 ± 1.0, Cu 99 ± 1.0, In 96 ± 1.1, In
10:1 99 ± 1.1, Cu 99 ± 1.5, In 95 ± 1.2, In
In(III):Mn(II) 1:10 0.1 99 ± 1.0, Mn 97 ± 1.5, In 95 ± 1.0, In
10:1 99 ± 1.0, Mn 98 ± 1.5, In 96 ± 1.3, In
a In(III) recovered using 1 mol L−1 HCl (three volumes).

Table 4
Binary separations of Ga(III) (1.0 × 10−3 mol L−1 ) using 0.5 mol L−1 Cyanex 272
Metal ions Molar ratio Acid molarity Metal ion remained in the Metal ion transferred into Metal ion recovereda from
(mol L−1 ) aqueous phase (%) the organic phase (%) the organic phase (%)

Ga(III):Ti(IV) 1:10 1 × 10−2 98 ± 1.0, Ti 96 ± 1.5, Ga 95 ± 1.0, Ga

10:1 97 ± 1.0, Ti 97 ± 1.0, Ga 94 ± 1.2, Ga
Ga(III):Ge(IV) 1:10 1 × 10−2 97 ± 1.0, Ge 97 ± 1.2, Ga 98 ± 1.0, Ga
10:1 98 ± 1.0, Ge 96 ± 1.1, Ga 98 ± 1.1, Ga
Ga(III):Tl(III) 1:10 1 × 10−2 97 ± 1.2, Tl 97 ± 1.0, Ga 97 ± 1.0, Ga
10:1 97 ± 1.0, Tl 97 ± 1.1, Ga 95 ± 1.0, Ga
Ga(III):Al(III) 1:10 1 × 10−2 88 ± 1.0, Al (i) 12 ± 1.2, Al (i) 9 ± 1.5, Al
(ii) 95 ± 1.3, Ga (ii) 94 ± 1.0, Ga
10:1 90 ± 1.0, Al (i) 10 ± 1.0, Al (i) 8 ± 1.0, Al
(ii) 96 ± 1.0, Ga (ii) 95 ± 1.2, Ga
Ga(III):Cd(II) 10:1 1 × 10−2 99 ± 1.0, Cd 96 ± 1.0, Ga 95 ± 1.0, Ga
1:10 99 ± 1.0, Cd 95 ± 1.0, Ga 94 ± 1.2, Ga
Ga(III):Zn(II) 10:1 1 × 10−2 95 ± 1.2, Zn 95 ± 1.3, Ga 94 ± 1.2, Ga
1:10 98 ± 1.0, Zn 96 ± 1.0, Ga 95 ± 1.5, Ga
Ga(III):Cu(II) 1:10 1 × 10−2 99 ± 1.2, Cu 97 ± 1.2, Ga 96 ± 1.5, Ga
10:1 99 ± 1.0, Cu 95 ± 1.8, Ga 94 ± 1.1, Ga
Ga(III):Mn(II) 1:10 1 × 10−2 97 ± 1.0, Mn 96 ± 1.0, Ga 94 ± 1.0, Ga
10:1 99 ± 1.0, Mn 94 ± 1.5, Ga 93 ± 1.0, Ga
Ga(III):Fe(III) 10:1 0.1 98 ± 1.0, Ga 97 ± 1.0, Fe 94 ± 1.2, Fe
1:10 98 ± 1.1, Ga 96 ± 1.0, Fe 93 ± 1.1, Fe
Ga(III):In(III) 10:1 0.1 96 ± 1.0, Ga 97 ± 1.5, In 96 ± 1.1, In
1:10 94 ± 1.5, Ga 96 ± 1.0, In 95 ± 1.2, In
a Ga(III) stripped using 0.1 mol L−1 HCl (two volumes). Fe(III) stripped using 3 mol L−1 HCl (two volumes). In(III) stripped using 1 mol L−1 HCl (three volumes).
Al(III) stripped using 1 × 10−2 mol L−1 HCl.
300 B. Gupta et al. / Separation and Purification Technology 57 (2007) 294–303

Table 5
Some important ternary separations involving In(III) and Ga(III) from hydrochloric acid medium using 0.5 mol L−1 Cyanex 272
Metal ions Molar ratio HCl (mol L−1 ) Metal ion remaining in the Metal ions recovereda from the
aqueous phase (%) organic phase (%)

In(III):Ga(III):Cu(II) 1:1:10 1 × 10−2 99 ± 0.91, Cu (i) 99 ± 0.83, Ga

(ii) 99 ± 0.81, In
1:10:1 99 ± 0.75, Cu (i) 97 ± 0.92, Ga
(ii) 99 ± 0.85, In
10:1:1 99 ± 0.75, Cu (i) 99 ± 0.75, Ga
(ii) 98 ± 1.0, In
In(III):Ga(III):Cd(II) 1:1:10 1 × 10−2 98 ± 0.85, Cd (i) 96 ± 1.0, Ga
(ii) 97 ± 0.92, In
1:10:1 99 ± 0.81, Cd (i) 99 ± 0.72, Ga
(ii) 95 ± 1.3, In
10:1:1 99 ± 0.93, Cd (i) 99 ± 1.0, Ga
(ii) 95 ± 1.2, In
In(III):Ga(III):Pb(II) 1:1:10 1 × 10−2 99 ± 0.82, Pb (i) 97 ± 1.0, Ga
(ii) 95 ± 1.2, In
1:10:1 99 ± 1.0, Pb (i) 96 ± 1.2, Ga
(ii) 95 ± 1.0, In
10:1:1 99 ± 0.79, Pb (i) 97 ± 1.0, Ga
(ii) 96 ± 1.3, In
In(III):Ga(III):Zn(II) 1:1:10 1 × 10−2 97 ± 1.3, Zn (i) 97 ± 1.2, Ga
(ii) 95 ± 0.91, In
1:10:1 96 ± 1.1, Zn (i) 99 ± 1.0, Ga
(ii) 99 ± 0.8, In
10:1:1 97 ± 1.5, Zn (i) 98 ± 1.0, Ga
(ii) 98 ± 1.1, In
In(III):Ti(IV):Tl(III) 1:1:10 3.0 99 ± 1.0, In (i) 96 ± 0.8, Tl
(ii) 99 ± 0.7, Ti
1:10:1 99 ± 1.0, In (i) 97 ± 0.9, Tl
(ii) 99 ± 0.8, Ti
10:1:1 99 ± 1.2, In (i) 95 ± 1.2, Tl
(ii) 99 ± 0.8, Ti
Ga(III):Ge(IV):In(III) 1:1:10 1 × 102 98 ± 1.0, Ge (i) 99 ± 1.0, Ga
(ii) 99 ± 1.0, In
1:10:1 97 ± 1.2, Ge (i) 99 ± 1.0, Ga
(ii) 99 ± 1.0, In
10:1:1 97 ± 1.0, Ge (i) 99 ± 1.2, Ga
(ii) 99 ± 1.0, In
Ga(III):Tl(III):Al(III) 1:1:10 (a) 1 × 102 (a) 87 ± 1.0, Al (a) (i) 99 ± 1.0, Ga
99 ± 1.1, Tl (ii) 10 ± 1.0, Al
(b) 3.0 (b) 98 ± 1.0, Al (b) 99 ± 1.0, Tl
1:10:1 (a) 86 ± 1.5, Al (a) (i) 99 ± 1.0, Ga
98 ± 1.0, Tl (ii) 11 ± 1.2, Al
(b) 97 ± 1.5, Al (b) 95 ± 1.5, Tl
10:1:1 (a) 87 ± 1.2, Al (a) (i) 99 ± 1.1, Ga
99 ± 1.3, Tl (ii) 10 ± 1.3, Al
(b) 97 ± 1.1, Al (b) (i) 98 ± 1.2, Tl

(i) and (ii) indicate the sequence in which the metal ions have been stripped from the organic phase.
a Ti(IV) stripped using 3% H O . Tl(III) stripped using 0.5 mol L−1 HCl (three volumes). In(III) stripped using 1 mol L−1 HCl (three volumes). Ga(III) stripped
2 2
using 0.1 mol L−1 HCl (two volumes).

3.14.2. Ga(III)
The separation of Ga(III) from most of the associa-
ted metal ions has been achieved at 1 × 10−2 mol L−1 HCl.
At this acidity Ga(III) is extracted quantitatively leaving
Ti(IV)/Ge(IV)/Tl(III)/Al(III)/Cd(II)/Zn(II)/Cu(II)/Mn(II) in the
aqueous phase. However, Al(III) is partially extracted with
Ga(III). The extracted Al(III) was selectively scrubbed from
the organic phase using 1 × 10−2 mol L−1 HCl followed by the
recovery of Ga(III) using two volumes of 0.1 mol L−1 HCl.
Ga(III)–In(III)/Fe(III) separation was achieved at 0.1 mol L−1
HCl. In(III)/Fe(III) are extracted into the organic layer while
Ga(III) remains in the aqueous phase. In(III) was scrubbed from
the organic phase using three volumes of 1 mol L−1 HCl and
Fe(III) employing 3 mol L−1 HCl.
 B. Gupta et al. / Separation and Purification Technology 57 (2007) 294–303 301

3.15. Ternary separations

3.15.1. In(III)
The separations involving In(III)–Ga(III)–Cu(II)/Cd(II)/
Pb(II)/Zn(II) were achieved by extracting In(III) and Ga(III)
quantitatively at 1 × 10−2 mol L−1 HCl while Cu(II)/Cd(II)/
Pb(II)/Zn(II) remained in the aqueous phase. Ga(III) was strip-
ped from the organic phase using 0.1 mol L−1 HCl followed
by the recovery of In(III) using three volumes of 1 mol L−1
HCl. The separation of In(III)–Ti(IV)–Tl(III) was attained at
3 mol L−1 HCl. Tl(III) and Ti(IV) were quantitatively extrac-
ted leaving In(III) in the aqueous phase. Ti(IV) and Tl(III)
were scrubbed from the organic layer using 3% H2 O2 and
0.5 mol L−1 HCl, respectively. The organic layer was washed
with water in between the use of two different stripping
agents.

3.15.2. Ga(III)
The separation of Ga(III)–Ge(IV)–In(III) was attained at
1 × 10−2 mol L−1 HCl. At this acidity In(III) and Ga(III)
were extracted leaving Ge(IV) in the aqueous layer. Ga(III)
and In(III) were recovered by equilibrating the organic phase
with 0.1 and 1 mol L−1 HCl, in that order. For the sepa-
ration involving Ga(III)–Al(III)–Tl(III) the aqueous phase
acidity was kept at 1 × 10−2 mol L−1 to extract Ga(III). Ga(III)
was recovered using 0.1 mol L−1 HCl. In order to separate
Tl(III)–Al(III) the acidity of the remaining aqueous phase was
adjusted to 3 mol L−1 HCl. Tl(III) was extracted leaving a
major portion of Al(III) in the aqueous layer. The coextracted
Al(III) was scrubbed from the organic phase using 3 mol L−1
HCl followed by the recovery of Tl(III) using 0.5 mol L−1
HCl.
4. Recovery
4.1. Recovery of indium from sphalerite and galena ores
Fig. 9. Recovery of In(III) from sphalerite and galena using Cyanex 272.
4.2. Recovery of gallium from bottom ash and
semiconductor waste
About 0.5 g of the gallium-coated portion of light emitting
diode waste was kept in contact with 5 mL of 2 mol L−1 HCl
for 24 h. The solution was filtered and the filtrate was made
up to 100 mL keeping the overall acidity at 1 × 10−2 mol L−1
HCl. In the case of bottom ash, about 5 g was kept overnight
in contact with 10 mL of 2 mol L−1 HCl and its solution was
made up to a known volume (250 mL) adjusting the acidity to
1 × 10−2 mol L−1 HCl. Dilute ammonia solution was used to
neutralize the excess acid. The LED waste solution and bot-
tom ash solution were analysed for Ga(III), Fe(III), Al(III),
Cu(II), Ni(II), Mn(II) and Zn(II) (Table 7). For the separation
and recovery of Ga(III) a 25 mL aliquot of LED or bottom ash
solution was equilibrated with 25 mL of 0.5 mol L−1 Cyanex
272 (Fig. 10). Ga(III) and Fe(III) were quantitatively extracted

About 2 g of finely powdered sphalerite or galena ore were

dissolved in 10 mL of concentrated HCl containing of a few
drops of concentrated (∼16N) HNO3 . The contents were boi-
led to near dryness. The residue was again boiled with 10 mL of
5.0 mol L−1 HCl and boiled till the volume reduced to 1 mL. The
resulting solution was cooled, filtered and made up to 100 mL
adjusting the acidity to 5 × 10−2 mol L−1 HCl. About 1 g of
ascorbic acid was added prior to the extraction process to reduce
Fe(III) to Fe(II). The ore solutions were then contacted with
equal volumes of 0.5 mol L−1 Cyanex 272 (Fig. 9). In(III) was
quantitatively extracted along with some amount of Zn(II) while
the other associated metal ions, viz., Ti(IV), Tl(III), Ga(III),
Al(III), Pb(II), Cd(II), Cu(II) and Fe(II), remained quantitati-
vely in the aqueous phase. The coextracted Zn(II) was stripped
using 5 × 10−2 mol L−1 HCl. Finally In(III) (∼95%) was reco-
vered using three volumes of 1 mol L−1 HCl with a purity of
∼99%.
The concentration of the metal ions in the initial and the Fig. 10. Recovery of Ga(III) from light emitting diode waste and bottom ash
finally recovered In(III) solutions is given in Table 6. using Cyanex 272.
302 B. Gupta et al. / Separation and Purification Technology 57 (2007) 294–303

Table 6
Recovery of In(III) from sphalerite and galena ores using 0.5 mol L−1 Cyanex 272
Metal ions Composition of initial solution Composition of final solution Percent recovery of In(III)
concentration (mg L−1 ) concentration (mg L−1 )

Sphalerite
In 12 ± 1 11.5 ± 1 95 ± 2
Zn 6806 ± 8 0.2 ± 0.02
Cd 21 ± 2 <0.01
Fe 14 ± 1 <0.01
Cu 12 ± 1 <0.01
Tl 8 ± 1 <0.01
Ti 7 ± 1 <0.01
Ga 5 ± 1 <0.01
Al 1 ± 0.2 <0.01
Galena
In 1.6 ± 0.2 1.49 ± 0.1 95 ± 2
Pb 1380 ± 5 <0.01
Zn 220 ± 2 <0.01
Fe 5 ± 1 <0.01
Cd 2 ± 0.2 <0.01
Cu 1 ± 0.1 <0.01
Mn 1 ± 0.1 <0.01

Table 7
Recovery of Ga(III) from LEDs and bottom ash using 0.5 mol L−1 Cyanex 272
Matrix Metal ions Composition of initial solution Composition of final solution Percent recovery of Ga(III)
concentration (mg L−1 ) concentration (mg L−1 )

LEDs Ga 8 ± 1 7.3 ± 1 91 ± 2
Fe 24 ± 2 <0.01
Ni 18 ± 1 <0.01
Al 10 ± 1 <0.01
Cu 2 ± 0.5 <0.01
Mn 1 ± 0.2 <0.01
Bottom ash Ga 4 ± 0.5 3.8 ± 0.5 95 ± 2
Al 254 ± 4 <0.01
Fe 216 ± 4 <0.01
Cu 43 ± 2 <0.01
Zn 27 ± 2 <0.01
Mn 11 ± 1 <0.01
Ni 2 ± 0.2 <0.01

along with some portion of Al(III) leaving other metals ions
in the aqueous phase. The extracted Al(III) was stripped using
1 × 10−2 mol L−1 HCl, followed by the recovery of Ga(III)
using three volumes of 0.1 mol L−1 HCl. Fe(III) was then scrub-
bed from the organic layer using 0.5 mol L−1 HCl. The recovery
of Ga(III) was ∼90–95% with a purity ∼99%. The results for the
recovery of Ga(III) from bottom ash and semiconductor waste
are tabulated in Table 7.
5. Conclusions
The present studies suggest that Cyanex 272 is a useful extrac-
tant not only for mutual separation of In(III) and Ga(III) but for
their separation from most of the commonly associated metal
ions. For the extraction of In(III) the extractant acts as a cation
exchanger while for Ga(III) it acts as a cation exchanger and a
solvating molecule at low and high acidities, respectively. The
role of Cyanex 272 in both of these capacities is well known.
The extraction does not require the addition of any modifier or
synergist and can be accomplished at room temperature. The
stripping agents used for separations are simple and convenient
for further processing of solutions. The developed conditions
of separations have been successfully extended to recover pure
In(III) from sphalerite and galena and Ga(III) from bottom ash
and electronic waste. The extractant possesses good hydrolytic
stability and regeneration power which favour its use on a large
scale.
Acknowledgements
The financial support to one of the authors by the Department
of Science and Technology (DST), New Delhi, India is gratefully
acknowledged. The authors are thankful to Cytec Canada Inc.
for the gift samples of Cyanex 272. The instrumental facilities
provided by CSIO (Chandigarh) and IIC (IIT Roorkee) for the
analysis of the samples are acknowledged.
 B. Gupta et al. / Separation and Purification Technology 57 (2007) 294–303
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