Electronic Supplementary Material (ESI) for Dalton Transactions.
This journal is © The Royal Society of Chemistry 2017
Electronic Supplementary Information
Speciation of indium(III) chloro complexes in the solvent extraction
process from chloride aqueous solutions to ionic liquids
Clio Deferm, Bieke Onghena, Tom Vander Hoogerstraete, Dipanjan Banerjee, Jan Luyten,
Harald Oosterhof, Jan Fransaer and Koen Binnemans*
-S1-
(k)*k3
(k)*k3
(k)*k3
(k)*k3
(k)*k3
k)*k3
2
4
6
8
10
12
0.5 M HCl
5
14
A
0
-5
1 M HCl
5
0
-5
3 M HCl
5
0
-5
6 M HCl
5
0
-5
9 M HCl
5
0
-5
12 M HCl
5
0
-5
2
4
6
8
10
12
14
-1
k(Å )
FT magnitude (a.u.)
1
15
10
5
0
15
10
5
0
15
10
5
0
15
10
5
0
15
10
5
0
15
10
5
0
2
3
4
5
B
0.5 M HCl
1 M HCl
3 M HCl
6 M HCl
9 M HCl
12 M HCl
1
2
3
4
5
R +  (Å)
Fig. S1 Indium K-edge k3-weighted EXAFS spectra (A) and the corresponding FTs (B) for the indium(III)
complexes in aqueous solutions as a function of the HCl concentration (5 g L-1 indium). Experimental
data (black) and theoretical fit (red) are shown.
-S2-
Intensity (a.u.)
0.5 M HCl
1.0 M HCl
3.0 M HCl
6.0 M HCl
9.0 M HCl
12 M HCl
200
100
0
-100
 (ppm)
Fig. S2 115In NMR spectra of the aqueous phase before extraction at 60 °C containing 5 g L-1 indium(III)
and varying HCl concentration: 0.5 M (─), 1 M (─), 3 M (─), 6 M (─), 9 M (─) and 12 M (─).
-S3-
0
1
n(IL)/n(InIL)
5
2
3
4
4
3
Intersection point
X = 1.24
Y = 1.32
2
Aliquat® 336, 0.5 M HCl
n(IL)/n(InIL)
5
4
3
2
Intersection point
X = 0.86
Y = 1.53
1
Aliquat® 336, 5 M HCl
n(IL)/n(InIL)
5
4
3
Intersection point
X = 1.16
Y = 1.24
2
1
Cyphos® IL 101, 10 M HCl
5
n(IL)/n(InIL)
6
Cyphos® IL 101, 0.5 M HCl
1
4
3
2
Intersection point
X = 0.92
Y = 0.95
1
Aliquat® 336, 10 M HCl
5
n(IL)/n(InIL)
5
4
3
2
Intersection point
X = 1.02
Y = 1.11
1
0
1
2
3
4
5
6
Added equivalents of IL
Fig. S3 Number of moles of ionic liquid over the number of moles of extracted indium (n(IL)/n(InIL)) as
a function of the number of ionic liquid equivalents added, at constant initial metal concentrations of
indium and 60 °C. Aqueous phase: initial indium(III) concentration of 50 g L-1.
-S4-
2
6
8
10
12
14
16
0.5 M
4
k)*k3
4
18
A
0
-4
-8
8
3 M HCl
(k)*k3
4
0
-4
-8
8
6 M HCl
(k)*k3
4
0
-4
-8
8
12 M HCl
(k)*k3
4
0
-4
-8
2
4
6
8
10
12
-1
k(Å )
14
16
18
0
FT magnitude (a.u.) FT magnitude (a.u.) FT magnitude (a.u.) FT magnitude (a.u.)
8
20
1
2
3
4
0.5 M HCl
5
B
15
10
5
0
20
3 M HCl
15
10
5
0
20
6 M HCl
15
10
5
0
20
12 M HCl
15
10
5
0
0
1
2
3
4
5
R +  (Å)
k3-weighted
Fig. S4 Indium K-edge
EXAFS spectra (A) and the corresponding FTs (B) for the indium(III)
complexes in Aliquat 336 as a function of the HCl concentration. IL phase obtained after extraction
containing 5 g L-1 indium. Experimental data (black) and theoretical fit (red) are shown.
-S5-
2
4
6
8
10
12
14
16
-1
5 g L In
18
A
(k)*k3
4
0
-4
-8
8
-1
60 g L In
(k)*k3
4
0
-4
-8
8
-1
120 g L In
(k)*k3
4
0
-4
-8
2
4
6
8
10
12
-1
k(Å )
14
16
18
0
FT magnitude (a.u.) FT magnitude (a.u.) FT magnitude (a.u.)
8
1
2
3
4
-1
20
5 g L In
5
B
15
10
5
0
60 g L-1 In
20
15
10
5
0
120 g L-1 In
20
15
10
5
0
0
1
2
3
4
5
R +  (Å)
Fig. S5 Indium K-edge k3-weighted EXAFS spectra (A) and the corresponding FTs (B) for the indium(III)
complexes in Aliquat 336 as a function of the indium concentration. IL phase obtained after extraction
containing 0.5 M HCl. Experimental data (black) and theoretical fit (red) are shown.
-S6-
A
Intensity (a.u.)
0.5 M HCl
1 M HCl
3 M HCl
6 M HCl
9 M HCl
12 M HCl
600
500
400
300
200
100
0
-100
 (ppm)
B
Intensity (a.u.)
0.5 M HCl
1 M HCl
3 M HCl
6 M HCl
9 M HCl
12 M HCl
600
500
400
300
200
100
0
-100
 (ppm)
Fig. S5 115In NMR spectra of the InCl3Cyphos IL 101 (A) and InCl3Aliquat 336 system (B) at 60 °C
obtained after extraction with 5 g L-1 indium(III) and varying HCl concentration: 0.5 M (─), 1 M (─), 3 M
(─), 6 M (─), 9 M (─) and 12 M (─).
-S7-
A
Intensity (a.u.)
5 g L-1 In
10 g L-1 In
20 g L-1 In
40 g L-1 In
60 g L-1 In
80 g L-1 In
100 g L-1 In
120 g L-1 In
600
500
400
300
200
100
0
-100
Intensity (a.u.)
 (ppm)
600
B
5 g L-1 In
10 g L-1 In
20 g L-1 In
40 g L-1 In
60 g L-1 In
80 g L-1 In
100 g L-1 In
120 g L-1 In
500
400
300
200
100
0
-100
 (ppm)
Fig. S6 115In NMR spectra of the InCl3Cyphos IL 101 (A) and InCl3Aliquat 336 system (B) at 60 °C
obtained after extraction with 0.5 M HCl and varying indium(III) concentration: 5 g L-1 (─), 10 g L-1 (─),
20 g L-1 (─), 40 g L-1 (─), 60 g L-1 (─), 80 g L-1 (─), 100 g L-1 (─) and 120 g L-1 (─).
-S8-
Intensity (a.u.)
600
A
0.25 M CaCl2
0.5 M CaCl2
1.5 M CaCl2
3.0 M CaCl2
4.5 M CaCl2
6.0 M CaCl2
500
400
300
200
100
0
-100
Intensity (a.u.)
 (ppm)
600
B
0.25 M CaCl2
0.5 M CaCl2
1.5 M CaCl2
3.0 M CaCl2
4.5 M CaCl2
6 M CaCl2
500
400
300
200
100
0
-100
 (ppm)
Fig. S6 115In NMR spectra of the InCl3Cyphos IL 101 (A) and InCl3Aliquat 336 system (B) at 60 °C
obtained after extraction with 5 g L-1 indium(III) and varying CaCl2 concentration: 0.25 M (─), 0.5 M (─),
1.5 M (─), 3 M (─), 4.5 M (─) and 6 M (─).
-S9-