Separation Methods Utilizing Oxalate‐HCl on Anion Exchange Resins
Dan McAlister and Phil Horwitz
Eichrom Workshop October 31, 2012
Anion Exchangers
H
C C
H2
CH3
CH2N+ CH3 ClCH3
-
Cl
R1 +
R2 N CH3
R3
R1
+ N
H
Cl
R2
R3
Strong Base Anion Exchange Resin (1x8)
1.2 meq/mL
TEVA
(Quaternary Amine)
0.65 meq/mL
Weak Base
(Tertiary Amine)
0.65 meq/mL
Anion Exchange
TcO4‐, ReO4‐, MoO42‐, WO42‐
Th(NO3)5‐, UO2Cl42‐, FeCl4‐
O
-
O
O
-
+ HCl
O
Strelow, et al., Analytical Chemistry, 44(14), pp 2352‐2356, 1972.
+
Speciation of 0.05 M Oxalic Acid vs [H ]
100
O
% Species
80
O
O-
HO
60
O
-
pKa1 = 1.2
O
O-
O
pKa2 = 3.7
40
O
20
O
HO
OH
0
1
10
0
10
-1
10
-2
-3
10
10
+
[H ], M
-4
10
-5
10
-6
10
Increasing HCl Concentration
O
-
O
O
O
-
O
HO
Mn+
O
O
→ MCl
-
O
HO
→ MClx‐
Chloride competition for extraction
O
OH
Example #1
Metal
Mg
Al
Ga
In
Ion
Charge
2+
3+
3+
3+
1
2.76
6.2
6.4
6
Oxalate logK
2
3
11.4
12.3
11.4
15.8
17.8
14.5
1
0.2
‐1.0
0.01
2.3
Chloride logK
2
3
3.6
11.4
4.0
14.5
1x8
5
Weak Base
TEVA
Dw Mg < 1
Dw Mg < 1
10
In
Ga
Al
4
10
3
10
2
Dw
10
1
10
0
10
Dw Mg < 1
-1
10
-2
10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
10
o
Elution on 2mL Cartridge of 1x8 Resin (50-100 m), 21(1) C, 2mL/min
3
10
2
10
0.05M
Oxalate
1.0M HCl
Al
Mg
1
10
mg/L
0.05M
Oxalate
0.5M HCl
0.05M
Oxalate
0.01M HCl
1.0 M
HNO3
Ga
In
0
10
-1
10
-2
10
-3
10
0
5
10
15
20
Bed Volumes
25
30
35
o
Elution on 2mL Cartridge of TEVA Resin (50-100 m), 21(1) C, 2mL/min
3
10
0.05M
Oxalate
0.5M HCl
0.05M
Oxalate
0.01M HCl
2
10
0.05M
Oxalate
1.0M HCl
Al
1
mg/L
10
In
Ga
Mg
1.0 M
HNO3
0
10
-1
10
-2
10
-3
10
0
5
10
15
20
Bed Volumes
25
30
35
o
Elution on 2mL Cartridge of Weak Base Resin (50-100 m), 21(1) C, 2mL/min
3
10
2
10
0.05M
Oxalate
1.0M HCl
Al
Mg
1
10
mg/L
0.05M
Oxalate
0.5M HCl
0.05M
Oxalate
0.01M HCl
1.0 M
HNO3
In
Ga
0
10
-1
10
-2
10
-3
10
0
5
10
15
20
Bed Volumes
25
30
35
Example #2
1x8
5
Weak Base
TEVA
10
U(VI)
Nb(V)
Ni(II)
V(V)
4
10
3
10
2
Dw
10
1
10
0
10
Dw Mn(II) < 1
Dw Mn(II) < 1
Dw Ni and Mn < 1
-1
10
-2
10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
10
o
Elution on 2mL Cartridge of 1x8 Resin (50-100 m), 21(1) C, 2mL/min
3
10
2
10
0.05M
0.05M
0.05M
Oxalate Oxalate Oxalate
0.2M HCl 1.0M HCl 4.0M HCl
0.05M
Oxalate
0.01M HCl
Ni(II)
Mn(II)
1
Nb(V)
V(V)
10
mg/L
1.0 M
HNO3
U(VI)
0
10
-1
10
-2
10
-3
10
0
5
10
15
20
25
Bed Volumes
30
35
40
45
o
Elution on 2mL Cartridge of Weak Base Resin (50-100 m), 21(1) C, 2mL/min
3
10
2
10
0.05M
0.05M
0.05M
Oxalate Oxalate Oxalate
0.2M HCl 1.0M HCl 4.0M HCl
0.05M
Oxalate
0.01M HCl
1.0 M
HNO3
U(VI)
1
Nb(V)
V(V)
Mn(II)
10
mg/L
Ni(II)
0
10
-1
10
-2
10
-3
10
0
5
10
15
20
25
Bed Volumes
30
35
40
45
o
Elution on 2mL Cartridge of TEVA Resin (50-100 m), 21(1) C, 2mL/min
3
10
2
10
0.05M
0.05M
0.05M
Oxalate Oxalate Oxalate
0.2M HCl 1.0M HCl 4.0M HCl
0.05M
Oxalate
0.01M HCl
U(VI)
V(V)
Mn(II)
1
1.0 M
HNO3
Nb(V)
10
mg/L
Ni(II)
0
10
-1
10
-2
10
-3
10
0
5
10
15
20
25
Bed Volumes
30
35
40
45
Example #3
1x8
5
Weak Base
TEVA
10
4
10
3
10
Cu(II)
Ti(IV)
Mo(VI)
2
Dw
10
1
10
0
10
Dw Co(II) < 1
Dw Co(II) < 1
Dw Co(II) < 1
-1
10
-2
10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
10
o
Elution on 2mL Cartridge of 1x8 Resin (50-100 m), 21(1) C, 2mL/min
3
10
0.05M
Oxalate
0.5M HCl
0.05M
Oxalate
0.01M HCl
2
10
0.05M
Oxalate
2.0M HCl
Ti(IV)
0.5M
NH4OH
1.0 M
NH4NO3
Cu(II)
Mo(VI)
1
10
mg/L
Co(II)
0
10
-1
10
-2
10
-3
10
0
5
10
15
20
25
Bed Volumes
30
35
40
o
Elution on 2mL Cartridge of Weak Base Resin (50-100 m), 21(1) C, 2mL/min
3
10
0.05M
Oxalate
0.5M HCl
0.05M
Oxalate
0.01M HCl
2
10
Ti(IV)
Cu(II)
Co(II)
1
0.05M
Oxalate
2.0M HCl
1.0 M
NH4NO3
Mo(VI)
10
mg/L
0.5M
NH4OH
0
10
-1
10
-2
10
-3
10
0
5
10
15
20
25
Bed Volumes
30
35
40
o
Elution on 2mL Cartridge of TEVA Resin (50-100 m), 21(1) C, 2mL/min
3
10
0.05M
Oxalate
0.5M HCl
0.05M
Oxalate
0.01M HCl
2
10
Ti(IV)
Cu(II)
Co(II)
1
0.05M
Oxalate
2.0M HCl
1.0 M
NH4NO3
Mo(VI)
10
mg/L
0.5M
NH4OH
0
10
-1
10
-2
10
-3
10
0
5
10
15
20
25
Bed Volumes
30
35
40
1x8
5
Weak Base
TEVA
10
4
10
3
10
Dw Li, Na, K,
Rb, Cs < 1
2
Dw
10
Dw Li, Na, K,
Rb, Cs < 1
Dw Li, Na, K,
Rb, Cs < 1
1
10
0
10
-1
10
-2
10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
10
1x8
5
Weak Base
TEVA
10
4
10
3
Pd(II)
Pt(II)
Au(I)
Pb(II)
10
2
Dw
10
1
10
0
10
Dw Mg, Ca, Sr,
Ba, Mn(II) <1
Dw Mg, Ca, Sr,
Ba, Mn(II) <1
-1
10
-2
10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
Dw Mg, Ca, Sr,
Ba, Mn(II) <1
1
-2
10 10
-1
10
0
10
HCl, M
1
10
1x8
5
Weak Base
TEVA
10
Zn(II)
Cu(II)
Be(II)
Cd(II)
4
10
3
10
2
Dw
10
1
10
0
10
Dw Be, Mg, Ca, Sr,
Ba, Mn(II) <1
Dw Be, Mg, Ca, Sr,
Ba, Mn(II) <1
-1
Dw Be, Mg, Ca, Sr,
Ba, Mn(II) <1
10
-2
10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
10
1x8
5
Weak Base
TEVA
10
4
10
3
10
2
Dw
10
1
10
Bi(III)
In(III)
Fe(III)
Ga(III)
Al(III)
0
10
-1
10
-2
10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
10
1x8
5
Weak Base
TEVA
10
4
10
3
10
2
Dw
10
1
10
Sn(IV)
Ti(IV)
Zr(IV)
Hf(IV)
0
10
-1
10
-2
10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
10
1x8
5
Weak Base
TEVA
10
4
10
3
10
2
Dw
10
1
10
Ta(V)
Nb(V)
V(V)
0
10
-1
10
-2
10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
10
1x8
5
Weak Base
TEVA
10
4
10
3
10
2
Dw
10
1
10
W(VI)
Mo(VI)
U(VI)
0
10
-1
10
-2
10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
-2
10 10
-1
10
0
10
HCl, M
1
10
k' on Weak Base Resin Oxidation
Element
State
Sn
IV
W
VI
Pd
II
Group
14
6
10
0.01
4
>10
9800
4
>10
4
0.10
4
>10
9900
4
>10
0.20
4
>10
9600
4
>10
Mo
VI
6
>10
>10
4
>10
Bi
III
15
5000
5000
>10
Pt
Ta
Cd
In
Nb
II
V
II
III
V
10
5
12
13
5
>10
N/A
N/A
8100
1200
4
>10
3400
2100
9000
1500
4
U
Zn
Ti
Fe
Zr
Hf
Ga
Pb
V
Al
Cu
Ni
Th
VI
II
IV
III
IV
IV
III
II
V
III
II
II
IV
An
12
4
8
4
4
13
14
5
13
11
10
An
>10
N/A
9300
N/A
N/A
N/A
2000
N/A
9486
7983
263
85
ppt
4
>10
50
2000
4
>10
6900
1200
1800
4.0
1300
200
17
0.5
ppt
4
3
M, HCl (0.05M Oxalic acid)
0.50
1.0
2.0
4
4
4
>10
>10
>10
9800
710
150
4
>10
9500
5000
4
>10
4
>10
4
>10
>10
5400
3000
8300
1000
4
>10
170
1400
4
>10
930
600
1100
4.4
400
340
8.0
<0.5
ppt
4
4
>10
>10
4500
4000
420
870
4
>10
9000
380
2600
260
570
140
15
14
3.7
0.5
<0.5
ppt
4
3
3
>10
< 0.5
1800
Re
VII
7
N/A
>10
>10
>10
Cr
III
6
N/A
< 0.5
< 0.5
< 0.5
Au
I
11
2300
2800
2700
2300
k' Co, Mn, Be, Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs <0.5 for all HCl concentrations
4
>10
4
>10
>10
4500
3700
41
91
4
3.0
4
>10
78
2500
4
>10
4
>10
>10
44
4900
51
5.8
4
>10
920
130
19
66
27
4.3
22
0.5
< 0.5
0.6
<0.5
ppt
4
3
>10
< 0.5
970
4.0
4
>10
130
1100
4
>10
4
4
>10
>10
45
4800
110
2.3
4
>10
33
4900
250
1.4
180
4
>10
12
200
1.0
1.2
92
25
0.5
< 0.5
3.2
<0.5
3.2
8200
4
>10
1.8
4
>10
0.2
<0.5
970
18
0.4
< 0.5
13
<0.5
< 0.5
>10
4
>10
0.8
4
>10
0.4
<0.5
1200
10
0.7
< 0.5
31
<0.5
< 0.5
3
>10
< 0.5
900
3
>10
< 0.5
830
4
4
4
3
k' on TEVA Resin Oxidation
Element
State
Group
M, HCl (0.05M Oxalic acid)
0.50
1.0
2.0
0.01
0.10
0.20
4
4
4
4
4
3.0
4
4.0
4
Sn
W
Pd
IV
VI
II
14
6
10
N/A
9800
9800
>10
9600
9200
>10
9200
9100
>10
4900
5000
>10
510
4800
>10
110
1300
>10
40
450
>10
45
180
Mo
VI
6
9600
9300
9200
9900
9600
5100
>10
4
>10
Bi
III
15
5100
4800
>10
4
>10
4
400
4
4
4
4
4
4
4
4
>10
4
>10
>10
4
4
Pt
Ta
Cd
In
Nb
II
V
II
III
V
10
5
12
13
5
N/A
N/A
N/A
8300
1000
>10
2100
650
250
1500
>10
2200
1200
180
1400
>10
3800
2000
38
310
>10
51
2900
16
29
>10
40
4800
25
6.1
>10
38
4100
47
4.1
>10
14
4300
78
2.3
U
Zn
Ti
Fe
Zr
Hf
Ga
Pb
V
Al
Cu
Th
VI
II
IV
III
IV
IV
III
II
V
III
II
IV
An
12
4
8
4
4
13
14
5
13
11
An
2100
N/A
2300
N/A
N/A
N/A
4200
N/A
3000
2700
18
ppt
2100
48
1400
6500
3800
6000
3000
0.7
310
110
2.2
ppt
1300
100
870
8800
2300
670
180
6.0
55
16
0.7
ppt
130
320
300
45
53
19
9.7
14
4.7
0.7
< 0.5
ppt
23
450
90
4.3
2.2
1.4
0.4
18
0.4
< 0.5
< 0.5
ppt
70
7700
6.7
130
0.4
1.0
55
19
0.4
< 0.5
< 0.5
40
350
9300
1.5
1100
0.2
<0.5
1500
12
0.6
< 0.5
< 0.5
36
>10
4600
0.4
1100
0.1
<0.5
3200
7.3
1.3
< 0.5
< 0.5
<0.5
3
3
3
>10
< 0.5
4600
3
>10
< 0.5
3400
3
>10
< 0.5
2300
3
>10
< 0.5
2300
Re
VII
7
N/A
>10
>10
>10
Cr
III
6
N/A
< 0.5
< 0.5
< 0.5
Au
I
11
1400
3900
4500
4600
k' Co, Mn, Be, Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs <0.5 for all HCl concentrations
4
3