Electronic Supplementary Material (ESI) for Dalton Transactions.
This journal is © The Royal Society of Chemistry 2015
Np(V) complexation with propionate in 0.1 – 4 M NaCl solutions at
20-85°C†
Supporting information
Aleksandr N. Vasiliev1,3, Nidhu L. Banik*,1, Rémi Marsac1, Daniel R. Froehlich1,2, Jörg Rothe1,
Stepan. N. Kalmykov3, Christian M. Marquardt1
*,1Karlsruher Institut für Technologie (KIT), Institut für Nukleare Entsorgung, P.O. Box 3640,
76021 Karlsruhe, Germany.
2Ruprecht-Karls-Universität
Heidelberg, Physikalisch Chemisches Institut, Im Neuenheimer Feld
253, 69120 Heidelberg,Germany
3Radiochemistry
Division, Chemistry Department, Lomonosov Moscow StateUniversity,
Moscow 119992, Russia.
*Email:
[email protected]
Table caption
Table S1: Stability constants for the formation of 1:1 complex (NpO2+ + Prop- = NpO2(Prop))measured in 0.51 m
NaCl solution as a function of temperature (23–85 °C), and extrapolated to I = 0.
Table S2: Composition of EXAFS samples 1-4.
Logβ0(T)
Temperature /°C
[NaCl] / molal
20
0.506
1.33 ± 0.10
23
0.506
1.26 ± 0.07
23
0.506
1.31 ± 0.06
40
0.506
1.41± 0.10
60
0.506
1.48 ± 0.10
70
0.506
1.57 ± 0.10
85
0.506
1.67± 0.13
Average ± 1σ
Table S1
Sample
[Np(V)] / mmol/L
[propionate-] / mol/L
pHc
[NaCl] / molal
1
0.77
0.48
5.5
0.51
2
0.77
0.48
5.1
1.02
3
0.77
0.48
5.0
2.09
4
0.77
0.48
5.0
4.37
Table S2
Figure caption
Figure S1:(a) Np(V) absorption spectra for various propionate concentration (I = 0.51m; T = 85°C, pHc = 5.0). (b)
Example of a deconvoluted spectrum ([Prop] = 0.10m; I = 0.51m; pHc = 5.0, T = 85°C).
Figure S2:(a) Np(V) absorption spectra for various propionate concentration (I = 3.14 m; T = 23°C, pHc = 5.0). (b)
Example of a deconvoluted spectrum ([Prop] = 0.14 m; I = 3.2 m; pHc = 5.0, T = 23°C).
Figure S3:Np(V) absorption spectra for NpO2+ aqueous ion and the EXAFS sample 1 (I = 0.51 m; T = 23°C, pHc =
5.0, [Prop]tot = 0.48 M). Deconvolution of the later spectrum shows that approximately 95% of the NpO2(Prop)
complex is formed.
Figure S4: Possible structural scheme of Np(V)-propionate complex in the solution a) Bidentate mode b)
Monodentate mode.
0.020
(a)
[NaCl] = 0.5 m
T= 85°C
[Prop]tot
Absorption
0.016
0m
0.04 m
0.012
0.05 m
0.10 m
0.008
0.004
0.000
960
0.015
0.013
965
970
975
980
985
995
1000
λ (nm)
(b)
Measured spectrum (symbol)
and fitted spectrum (line)
[Prop]tot = 0.10 m
0.011
Absorption
990
NpO2+
0.009
NpO2(Prop)
0.007
0.005
Residual
0.003
0.001
-0.001
960
965
970
975
980
λ (nm)
Figure S1
985
990
995
1000
0.012
(a)
[NaCl] = 3.2 m
T= 23°C
[Prop]tot
0.010
0m
Absorption
0.008
0.02 m
0.03 m
0.006
0.07 m
0.10 m
0.004
0.002
0.000
960
0.009
965
970
975
980
λ (nm)
985
990
995
1000
(b)
Measured spectrum (symbol)
and fitted spectrum (line)
[Prop]tot = 0.10 m
0.007
Absorption
NpO2+
0.005
NpO2(Prop)
0.003
Residual
0.001
-0.001
960
965
970
975
980
λ (nm)
Figure S2
985
990
995
1000
Absorption
0.22
0.20
0.18
0.16
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
-0.02
[Np(V)]tot = 0.77 mM
[NaCl] = 0.5 M
T = 23°C
[Prop]tot = 0 M
[Prop]tot = 0.5 M
Measured spectrum (symbol)
and fitted spectrum (line)
Residual
970
975
980
985
λ (nm)
Figure S3
990
995
1000
O
OH2
O
Np
O
OH2
OH2
O
a)
O
H2O
Np
O
O
O
b)
Figure S4
OH2
OH2
OH2