Redox and molecular speciation of actinyl ions in aqueous

and deep eutectic solvent media

By

Ashutosh Srivastava
CHEM01201704008

Bhabha Atomic Research Centre,

Mumbai-400085, India

A thesis submitted to the

Board of Studies in Chemical Sciences
In partial fulfillment of requirements For the Degree of

DOCTOR OF PHILOSOPHY
Of
HOMI BHABHA NATIONAL INSTITUTE

April, 2023
 STATEMENT BY AUTHOR

This dissertation has been submitted in partial fulfillment of requirements for an advanced

degree at Homi Bhabha National Institute (HBNI) and is deposited in the Library to be made

available to borrowers under rules of the HBNI.

Brief quotations from this dissertation are allowable without special permission, provided that

accurate acknowledgement of source is made. Requests for permission for extended quotation

from or reproduction of this manuscript in whole or in part may be granted by the Competent

Authority of HBNI when in his or her judgment the proposed use of the material is in the

interests of scholarship. In all other instances, however, permission must be obtained from the

author.

Ashutosh Srivastava

ii
 DECLARATION

I, hereby declare that the investigation presented in the thesis has been carried out by me. The

work is original and has not been submitted earlier as a whole or in part for a degree /diploma

at this or any other Institution / University.

Ashutosh Srivastava

iii
Dedicated to...........

My Parents
&
Family

iv
 Acknowledgement
“Research is an unending quest to unravel the truth, which has widened human vision,
opened newer boulevards, and lightened the dark vague facets of science.”

I would like to thank God, for letting me through all the difficulties. I have experienced your
guidance day by day and without your blessings, this study would not have been possible.
As one flower makes no garland, this dissertation would not have been accomplished without
the support and encouragement of numerous peoples including my family, friends,
colleagues, and well-wishers who contributed in many ways for its successful completion.
First and foremost, I would like to express my deep and sincere gratitude to my guide Dr.
Neetika Rawat for her continuous support, patience, motivation, enthusiasm, erudite
suggestions, and friendly nature throughout the tenure of my Ph.D. I have been fortunate to
have a mentor like her who gave me freedom to explore on my own and to investigate novel
research, and at the same time providing valuable guidance and teaching me how to question
my thoughts and express ideas. A special thanks to Prof. B. S. Tomar for his constant
encouragements and supports; I had started the present thesis work under his direction. I
must thank to Dr. A. K. Satpati for his motivation, valuable advice, discussions and clearing
my scientific doubts.
I would also like to thank my doctoral committee members Dr. S. Kannan, Dr. P. K.
Mohapatra, Dr. T. K. Ghanty and Dr. A. Bhattacharya for their valuable time,
encouragement, critical evaluation of works and insightful comments and suggestions during
the progress review and pre-synopsis presentations. Once again, my sincere thanks to Dr. P.
K. Mohapatra, Associate director RC & I group and Head Radiochemistry division, BARC,
Mumbai for his interest, unlimited support, and motivation. His valuable suggestions for
shaping layout of the chapters of present thesis are highly appreciated.
My sincere thanks also go to my senior colleagues Dr. M. S. Murali, Dr. S. Chaudhury, Dr.
Ankita Rao, Dr. Rama Mohan Rao Dumpala, Dr. Pranaw Kumar and Dr. S. A. Ansari for
their motivation, support, fruitful discussions, unconditional guidance and help whenever I
needed. In addition, I specially want to thank all co-authors in my all publications for their
great scientific contributions. I also thank my lab-mates Shiny S. Kumar, Jisha Pillai, Ritu
Singh and Pooja for their cooperation, moral support and help during this work. I must
thank Dr. Bal Govind Vats and Dr. Praveen Kumar Verma for their support and help.
Finally, words are not sufficient to express my gratitude to my cherished family members who
mean a lot to me. I will always be indebted infinitely to my parents for their spiritually
limitless love, care, sacrifice, motivation, and support throughout my life. I am grateful to my
elder brother (Kinshuk) and sisters (Kanak and Anupama) for their deep love, motivation,
confidence and desired the best for me always. My special heartily thanks to my wife
Anupriya for her unconditional love, endless support, devotion, encouragement, and
continuous faith in me to purse my dreams. As a decent companion she helps me always
overcoming all hurdles of my life. Special thanks to my parents-in-laws for their love and
support. I would like to express my love to my daughter Ashree who gave me strength to
accomplish my Ph.D.

Ashutosh Srivastava

v
 Contents

Chapter 1. Introduction 1
1.1 Introduction 2
1.2. Indian Nuclear power Programme 3
1.3. Nuclear Fuel Cycle, types, and Challenges 3
1.4. Radioactive waste, classification, and storage 5
1.4.1. Solid radioactive waste 5
1.4.2. Gaseous radioactive waste 5
1.4.3. Liquid waste 5
1.4.4. Storage of nuclear radioactive waste: Deep geological repository (DGR) 6
1.5. General Properties of Actinides 7
1.5.1. Electronic Configuration 7
1.5.2. Oxidation States, ion types, and redox potential 7
1.5.3. Complexation, hydrolysis, and polymerization 9
1.5.4. Aqueous Speciation 11
1.5.5. Molecular-orbital diagram 12
1.6. Speciation definition and its roles in actinide chemistry 13
1.6.1. Environmental aspects of Actinide chemistry 16
1.6.2. Dissolution and analysis 23
1.6.3. Stability of unusual oxidation state in solution 32
1.6.4. Separation schemes advancement (oxidation states or designing novel 35
ligands)
1.7. Choice of Complexing medium (chelating ligands and novel solvents) 36
1.8. Green and Sustainable Chemistry 43
1.9. Motivation of the work 44
1.10. Scope of the Thesis 46
1.11. Chapters’ distribution 49

Chapter 2. Experimental and Instrumentations 50

2.1 Introduction 51
2.2. Sample preparation 51
2.3. Summary of used Techniques 54
2.3.1 Electrochemical methods, experimental set-up, and parameters 54
2.3.2 UV-Visible absorption spectroscopy 70
2.3.3 EXAFS 71
2.3.4 Calorimetry 73
2.3.5 Electro-spray ionization mass spectrometry (ESI-MS) 75
2.3.6 Theoretical calculations 77
2.4 Other supporting techniques 79
2.5 Details about the equations 81
2.6 Determination of stability constant of complex 83
2.7 Green Chemistry Matrices 85

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2.8. Detection limit of various technique and advantages of 86
electrochemistry for speciation

Chapter 3. Redox Speciation of Uranyl with Citrate and Phenylphosphonic 88

acid (carboxylate and phosphonate based organic chelators)
3.1. Introduction 89
3.2. Experimental and Instrumentations 92
3.3. Results and Discussions 92
3.3.1. Speciation with varying pH 92
3.3.2. Kinetic study of U(VI)Citrate system 97
3.3.3. Reduction Mechanism 100
3.3.4. Chronoamperometry 101
3.3.5. In Situ Spectroelectrochemical study 102
3.3.6. Determination of stability constant 104
3.3.7. Redox behavior with pH 106
3.3.8. The Eh-pH plot 107
3.3.9. The Ep vs. log ν plot 108
3.3.10. Estimation of number of electron transfer at pH 5 108
3.3.11. The ip vs. √ν plot 108
3.3.12. Determination of heterogeneous electron transfer rate constant for 109
UO2PhPO3
3.3.13. Reduction mechanism 109
3.3.14. ESI-MS measurements 109
3.3.15. Determination of stability constant of U(VI)-PPA complex 110
3.4. Conclusions 110

Chapter 4. Electrochemical, Spectroscopic and Theoretical Studies on 123

Redox Speciation of Neptunium with Phenylphosphonic Acid
4.1. Introduction 124
4.2. Experimental and Instrumentation 126
4.3. Results and discussion 126
4.3.1. Redox characteristic with pH
4.3.2. Kinetic Study of reduction process of Np-PPA complexes 129
4.3.3. Reduction mechanism 130
4.3.4. Complexation mechanism 130
4.3.5. Spectrophotometric Studies 131
4.3.6. DFT Calculations 132
4.3.6.1. Structure of NpO2(H2O)5+ and NpO2(H2O)52+ 132
4.3.6.2. Complexation of Np(V) with PPA 133
4.3.6.3. Complexation of Np(VI) with PPA 133
4.3.7. Determination of stability constant of [NpVO2PhPO3]- 134
4.4. Conclusions 134

vii
Chapter 5. Chemical and Redox Speciation of Uranyl ions with three 143
heterobifunctional Phosphonocarboxylate Chelates
5.1. Introduction 144
5.2. Experimental, Instrumentations and Equations 146
5.3. Results and Discussion 146
5.3.1. Protonation of PCs 146
5.3.2. Aqueous speciation (molecular and redox) of uranyl(VI) with PCs 146
5.3.2.1. Molecular speciation (Stoichiometry and Thermodynamic) and physical 146
evidence by UV–Visible spectrophotometry, Calorimetry and ESI-MS
5.3.2.2. Redox Speciation 148
5.3.3. Structural studies-binding mode: (EXAFS and DFT) 152
5.3.3.1. EXAFS study 152
5.3.3.2. Theoretical Study (DFT calculations) 153
5.3.4. Pathways of electron transfer (reduction-mechanism) 156
5.3.5. Aqueous speciation (stability and structure) of uranyl(V) with PCs 156
and Spectroelectrochemical evidence
5.3.6. Aqueous speciation modelling of uranyl(VI) and uranyl(V) with PCs 158
5.4. Conclusions 160

Chapter 6. Speciation of Actinides in Deep eutectic solvents 177

6.1. Introduction 178
6.2. Experimental 181
6.3. Results and Discussion 181
Part (a)
6.3.1. Direct Sequestration and Characterization 181
6.3.2. Speciation studies: (i) Redox speciation by electrochemistry and In situ 183
UV-vis spectroelectrochemistry
(ii) Molecular speciation by EXAFS 188
6.3.3. Molecular dynamics (MD) and Density functional theory (DFT) 189
simulations
6.3.4. Interaction of Uranyl with Maline in aqueous phase by Luminescence 191
and Solution Thermodynamic Studies
6.3.5. Uranium Analysis methodology 192
Part (b)
6.3.6. Characterizations 194
6.3.6.1 Physical properties of imidazolium-based DES 194
6.3.6.2 Karl Fischer Titrations 195
6.3.6.3 IR spectra 195
6.3.6.4 TGA-DSC data 195
6.3.6.5 UV-Visible spectral data 197
6.3.7. Dissolution Mechanism 197
6.3.8. Redox Speciation of uranium oxides dissolved in DES 197
6.3.8.1. Potential window and redox behaviour of the DES 1 and 2 197
6.3.8.2. Voltammograms 198

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6.3.8.3. Validation of Calibration plots by redox-titrimetric biamperometry 202
6.3.8.4. Scan rate variation and determination of transport and kinetic 202
parameters
6.3.8.5. DES vs. Aqueous 204
6.3.8.6. Reduction-Mechanism 205
6.3.9. In situ spectroelectrochemical Studies 206
6.3.10. Simulation studies 208
Part (c) 209
6.3.11. Redox speciation of Americium in CDHC-MA DES 209
6.4. Conclusions 211

Chapter 7. Summary and Future outlooks 238

Appendix 244-264
References 265-278
Publications 279

ix
 Figures, Tables and Schemes

Figures Caption Page

no

Figure 1.1 Indian three stage nuclear program 3

Figure 1.2 Nuclear fuel cycle 4
Figure 1.3 Redox potential and stable oxidation states of actinides 9
Figure 1.4 Aqueous species distribution of Uranyl in (a) absence (b) presence of 12
carbonate
Figure 1.5 Molecular orbital diagram of uranyl (VI) ion 13
Figure 1.6 Schematic diagram of Metrical speciation in complexing medium 15
Figure 1.7 Importance of speciation nuclear fuel cycle 16
Figure 1.8 Overview of actinide behaviour in the environment 18
Figure 1.9 Possibilities of electron transfer process and associated kinetic behaviour 22
Figure 1.10 Scheme of the general idea of metal oxide processing in non-aqueous 26
medium
Figure 1.11 Geometry of Pentavalent uranium (UO2+) in cation-cation interaction (CCI) 33
Figure 1.12 Choice of complexing agents 37
Figure 1.13 Schematic diagram of DES synthesis 37
Figure 1.14 Structures for several HBAs and HBDs for DES synthesis 39
Figure 1.15 Phase diagram of a two-component mixture representing the eutectic point 40
Figure 1.16 Schematic diagram for actinide metal ion hijacking by DES 43
Figure 1.17 The Principles of Green Chemistry 44
Figure 1.18 Pictorial representation of chapter distribution in present dissertation 49
Figure 2.1 Experimental methodologies used for speciation studies 51
Figure 2.2 Synthesis of Imidazolium based DES 53
Figure 2.3 Pictorial representation of series of steps during electrodic reaction 55
Figure 2.4 E-T curve and cyclic voltammetry plot with varying concentration profiles 57
1 to 7
Figure 2.5 Types of electron transfer at electrode 58
Figure 2.6 (a) The waveform of DPV and (b) the differential pulse voltammogram 60
Figure 2.7 (a) Potential modulation (b) Single potential cycle in square-wave 61
voltammetry (c) typical square-wave voltammogram
Figure 2.8 (a) Potential-time waveform (b) change of concentration profile with time 63
(c) typical current-time response
Figure 2.9 (a) Current-time waveform (b) typical potential-time response 64
Figure 2.10 Spectroelectrochemistry principle and set-up 64
Figure 2.11 (a) Three electrode set-up (b) schematic diagram of a three electrode potentiostat (c)
Potentiostats used in the present studies 69
Figure 2.12 The representative XAFS spectra showing various regions of XAFS (XANES,
EXAFS etc.) and information obtained from them
73
Figure 2.13 Basic component of ESI-MS 76
Figure 2.14 Schematic representation of the electro-spray ionization process 76

x
Figure 3.1 Cyclic voltammetry curves: (a) [UO22+]= 10-5 M, (i) in absence of Citrate at 112
pH 4 (ii) in presence of [Citrate]= 5x10-3 M at pH 4 (iii) same as (ii) at pH
6.5; (b) [UO22+]= 10-3 M, (i) in absence of Citrate at pH 4 (ii) in presence of
[Citrate]= 5x10-2 M at pH 4 (iii) same as (ii) at pH 6.5 (c) Square wave
Voltammetry curves with varying pH, Condition: [UO22+]= 10-3 M,
[Citrate]= 1x10-3 M (d) Variation of cyclic voltammograms with scan rates
Figure 3.2 Eh-pH plots, Condition: (a) [UO22+]= 10-5 M, [Citrate]= 5x10-3 M and I= 0.1 113
M NaClO4 (b)[ UO22+] = 10-3 M , [Citrate]= 5x10-2 M and I= 0.1 M NaClO4;
(c) for Peak II (d) for Peak III, both (c) & (d) are at [UO22+]= 10-3 M,
[Citrate]= 1x10-3 M and 0.1 M NaClO4.
Figure 3.3 (a) E vs. logν plot for peak I and (b) i vs. √ν plot (c) is the variation of peak 114
current functions (i/√ν) with scan rates at pH 4 while variation of
chronopotentiometric constant (iτ1/2 ) with i for several values of pH is in
(d), Conditions: (a) to (d) [UO22+]= 10-5 M, [Citrate]= 5x10-3 M and I= 0.1
M NaClO4.
Figure 3.4 (a) E(V) vs. log [1-(t/τ)1/2] plots at pH 4 (b) Variation of 115
chronopotentiometric constant (iτ1/2) with pH at fixed i = 10x10-8 A. (c)
Variation of Peak Current function (i/√ν) with pH at 50 mV/sec scan rate
(d) Variation of E(t=0) with log i at pH 5
Figure 3.5 Plot of i(A) vs. t(sec) with varying pH is in (a) and (b) is the plot of i(A) vs. 116
t-1/2. Condition: (a) and (b) [UO22+]= 1x10-5 M, [Citrate]= 5x10-3 M and I=
0.1 M NaClO4.
Figure 3.6 (a) & (b) are the absorption spectra with varying potential from -0.01 V to - 116
1 V after every 25 min. (c) and (d) are the absorption spectra measured with
varying both potential (from -0.1 V to -1 V) and time of pentavalent
uranium. The appearance of absorption bands are at 732, 743, 756, 774,
785, 798 and 982.8 nm respectively. Condition: (a) to (d) [UO22+]= 4x10-3
M, [Citrate]= 4x10-3 M and I= 0.1 M NaClO4
Figure 3.7 . The Variation of Ep (a) with [UO22+] concentration at fixed [Citrate]= 117
1x10-2 M, I= 0.1 M NaClO4 and pH 4; (b) The variation of F0[UO22+ Conc.]
with [UO22+ Conc.] at pH 4
Figure 3.8 (i) and (ii) are the CV plots (a) UO22+ at 10-5M in absence of PPA and (b) in 119
presence of 5x10-3M PPA conc. (i) at pH 4 (ii) at pH 5. The 3D plots of (iii)
CV at pH 4 and 4.5 (iv) DPV at pH 4 and pH 4.5. The 3D plots of (v) CV
and (vi) DPV at pH 4,7 and 9
Figure 3.9 The Eh-pH plot (i) for reduction peak I and (ii) reduction peak II. (iii) Plot 120
of F0 (PPA) vs. [PPA Conc.]
Figure 3.10 The i(A) vs E(V) plot with increasing scan rate from 50 to 100mV/s (a) at 121
pH 3 ; (b) at pH 5. The E vs logν plot for peak I (c) at pH 3 and (d) at pH 5.
The i(A) vs √ν plot (e) at pH 3; (f) at pH 5.
Figure 4.1 (a) Cyclic voltammetry curves: [Np]=10-5 M and I= 0.1 M NaClO4, Black 136
voltammogram is in absence of phenylphosphonic acid at pH 2.5 while Red
voltammogram is in presence of [PPA]= 1x10-3 M at same pH. (b)
Differential pulse voltammetry curves: at same solution conditions as
described in above.
Figure 4.2 Eh-pH plots, (a) For reduction peak I and (b) For reduction peak II; 136
Condition: [Np]=10-5 M, [PPA]= 1x10-3 M and I= 0.1 M NaClO4.

Figure 4.3 (a) Variation of cyclic voltammograms with scan rates from 20 mV/sec to 137
90mV/sec. (b) E vs. logν plot for Np(V)-Phenylphosphonate (Reduction
peak II); Condition: at [Np]=10-5 M, [PPA]= 1x10-3 M and I= 0.1 M
NaClO4 (c) and (d) are i vs. √ν plot for Np(VI)-Phenylphosphonate
(reduction peak I) and Np(V)-Phenylphosphonate (reduction peak II);

xi
 Condition: (a)-(c) at [Np]=10-5 M, [PPA]= 1x10-3 M and I= 0.1 M NaClO4

Figure 4.4 Schematic representation for the complex formation of Np(H2O)5 by 138
PhPO3H2
Figure 4.5 The absorbance spectra (left) and the molar absorbance (right) of the NpO2+ 138
- PPA complexation. ([NpO2+] = 4.23 X 10-5 M with 0.5 M PPA at pH 2)

Figure 4.6 Correlation between the stability constant (log β) and the magnitude of 139
wavelength shift (∆λmax) where, ∆λmax = λ(NpO2L)-λ(NpO2+)

Figure 4.7 Optimised structure of Np(V) and Np(VI) complexes with PPAH- and PPA2- 139
(A) Np(V) with PPAH-- NpO2PPAH (B) Np(V) with PPA2- -NpO2PPA- (C)
Np(VI) with PPAH-- NpO2PPAH+ (D) Np(VI) with PPA2- - NpO2PPA (Red
– Oxygen, Blue – Neptunium, yellow – Phosphorous, Gray – Carbon, white
– Hydrogen)
Figure 4.8 The variation of F0[PPA Conc.] with [PPA Conc.] 140
Figure 5.1 The complexation of uranyl(VI) with Phosphonopropionate (3-PPA) (i) 162
Absorption spectra with increasing the addition of 3-PPA; (ii) The
absorption spectra of individual species: free uranyl(VI) and 1:1 UO22+-3-
PPA complex. (iii) Hyperquad fitted speciation diagram for the
complexation of uranyl with phosphonoacetate (PAA) ([UO22+] = 0.003 M,
[PAA] = 0.02 M).
Figure 5.2 Cyclic Voltammetry Plots of Uranyl(VI) and its complexes with PCs. (i) 163
[UO22+]= 10-5 M (ii-iv) [UO22+] with [PFA], [PAA] and [3-PPA] at 5x10-4
M respectively (v) [PAA]= 5x10-4 M; all at I= 0.1 M NaClO4 and pH=4.
Figure 5.3 (i) Eh-pH plots of [UO22+]= 10-5 M with [3-PPA]= 5x10-4 M, (ii) i(A) vs. 164
E(V) plot with varying scan rates 10-100 mV/sec and (iii) E vs. log ν plot of
UO22+ with 3-PPA, (iv) i(A) vs. √ν plot of UO22+-3-PPA.
Figure 5.4 The different electrochemical plots of UO22+-PAA. (i) is the variations of 165
peak current functions (i/√ν) with scan rates (CV). (ii) is the variation of
chronopotentiometric constants (iτ1/2) with i(A) (CP). (iii) is the plots of
i(A) vs. t-1/2 (CA). (iv) is the E(V) vs. log [1-(t/τ)1/2] plots (CP). i(A) and
E(V) are considered as icom and Ecom.
Figure 5.5 i) Normalized XANES spectra of UO2CO3, U(VI)-PAA, U(VI)-PFA and 166
U(VI)-3-PPA at U L3-edge. (ii) Fourier transformed EXAFS spectra of
U(VI)-PFA, U(VI)-PAA and U(VI)-3-PPA at U L3-edge. The experimental
spectra are represented by Scatter points and the theoretical fit is
represented by Solid line.
Figure 5.6 Optimized DFT structures: (a) Structures for the optimized geometries of 167
Uranyl(VI)- monoprotonated CP complexes. (Colour code of atoms: Blue -
Uranium, Red - Oxygen, Gold - Phosphorous, Grey - Carbon and White -
Hydrogen). (b) Structure for the optimized geometries of uranyl(V)-CP
complex. (Colour code of atoms: Blue-Uranium, Red-Oxygen, Gold-
Phosphorous, Grey-Carbon and White-Hydrogen).
Figure 5.7 Spectroelectrochemical electrolysis data at pH 4. (a) is the absorption 168
spectra with varying cathodic potentials in the wavelength region 375 nm to
550 nm (b) is the absorption spectra with varying cathodic potentials in the
wavelength region 560 nm to 1000 nm
Figure 5.8 Speciation plots of uranyl(VI) and uranyl(V). (a) Uranyl(VI) with 3-PPA 169
(H- is the -OH group, M is uranyl(VI) and L is 3-PPA) (b) uranyl(V) with
CP (PAA), citrate and carbonate chelators (c) percentage of pH region of
uranyl(v) stability with organic chelators.

xii
Figure 6.1 Characterization: (a) IR spectra of UO3 and UN dissolved Maline solution. 214
TGA plots (b) Wt% loss versus Temperature (c) The UV-Visible absorption
spectra of UO3 dissolved in Maline solution, blank Maline and UO22+ and
malonic acid complex in aqueous solution.
Figure 6.2 Redox speciation of Uranium matrices in Maline. Cyclic voltammetry plots 215
of (a) UO3, UN, UO2, U3O8 and blank Maline (b) U std., U metal and U3Si2
(c) PuO2 and (U, Pu)O2 (d) Scan rates variation studies by Cyclic
voltammetry (CV) on UO3 dissolved in Maline.
Figure 6.3 Insitu UV-visible Spectroelectrochemical Data. (i) Absorbance spectra of 216
U(VI) in Maline with applied cathodic potentials. (ii) and (iii) are the
appearance of new absorption peaks with applied cathodic potentials related
to U(IV) and U(V) species in Maline respectively.
Figure 6.4 (i) Normalised XANES spectra at U L3-edge along with standard samples. 217
(ii) Fourier transformed EXAFS spectra of U sample at U L3-edge in (a) R
space and (b) K space along with the best fit. The experimental spectra are
represented by Scatter points and the theoretical fit is represented by Solid
line.
Figure 6.5 (a) Equilibrated structure of the Maline system containing Uranyl ion in the 218
presence of water molecule. System representation with 5% water. color
code: Steel: UO2 species; Red & White: H2O; Cyan: Cl; rest are malonic
acid and choline (b) Optimized structures of [UO2-(MA)2-(H2O)2]2+ (c) The
calculated energy levels (eV) of the MOs of the [UO2-(MA)2-(H2O)2]2+
complex using B3LYP/TZ2P/ZORA level of theory.
Figure 6.6 (a) The luminescence intensity of Uranyl with increasing concentration of 219
Maline (b) Comparison of luminescence intensity of Uranyl with Malonic
acid and Maline at two different concentrations (c) The absorption spectra
for Uranyl titration with Maline (d) Deconvoluted spectra representing the
absorption profile for the pure components (e) Raw calorimetric data for the
interaction of Uranyl with Maline (f) Integrated Data showing the
cumulative heat released on successive additions of DES solution to fixed
volume of Uranyl solution; [UO22+] = 0.01 M, [DES] = 0.48 M
Figure 6.7 (a) Differential pulse voltammetry plots with increasing concentration of 220
UO3 (b) Calibration Plot of UO3 dissolved in Maline solution obtained with
increasing concentration (c) Electrochemical interference study on UO3
dissolved Maline with other metal ions dissolved Maline (d) Selectivity of
Maline for different dissolved metal ions.
Figure 6.8 (a) measured density of DES 1 with varying temperature and fitting (b) 225
measured viscosity of DES 1 and fitting (c) Thermograms obtained in DSC
for pure components.
Figure 6.9 (a) IR spectra of the UO3 and UO2 dissolved in DES 1 (b) UV-Vis spectra 226
of UO3 dissolved DES 1 (c) TGA data of the UO3 and UO2 dissolved in
DES in terms of the wt % loss with temperature (d) derivative plot (e)
electrochemical potential window and redox peaks of DESs.
Figure 6.10 (a) and (b) are the CV and DPV plots for the oxides of uranium dissolved in 227
DES 1. (c) and (d) are the CV and DPV plots for the oxides of uranium
dissolved in DES 2. The concentration of uranium oxides ~ 4.5 to 5 mg/ml.
Figure 6.11 (a) and (b) are the DPV plots with increasing concentration of UO3 (peak I 228
and II) in DES 1. (c) and (d) are the ip(A) versus conc. UO3 plots in DES 1
(e) Ep vs. concentration of UO3 in DES 1
Figure 6.12 (a) is the recorded DPV plots for U3O8 by varying its concentration (DES 229
2). (b) (i) to (iii) are the ip(A) vs conc. U3O8 plots for reductive peaks I to
III.

xiii
Figure 6.13 (i) and (ii) are the scan rates variation studies on uranium oxides dissolved 230
in DES 1 in cyclic voltammetry (CV). (a) is the CV plots recorded with
varying scan rates. (b) is the E vs. logν plots. (c) is the ln|ip| vs. Ep-Ef plots
(d) is the i(A) vs. √ν plots of their respective uranium oxides.
Figure 6.14 In situ UV-visible Spectroelectrochemical Data. (a) Absorbance spectra of 231
U(VI) in DES 1 with applied cathodic potentials. (b) and (c) are
appearances of new absorption peaks with applied cathodic potentials
related to U(V) and U(IV) species in DES 1 respectively.
Figure 6.15 In situ UV-visible Spectroelectrochemical Data. (a) Absorbance spectra of 232
U(VI) in DES 2 with applied cathodic potentials with the isosbestic point.
(b) (i) to (iii) showing the appearance of new absorption peaks with applied
cathodic potentials related to U(V) species in DES 2 respectively
Figure 6.16 MD simulation results: (a) Geometries of (i) C8mimBr and (ii) malonic acid 233
molecules. (b) Enlarged picture of DES-uranyl system. (i) UO2-Br2, UO2-
Br3 and UO2-Br4 and (ii) UO2-2malonic acid. Here, U: pink; O: Red; Br:
light blue; malonic acid: Blue. DFT simulation results: (c) Optimized
structures of [UO2-(MA)2-(Br)2] (d) The calculated energy levels (eV) of
the MOs of the [UO2-(MA)2-(Br)2] complex using B3LYP/TZ2P/ZORA
level of theory.
Figure 6.17 (i) (a) Latimer diagram for Am in 1 M perchloric acid (b) dissolved sample 234
of Am-oxide in DES (c) UV-Visible absorption spectra of Am in DES (ii)
(a) CV plots of Am-oxide in CDHC-MA and blank CDHC-MA (b) DPV
plots with increasing concentration of Am in CDHC-MA (c) CV plots with
varying scan rates from 10 mV/sec to 150 mV/sec (d) the ip vs. √ν plot

Table and Caption Page

Schemes no

Table 1.1 Classifications of Solid and Gaseous waste 6

Table 1.2 Classification of DESs 38
Table 2.1 Diagnostic criteria for ET-processes in terms of various redox parameters 59
Table 2.2 Detection limits of various techniques for speciation of actinides 87
Table 3.1 The observed slopes and calculated value of number of protons from Eh- 117
pH plots
Table 3.2 The observed slope and calculated value of D0 from i vs. √ν plot 118
Table 3.3 The value of αn and k0f,h − 2−
for [UO2Cit] and [(UO2)2Cit2] at lower and 119
higher current densities

Table 3.4 The species with their m/z values 122

Table 4.1 The observed slopes and calculated value of number of protons from Eh- 140
pH plots.
Table 4.2 The observed slope and calculated value of D0 from i vs. √ν plot. 140
Table 4.3 The stability constant, λmax, ∆λmax and molar absorbance of the 1:1 141
complex of NpO2+ with PPA along with the available literature data on
1:1 NpO2+ complexes of some dicarboxylate (acronym full forms: mal-
malonic acid, oda- oxydiacetic acid, ida- iminodiacetic acid, ppa- phenyl
phosphonic acid)
Table 4.4 Calculated energies of all the species (EX) and interaction energies of 141
Np(V) and Np(VI) complexes (∆E)

xiv
Table 4.5 Bond distances (Å) in all the Np species involved in complexation process 142
Table 5.1 Protonation constants for three Phosphonocarboxylates. (Experimental 170
conditions: T = 298 K, P = 0.1 M Pa and I =1.0 M NaClO4).
Table 5.2 Assignment of Species from m/z values obtained in ESI-MS spectra. 171
Table 5.3 Thermodynamic parameters for the complexation of Uranyl with three 172
PCs. (Experimental conditions: T = 298 K, P = 0.1 M Pa and I =1.0 M
NaClO4, [UO22+] = 0.003 M, [L] = 0.02 M; L = PFA/PAA/3-PPA).

Table 5.4 Summary of Cyclic Voltammetry data of UO22+-PCs and comparison of 172
potential of U(VI)/U(V) redox couple with various complexing chelators.

Table 5.5 Summary of electrochemical parameters obtained from fitting of Plots. 173
Table 5.6 Bond length, coordination number and disorder factor obtain by EXAFS 174
fitting for U(VI)-PCs at U L3-edge.
Table 5.7 The binding energy (B.E) and free energy of formation for all the three 175
uranyl(VI)-CP complexes in gaseous as well as aqueous phase
Table 5.8 The calculate bond distances (in A0) between the uranium and the 175
coordinating atoms in stable optimized geometries of uranyl(VI)-CP
complexes.
Table 5.9 Stability constant, bond distances and partial charges of Uranyl(V)-CP 176
complexes
Table 6.1 Electrochemical thermodynamic and kinetic parameters of U matrices in 221
Maline. (Irrev. = Irreversible redox behaviour)
Table 6.2 Bond length (R (Å), phase-corrected), coordination number (N) and 222
disorder factor (s2) obtain by EXAFS fitting.

Table 6.3 Analytical figures of merit and validation of developed analytical 222
methodology for Uranium matrices sample determination in Maline.
Table 6.4 Comparison of Green metrics of present methodology (direct sequestering 223
and analysis of uranium matrices with Maline supramolecular scaffold)
and previous method (i.e., hazardous acidic/additives dissolution and
biamperometery analysis).
Table 6.5 The observed and calculated weight loss along with the liberated 235
molecules at various temperatures in TG-DSC.
Table 6.6 Redox thermodynamic, Diffusion coefficient and kinetic parameters of 236
UO3 and UO2 in DES

Table 6.7 Validation of calibration plots of DES 1 and 2 by concentration 236

determination of uranium oxides.
Table 6.8 The calculated values of structural parameters in simulated systems and 237
the calculated values of Gibbs free energy (kcal/mol) of complexation in
the gas phase.
Table 6.9 Experimentally and theoretically obtained parameters of Am in DES 237
Scheme 3.1 The Pka values of (a) Citrate (b) Phenylphosphonic acid (PPA) 91

Scheme 5.1 Structure of Phosphonocarboxylates 145

xv
Scheme 5.2. Coordination modes of PC chelators 161

Scheme 5.3 Pathway of electron transfer (reduction-mechanism) of Uranyl(VI)-PC 161

complexes

Scheme 6.1 The plausible reduction mechanism of UO3 in Maline 213

Scheme 6.2 Dissolution procedure 224

Scheme 6.3 Mechanistic electron transfer process 224

xvi
 List of Abbreviation

NFC Nuclear fuel cycle

SNF Spent Nuclear Fuel
HLW High Level Waste
LLW Low Level Waste
DGR Deep geological repository
NMs Nuclear materials
IAEA International atomic energy agency
DA Destructive analysis
NDA Non-Destructive analysis
ECE Electron transfer coupled chemical electron
transfer
ICI Irreversible electron transfer coupled
chemical irreversible electron tranfser
PCET Proton coupled electron transfer
SET Single electron transfer
Aq Aqueous
Non-Aq Non-Aqueous
IL(s) Ionic liquid(s)
PPA Phenylphosphonic acid
PFA Phosphonoformic Acid
PAA Phosphonoacetic Acid
3-PPA 3- Phosphonopropanoic acid
DES(s) Deep Eutectic Solvent(s)
PC Phosphonocarboxylate
EXAFS Extended X-ray Absorption Fine Structure
CV Cyclic Voltammetry
DPV Differential pulse voltammetry
SWV Square wave voltammetry
ESI-MS Electro-spray ionization mass spectrometry
CP Chronopotentiometry
CA Chronoamperometry
PUREX Plutonium Uranium reduction extraction
SANEX Selective ActiNide Extraction
SESAME SElective Separation of AMericium by
Electrochemical means
IMHB Intramolecular Hydrogen Bonding
DFT Density functional theory
MD Molecular dynamics
SEC Spectro-electrochemistry

xvii
 SYNOPSIS

Nuclear energy, a mature technology and low carbon energy source, is going to be one of the

major sources of energy as the demand for energy and concern of reducing harmful

greenhouse gas emission grows worldwide. Actinides viz., uranium (U) and plutonium (Pu)

are used as a fissile material for nuclear reactor, which on irradiation in nuclear reactor

generates the large volume of spent nuclear fuel (SNF) consisting of highly radioactive

unused fuels, minor actinides, and fission products. The reprocessing and safe management

of nuclear waste of SNF are important concern for sustainable development of nuclear

energy. Aqueous (Aq) solution occupies a strategic place in both front and back end of

nuclear fuel cycle (NFC) related to (1) hydrometallurgical processing and reprocessing

namely, dissolution, solvent extraction, and recovery of actinides, and (2) assess the safety of

nuclear waste disposal. Non-aqueous (Non-Aq) solvents such as ionic liquids and deep

eutectic solvents etc. are the new generation of media being explored globally for various

industrial applications including nuclear industry. The solution chemistry of the early actinide

elements (U, Np, Pu and Am) are of vital importance and interesting to the nuclear industry.

One of the important feature of early actinide elements is the formation of actinyl ions

(AnO2n+; n= 1, 2). Actinyl ions are the important species in the nuclear fuel cycle because of

their multifaceted and highly characteristic chemical behavior [1-4]. These ions have dynamics

behaviour in Aq solution and can form stable complexes and nanoclusters with various

organic and inorganic ligands in Aq and Non-Aq solvents. The chemical behaviour of actinyl

ions, such as complex formation, dissolution, solubility, sorption, precipitation, and

immobilization, depend on several key factors of solutions chemistry such as hydration,

hydrolysis, solubility product, coordination modes, redox potentials, and stability constants [1-
4]
. Thus, understanding the solution chemistry of early actinides, particularly actinyl ions, in

Aq and Non-Aq are crucial. Novel research with the aim of probing direct metrical

xviii
information about redox and molecular speciation of actinyl ions in both Aq and non-Aq as a

function of physicochemical conditions are quintessential requirement for (1) describing in-

depth solution chemistry, (2) efficient design of separation processes, and (3) fundamental

understanding migration of actinyl ions in environment. This will help in the advancement of

reprocessing of SNF and the geological disposal strategies of nuclear wastes and to mitigate

challenges of NFC.

Traditional approaches of reprocessing of SNF fall into two major categories as

aqueous based hydrometallurgical i.e., PUREX (Plutonium Uranium Reduction Extraction)

and pyrochemical processes. The complexity of these processess and resulting technical

challenges toward sustainable nuclear energy necessitates various research activities related

to the development of alternative methods based on Non-Aq, viz. ionic liquids (ILs) and deep

eutectic solvents (DESs). Furthermore, for chemical quality control, nuclear material

accounting, and nuclear forensic applications, the routine analysis of nuclear materials (NMs)

samples or environmental surface swipe samples in analytical laboratory requires the

development of novel fast dissolution methods using less hazardous chemicals to avoid time

consuming dissolution procedures involving hazardous/corrosive inorganic acids and

generation of harmful NOx gases. Non-Aq method for reprocessing of SNF and dissolution of

NMs has numerous advantages, such as minimum waste generation, excellent thermal and

radiation stability, lower criticality risk, compact infrastructure, and wide electrochemical

windows. DESs are the nascent entries to the repertoire of Non-Aq chemical media and

represent an environmentally benign “green and sustainable” alternative to the conventional

organic solvents and ionic liquids in the 21st century. DESs have emerged as a new type of

designer solvents and have synthesized by combining a hydrogen bond acceptor (HBA) and a

hydrogen bond donor (HBD), which can form eutectic mixture with large depression in
[5]
melting point through extensive hydrogen bonding interactions . DESs have many

xix
favorable characteristics such as easy preparation, a large electrochemical window

(promising electrolyte), non-toxicity, biodegradability, unique salvation potential, tunable

physicochemical properties. DESs can be used to diverse filed of research viz., metal and

metal oxides processing, electrochemistry, extraction, and metal recovery processes.

Speciation is a significant chemical aspect for Aq and non-Aq solution chemistry of

actinides. IUPAC defines speciation as “species distribution based on their oxidation states

or stoichiometries.” Metrical knowledge about a metal ion’s speciation of actinides in

solutions depends basically on three main factors (1) Actinide redox processes, (2) Solid

actinide phases, and (3) Complexation reactions [1-4]. The actinide speciation in solution is a

daunting task and are highly challenging because (1) unlike most elements of the periodic

table, there is absence of geologic precedent, (2) their diverse chemistries, including rich

redox behavior, radioactivity, and susceptibility towards hydrolysis and condensation

[1, 3]
reactions , and (3) the relative stabilities of the actinide oxidation states and the types of

complexes formed with the actinide cations in these states vary for Aq and Non-Aq solutions.

In addition, speciation of actinides is very mobile and the effect of pH on their speciation is

still couched. Based on aforesaid reasons, the independent knowledge of chemical behavior

of early actinides is critical in determining a robust description of solution speciation.

Therefore, attempts should be made to provide cohesive database on redox and molecular

speciation for in-depth understanding of Aq and Non-Aq solution chemistry of early

actinides. Speciation is a cornerstone of different facets of nuclear fuel cycle and it may be

accomplished as below: (i) Actinide environmental aspects (aqueous chemistry), (ii)

Dissolution, analysis, and recovery in non-aqueous medium (ILs and DESs), (iii) Stability of

unusual oxidation state in solution, and (iv) Separation schemes advancement (oxidation

states based or designing novel ligands)

xx
(i) Actinide environmental aspects (aqueous chemistry): The presence of chelating ligands

and redox environment are two im

important
portant factors which affects the fate and distribution of
[1-4]
4]
actinides in the environment . The complexation of actinides with chelating agents alters

their redox, hydrolysis and diffusion behavior and thereby retards or enhances the migration.

The conversion
ersion from an oxidized/potentially mobile form to a more reduced/potentially less

mobile form is an approach for immobilization of actinides.

(ii) Dissolution, analysis and recovery in Non

Non-Aq medium (DESs): Reactivity of the

metal in the dissolved non-aqueous

ueous medium depends on the metal species formed through

dissolution in ILs or DESs since it affects the metal matrices processing and electrochemical

behavior, such as solubility, dissolution mechanism, complexation and interaction with their

constituents,, and redox potentials [5]. Metal species dissolved in DESs will experience a very

strong ionic atmosphere and hence its chemistry fundamentally will be different from

traditional molecular solvents. Foreseeing the applications of DESs as a novel media, probing
pr

the mechanistic redox and molecular speciation are essential to understand the chemistry and

the mechanism that is occurring in processing and solvent extraction and the redox

parameters for actinides analysis and recovery by electrochemistry.

xxi
(iii) Stability of unusual oxidation state in solution: Pentavalent uranium (UVO2+) has

historically been reported as unusual (rare) oxidation state of uranium in the comprehensive

1969 review of “U(V) chemistry” by Selbin and Ortego et al. [6] in Aq solution. It is unstable

and rapidly undergoes disproportionation in Aq solution. Hence, gaining information about

Aq speciation of pentavalent uranium is highly challenging, resulting in its elusive Aq

chemistry and a knowledge gap related to the comprehensive understanding of its stability

and structure in the Aq solution. Its Aq speciation plays a crucial role in the solubility and

mobility of uranium in the environment and in investigating the mechanism of biotic and

abiotic reduction of uranyl species in the environment.

(iv) Separation schemes advancement (oxidation states based or designing novel

ligands): Separations of actinides can be achieved either by (a) determination and control of

actinide in different oxidation states or (b) designing novel ligands for complexation of

actinides/actinyl ions. (a) Early actinides (U, Np, Pu and Am) exist in more than one

oxidation states and every oxidation state has different chemical behavior in solution.

Separation techniques/methods i.e., PUREX and SESAME exploit the distinct variation in the

chemical makeup

and behavior of

different oxidation of

actinides in solution

and thus making it

feasible to easily

partition/separate

one state from

another. (b) Chelating ligand with stereognostic coordination platform tends to form an

intramolecular hydrogen bond (IMHB) with the oxo group of the actinyl ions and imparts

xxii
 [7-8]
specificity and/or selectivity towards actinyl ions binding . Therefore, to develop and

optimize new separations chemistries, the speciation of early actinides is important.

Choice of Complexing medium (chelating ligands and novel solvents): The principles

about choice of chelating ligands, chemical media, and ligand designing should be depending

on their relevant application and important role in mind so that new research activities can

assist in actinides’ separation, geosphere migration predication, dissolution and analysis,

redox control, and actinyl-oxo bond (i.e., O=U=O) activation. Keeping these in mind, in the

present dissertation, the chelating ligands and chemicals media, as discussed below [Fig. 2],

have been prudently chosen to cover all speciation aspects discussed under title (i) to (iv) and

their respective “redox and molecular speciation” data with “actinyl ions” were generated.

Literature review: Despite the extensive spectroscopic studies on UO22+-Citrate system, no

systematic study has been carried out on the speciation of UO22+ in citrate medium

considering its redox behavior. In addition, many discrepancies exist among published data

and a knowledge gaps remain related to its accurate speciation prediction in citrate medium.

The redox speciation of U with phosphonate-based ligands is not available in literature. There

is no report in the literature on aqueous solution chemistry of Np in presence of

phenylphosphonic acid as chelating agent. Aqueous speciation studies on pentavalent uranyl

species are scarce in literature. The aqueous speciation, solution thermodynamics, redox

characteristics, and coordination modes on the interaction of uranyl with

phosphonocarboxylate ligands have not been reported in literature. Literature is scarce on the

electrochemical studies on f-block elements in DES. Literature survey further implies the

lack of direct sequestration of U ions from their diverse solid matrices and their fundamental

chemical aspects (i.e., speciation) in Maline, imidazolium cation based DESs. Furthermore,

the green analysis methodology for U in DES has not been reported.

xxiii
Chapter 1: Introduction: This chapter start with providing some background
background about the

growing demand for nuclear energy, nuclear programme in India, nuclear fuel cycle (NFC),

nuclear waste and its types, and the various pathways of actinides release into the

environment. An overview of general properties of actinides is given.

ven. Subsequently, the

definition of speciation is presented. In addition, the redox and molecular speciation was

described in details. The scenario of possible interaction of actinides, which governs the fate

and transport of actinides in environment, are discussed. A brief discussion about important

role of speciation of actinides in various area of NFC is discussed in terms of four major

applications. The role of complexing agents towards actinides speciation is highlighted. The

explanation for choice of different complexing agents is given. Finally, the motivation for the

work carried out and the scope of dissertation are discussed.

Chapter 2: Experimental and Instrumentations: In this chapter, the details about the

procedures for the preparation, standardization

standardization and synthesis of U and Np solutions, organic

chelators, deep eutectic solvents, used in the present thesis are discussed. The source of the

actinide’s solid matrices and

setup for their dissolution

procedure are discussed. The

details investigations about

the redox and molecular

speciation of actinides were

performed by multi-

technique approach [Fig 3].

A brief description about each technique used for speciation studies are discussed. Since

electrochemical methods have been extensively used, in depth description about

electrochemistry and in-situ

situ spectro-electrochemistry
spectro electrochemistry are provided. Different equations used

xxiv
to calculate physicochemical parameters, stability constant, energetics, green chemistry

metrics, coordination numbers and bond distances of actinyl ions are discussed.

Chapter 3: Redox Speciation of Uranyl with Citrate and Phenylphosphonic acid

(carboxylate and phosphonate based organic chelators): In this chapter, the speciation of

uranyl (UO22+) with (1) citrate and (2) phenylphosphonic acid (PPA) were investigated on the

basis of its redox behaviour using electrochemical methodology with varying physiochemical

conditions. The UO22+ in citrate media exists as UO22+, monomer [UO2Cit]-, dimer

[(UO2)2Cit2]2- and polymeric species. [UO2Cit]- and [(UO2)2Cit2]2- were found to be reduced

in two irreversible one-electron steps, with a chemical reaction coupled between them (ICI

reduction mechanism), to a stable [UIVCit]+ species at pH ≤ 5 and via a single reduction step

with two-electron transfers at pH > 5. Chronopotentiometry and chronoamperometry

techniques were applied to corroborate the finding of an ICI reduction mechanism and to

evaluate electron-transfer kinetic (k0 and α) parameters. In the presence of PPA, the UO22+

has been found to form 1:1 dominant species, i.e., UO2PhPO3, over a wide pH range. Cyclic

voltammetry and differential pulse voltammetry were used to investigate the redox behavior

of UO2PhPO3 species, Eh-pH plot and electron-transfer kinetic (D0, ks and α) parameters.

Using the Deford–Hume formula, the stability constant (log β) of [UO2Cit]- and UO2PhPO3

species were calculated to be (6.8 ± 0.11) and (6.98 ± 0.12), respectively. ESI-MS studies on

solutions of varying UO22+: citrate/PPA ratios and pH were used to confirm complex

stoichiometries. Spectroelectrochemical measurements were carried out to validate the

chemical reaction interposed between the two-electron transfer steps and to provide evidence

of a new pentavalent species, i.e., [UVO2Cit]2- in an aqueous system.

Chapter 4: Electrochemical, spectroscopic, and theoretical studies on redox speciation

of neptunium with Phenylphosphonic acid: This chapter aimed at investigating the redox

and complexation of Np with phenylphosphonic acid (PPA) using electrochemical and UV–

xxv
Visible absorption spectroscopy and DFT calculations. The cyclic voltammetric (CV)

measurement indicates the complexation of both oxidation states (V & VI) of Np with

[PhPO3]2-. The presence and stability region (via Eh-pH plot) of new species of Np-PhPO3 in

two different oxidation states (V & VI) in aqueous solution are identified. The kinetics for

reduction of Np complexes in different oxidation states are explored by evaluation of

electron-transfer kinetic (D0, ko and α) parameters by CV. The spectral parameters, namely

λmax and its molar extinction coefficient (ε) are obtained from UV-Visible spectrophotometric

measurements. The electrochemical as well as UV–Visible spectrophotometric measurements

showed the formation of 1:1 complex only and the stability constant (logβ) obtained for the

same from both the methods found to agree with each other. DFT calculations are carried out

to optimize the geometries of Np-PhPO3 complexes in +5 and +6 oxidation states, to identify

the most probable coordination mode and energetic of complex formation reaction.

Chapter 5: Chemical and Redox Speciation of Uranyl ions with three heterobifunctional

Phosphonocarboxylate Chelates: In this chapter, redox and molecular speciation of uranyl

with three phosphonocarboxylate ligands, which are differing in CH2 spacer, were probed

with varying physicochemical conditions using multi-technique approach. The stoichiometry

and thermodynamic parameters (logβ, ∆G, ∆H and ∆S) of UO22+-phosphonocarboxylate

complexes were evaluated from UV-visible spectrophotometric and calorimetric titration.

ESI-MS studies demonstrate the physical evidence of the dominance of MLH type of

complexes. Formal (Efcom) and peak (Epcom) potentials, Pourbaix diagrams (Eh-pH plots),

heterogeneous electron-transfer kinetic (D0, kof and αn) parameters and mechanistic electron

transfer process of complexes were acquired from cyclic voltammetry (CV). Structural

analysis of complexes investigated by EXAFS and DFT calculations revealed the

heterobidenticity of three phosphonocarboxylates and stereognostic intramolecular hydrogen

bond between -OH of ligands and axial oxygen of UO22+. Interestingly, the absence of

xxvi
disproportionation of uranyl(V) and hence its aqueous redox stability with

phosphonocarboxylate ligands was observed in a wider pH range (1.5-8.0). Presence of new

pentavalent uranyl(V) species with the phosphonocarboxylates in the aqueous was proposed

and their stability and structure were determined. Spectroelectrochemical measurements were

employed to provide evidence of existence of uranyl(V) species and its electronic absorption

spectra.

Chapter 6: Speciation of actinides matrices in deep eutectic solvents: In this chapter,

dissolution, speciation, and analysis of uranium (U) and americium (Am) oxide were probed

in deep eutectic solvents (DESs). Seven U matrices (UO3, UN, UO2, Rb2U(SO4)3, U metal,

U3Si2, and (U, Pu)O2 were dissolved in Maline without any external additives. New DESs

were synthesized by taking (1) 1-methyl-3-decylimidazolium bromide as HBA and malonic

acid (MA) and diglycolic acid (DGA) as HBD, and (2) Choline dihydrogen citrate and

malonic acid (CDHC-MA) in 1:1 ratio. Dissolution of uranium oxides (UO3 and UO2) were

explored in imidazolium based two DESs. The cyclic voltammetry, differential pulse

voltammetry and in-situ spectroelectrochemical measurements were performed to probe the

redox speciation of dissolved U matrices in above DESs. The cyclic voltammetry of Am in

CDHC-MA DES was carried out only to know the feasibility of its conversion to higher

oxidation state in the form of actinyl ion. Redox thermodynamics (peak potential and formal

redox potential), transport property (diffusion coefficient D0), electron transfer kinetic

parameters (αn and k0) and mechanistic electron transfer of the dissolved U in above DESs

were investigated. Under molecular speciation, the structural analysis on UO3 dissolved in

Maline was conducted by EXAFS. Theoretical simulations (MD and DFT) were performed to

support the experimental results and to acquire diffusion, optimized structure, probable

equatorial coordinating atoms, binding energy, and molecular orbital diagram of U species in

above DESs. Luminescence, absorption spectroscopy, and calorimetry titration studies

xxvii
provide information about the interaction of uranyl with Maline. Green analysis methodology

was developed through U samples digestion in Maline followed by voltammetric

determination of U in nuclear material samples and green chemistry metrics were calculated

to authenticate the greener aspects of the methodology.

Chapter 7: Summary and Future outlooks: This chapter provides the summary about the

results of the studies performed as a part of the thesis and suggest some future scopes relevant

to the speciation of actinides. Citrate, phenylphosphonic acid (PPA) and

phosphonocarboxylate chelating ligands form very stable aqueous soluble complexes of U

and Np, which are quite persistent over a wide range of Eh-pH. The order of stability constant

(logβ) and redox potential of uranyl with these ligands were found to be as

citrate<phenylphosphonate<phosphonocarboxylate. In phosphonocarboxylates, the chelation

in combination with the intra-molecular hydrogen bonding enhanced their complexation

tendency towards UO22+. The association of couple chemical reaction was discovered with

electron transfer (ET) steps for UO22+ complexes with citrate and phosphonocarboxylate,

suggesting reduction mechanism as ICI and PCET in citrate and phosphonocarboxylates,

respectively. Deep eutectic solvents namely Maline and imidazolium cation based DESs

shows encouraging solvation potential for diverse kinds of U matrices. Furthermore, these

DESs work as designer solvents for quantitative green analysis of U based NMs.

Interestingly, the pentavalent uranyl (UO2+) species was detected to be redox stable in a

wider pH in presence of citrate and phosphonocarboxylates in aqueous solution and their

respective stability constant (logβ), structure and the electronic absorption spectra were

reported. As future research, development of new methodologies for (1) redox based selective

separations of actinides, (2) molecular recognition of actinides through activation of oxo

group of actinyl, (3) isolation of pentavalent uranyl species, and (4) actinides’

xxviii
electrodeposition, electrocatalytic recovery, extraction, and separation using DESs, are

anticipated.

References:

1. Silva, R. J., and H. Nitsche. Radiochimca Acta 70, no. Supplement (1995): 377-396.

2. Altmaier, Marcus, Xavier Gaona, and Thomas Fanghänel. Chemical reviews 113, no. 2
(2013): 901-943.

3. Maher, Kate, John R. Bargar, and Gordon E. Brown Jr. Inorganic chemistry 52, no. 7
(2013): 3510-3532.

4. Jones, Matthew B., and Andrew J. Gaunt. Chemical Reviews 113, no. 2 (2013): 1137-
1198.

5. Smith, Emma L., Andrew P. Abbott, and Karl S. Ryder. Chemical reviews 114, no. 21
(2014): 11060-11082.

6. Selbin, Joel, and J. D. Ortego. Chemical Reviews 69, no. 5 (1969): 657-671.

7. K. N. Raymond et al. 1992. Journal of the American Chemical Society, 114(21), 8138-
8146.

8. S. Kannan et al. 2017. Dalton Transactions, 46(48), pp.16939-16946.

xxix
 Chapter 1

Introduction

Aim: This chapter aimed to provide some background about the (i) growing demand of

nuclear energy and nuclear power programme in India, (ii) nuclear fuel cycle (NFC) and

associated challenges, nuclear waste, and its types and (iii) general properties of actinides.

The term “speciation” is defined and the important role of speciation of actinides in various

area of NFC is briefly discussed. The choice of complexing agents presented with their

substantial applications. The terminology of green and sustainable is described. Finally, the

motivation of works, scope of the dissertation and chapters’ distribution are given.

1
1.1. Introduction

Nuclear energy is a zero-emission clean and sustainable source of electricity and a

promising alternative to fossil fuel in India as well as other countries. It is a low-carbon

energy source, which has the possibility of reducing greenhouse gas concentration in the

atmosphere and capable of meet future energy needs [1-2]. Nuclear energy is a form of energy

released from the nucleus in two ways: fission or fusion. As for 2022, the nuclear energy is

used by ~ 30 countries and amounts for a total of 11% of the worldwide produced electricity
[3-5]
. Because of rise in global electricity demand and to avoid the drastic change in climate

from negative impacts of fossil fuels, the production of electricity from non-fossil fuel source

viz., nuclear, wind, hydro solar etc., is in high demand. The nuclear fuel materials have fissile
235 233 239 [6]
isotopes such as U, U and Pu , which on interaction with neutrons undergo fission

and released enormous amount of energy (200 Mev). In comparison to fossil fuels, nuclear

energy requires less quantities of fuel. From the nuclear energy industry, an estimate is to
[5]
increase the total electricity production for the year 2050 ranges between 24%-184% .

Unlike fossil fuel-based electricity production, the side product of the nuclear power reactor,

the “burnt” nuclear fuel (called as spent nuclear fuel (SNF)) must be reprocessed and/or

contained and maintained for a period long enough to allow the long lived toxic radioactive

nuclides to decay towards their decay chain in final non-radioactive form due to its long-term

and high radiotoxicity [7-8]. These radioactive nuclides are mostly fission products and trans-

uranic elements (minor actinides (MAs) and plutonium) which are produced as a side product

of the reactor nuclear reaction. Thus, benefit of nuclear energy production comes with the

inevitable hazards of long-lived radionuclides and a major drawback of nuclear energy is the

disposal of SNF. Therefore, the reprocessing of SNF and management of nuclear waste

became the key issues for the sustainable development of nuclear energy.

2
1.2. Indian Nuclear power Programme: Dr. Homi Jahangir Bhabha (initiator of Indian

atomic energy program) envisaged a three-stage Indian nuclear power program in 1954, as

discussed below [Fig. 1.1] [9].

Stage 1: Natural uranium is used as fuel uranium and heavy water as moderator and coolant

in pressurized heavy water reactors (PHWR) to generate electricity and 239Pu. The spent fuel

obtained from PHWRs is reprocessed to recover the residual uranium (U) and plutonium (Pu)

from the fission products.

Stage 2: This stage is based on the fast reactor technology and involves utilization of

plutonium recovered from PHWRs. Plutonium obtained from the Ist stage is mixed with

uranium (as a mixed-oxide (MOX) or as metallic fuel) and used in the Fast Breeder Reactors
238
(FBRs). For power production, the FBRs will fission Pu and breed more it from the U. In

FBRs, the fertile Thorium (Th) used as a blanket to breed more fuel via producing 233U.

Stage 3: This stage plan to achieve the power generation from vast thorium reserves, which
233
found in India, in place of U. It utilizes the fissile U, generated in the IInd stage, as a fuel.
232
Power will be generated from the Th-233U fuel aided by plutonium and this could be

accomplished through developing an advance heavy water reactor (AHWRs).

Figure 1.1. Indian three stage nuclear program

1.3. Nuclear Fuel Cycle, types, and Challenges:

3
 Nuclear fuel cycle (NFC) is a series of industrial process involving various activities
[7]
[Fig. 1.2] to produce electricity from uranium in a nuclear power reactor . The cycle starts

with the milling mining of uranium and ends with the disposal of nuclear waste in a proper

way. Being a strategic material and radioactive in nature, the used nuclear fuel needs to be

taken care of for reuse and disposal. Based on various activities, as shown in Fig. 1.2, the

NFC is mainly classified in two parts ‘front end’ and ‘back end.’ The front end is associated

with the preparation of the fuel and the ‘service period’ in which fuel is used during reactor
[7]
operation . The steps associate with front end is mining and milling, conversion,

enrichment, and fuel fabrication. Nuclear fuel burns in reactor to produce electricity and

generates unused nuclear fuel which is known as SNF. The back-end of NFC basically deals

with the safe management of SNF including its temporary storage, reprocessing, reuse, and

disposal of radioactive waste via various treatment to lower its radioactivity. Based on the

management of spent fuel, NFC further can be categorized into two types viz., open, and

closed fuel cycles. If spent fuel is not reprocessed, the NFC is referred to as ‘open’ or ‘once-

through’ fuel cycle while spent fuel is reprocessed, and recycled, it is referred to as ‘closed’.

Figure 1.2. Nuclear fuel cycle

4
 The major challenges which NFC and nuclear energy production faces are (i) the

requirement for continuous enhancement of safety and safety culture to avoid nuclear

accident, (ii) the need to control the spread of technologies and materials that may be used for

non-peaceful purposes, (iii) the storage of SNF and the appropriate operation of reprocessing

and recycling to recover unused fissile materials, (iv) the increased fission product,

transuranic and activation product inventories from high burn-up along with higher decay

heat and neutron sources, and (v) the proper management and disposal execution of highly
[8]
radioactive wastes, especially for HLW . The separation of minor actinides from HLW is

also difficult task. To make the nuclear sector a substantial contribution to meeting the

world’s energy demand, above challenges require consistent effort to resolve, nuclear fuel

cycle technologies should be pursued to enhance longer-term sustainability, and aim of

national and international efforts should be to enhance the safeguards and non-proliferation.

1.4. Radioactive waste, classification, and storage:

IAEA defines Radioactive waste as “any material that contains or is contaminated

by radionuclides at concentrations or radioactivity levels greater than the exempted

[10]
quantities established by the competent authorities and for which no use is foreseen” . It

arises in a wide range of concentrations and in a variety of physical and chemical forms viz.,

solid, liquid and gases. Based on their form the radioactive wastes are classified as below:

1.4.1. Solid radioactive waste: These wastes are classified as combustible, non-

combustible, compressible, and non-compressible.

1.4.2. Gaseous radioactive waste: It includes gaseous fission products generated due to

radiolysis.

Depending on radioactivity, the category of solid and gaseous wastes is given in Table 1.1.

1.4.3. Liquid waste: Based on level of radioactivity and as per IAEA safety and protection

guidelines, the classification of radioactive waste obtained are given below:

5
Table 1.1. Classifications of Solid and Gaseous waste [11]

Solid Gaseous
Category
Surface Dose (mGy/hr) Activity Level (Bq/M3 )
I <2 < 3.7
II 2-20 3.7- 3.7x 104
III >20 >3.7 x 10 4
IV Alpha bearing

(i) Exempt Waste (EW): Waste that follows the criteria for clearance, exemption, or

exclusion from regulatory control.

(ii) Very Short-Lived Waste (VSLW): This kind of waste primarily is radionuclides with very

short half-lives. Waste that can store for decay for a limited period upto a few years and

afterward be cleared from regulatory control.

(iii) Very Low-Level Waste (VLLW): Waste of this kind does not meet the criteria of EW and

does not require a high level of containment and isolation. It is suitable for disposal in near

surface landfill type facilities with limited regulatory control.

(iv) Low Level Waste (LLW): Waste under this type is above clearance levels and requires

robust isolation and containment for periods of up to a few hundred years and is appropriate

for disposal in engineered near surface facilities.

(v) Intermediate Level Waste (ILW): Waste that requires a greater degree of containment and

isolation than that provided by near surface disposal and it needs disposal at greater depth.

ILW may contain long-lived radionuclides, particularly, alpha emitting radionuclides

(vi) High Level Waste (HLW): Waste with (i) large amounts of long-lived radionuclides that

need to be considered in the design of a disposal facility or (ii) levels of activity concentration

high enough to generate significant quantities of heat by the radioactive decay process.

1.4.4. Storage of nuclear radioactive waste: Deep geological repository (DGR): Deep is

the preferred route for the final disposal of the nuclear wastes containing SNF and HLW. The

6
nuclear wastes are placed inside DGR which is based on a multibarrier system containing

engineered barrier system and natural geological barrier for complete isolation of radioactive

waste from biosphere for hundreds of thousands of years. The host rock constitutes the

natural geological barrier whereas the engineered barrier system consists of waste form,

canisters, overpack, buffer and backfill material. For long-term safety of DGR, natural

geological barrier should have various features such as high strength, high thermal

conductivity, low thermal expansion, high sorption capacity, no ingress of water from

surrounding and minimum interaction with canister and fluid while the backfill/buffer

material should have high swelling potential, high radionuclide retention capacity, low
[12]
hydraulic conductivity, and low gas permeability . Though the release of actinides from

the repository to biosphere is negligible however due to decay heat and corrosion of canisters,

the release of radioactive actinides to the biosphere through aqueous medium is anticipated.

1.5. General Properties of Actinides:

1.5.1. Electronic Configuration: The actinides correspond to the filling of the 5f electron

shell as their electron configuration is [Rn]5fn6dm7s2 (where n= 0-14; m= 0, 1-2). Lighter

Actinides (Ac to Np) show greater tendency to retain 6d electrons due to smaller energy

differences between 6d & 5f orbitals, relative to that between 5d and 4f orbitals of

lanthanides. 5f orbitals of Pu and subsequent actinides are of lower energy than 6d orbitals,

therefore, the electrons are filled in 5f orbitals with no electrons in 6d orbitals.

1.5.2. Oxidation States, ion types, and redox potential: In contrast to lanthanides, the

actinides, particularly early elements of the series exhibit more variation in their oxidation

states and have multiple oxidation states such as +4, +5, +6 and +7. This is due to the close

proximity of the energy level of the 7s, 6d, and 5f electrons. In aqueous solution, the

ionization energy and hydration energy are two important factor that are responsible for

the conversion of one oxidation state to another and the most stable oxidation state of

7
actinide is decided by a combination of these two factors. Actinides in second half of the

series, i.e., beyond americium, shows +3 as the most stable oxidation state because with

increasing atomic number the 5f-orbital is comparatively stabilized than the 6d and 7s.

Hence, the second half of actinides behaves like lanthanides. The prevalent oxidation

states of the actinides are given in Fig. 1.3. The actinides in +3 and +4 oxidation states

generally exists a M3+ and M4+ hydrated ions in solution whereas in higher oxidation

states such as +5 and +6, due to very high ionic potential, the actinide ions form the

oxygenated species of the general type MO2+ and MO22+, which are named as actinyl

ions. The actinyl ions are remarkably stable due to strongly covalent bonded symmetrical

linear (or very nearly linear) O=M=O ions and during variety of chemical transformation

it persists as a single unite. The formation of oxygenated species decreases the effective

charge on actinyl ions and thus the order of effective charge on different oxidation states

of actinides are as M4+>MO22+ (~3.3±0.1)>M3+>MO2+ (~2.3±0.2) [13-15]

. The +7

oxidation mostly found in case of Np and Pu in alkaline aqueous solution in the form of

MO4(OH)23-. The redox potentials of early actinides are shown in Fig. 1.3. The redox

behaviour of early actinides is very complex due to (i) disproportionation of UO2+,

NpO2+, and Pu4+, and (ii) small difference in redox potential, especially in case of Pu,

which leads the simultaneous existence of all four-oxidation state of Pu in aqueous

solution in comparable concentration. These tendencies of early actinides complicate their

prediction in geochemical conditions with varying physicochemical conditions. The

disproportionation reaction of pentavalent actinyl ion (MO2+) ion, where M= U and Np,

can be explained as 2 + 4 

⟷  
+  +  . The equilibrium

constant (log K) value at 25ºC for disproportionation of UO2+ and NpO2+ are reported to

be 9.30 and -6.72, respectively [15]. The presence of hydrogen ions (i.e., high acidity) and

complexing ions (such as F- and SO42-), which can complex strongly with M4+ and

8
MO22+ ions have dominant effect on disproportionation reaction of MO2+ ion. The

Pourbiax diagram, (Eh-pH plot), is a useful tool to know the dominancy of actinides’

oxidation state, stability region and speciation as a function of pH and electrochemical

potential in water as a solution. In environmental condition, the water is transporting medium

for actinide. Water itself has oxidation and reduction characteristics which provides boundary

on the oxidation states stability of actinide in aqueous solution. Thus, the first step for

constructing the Pourbiax diagram for actinide is to get an idea about the chemical stability

area of water (oxidation and reduction). The upper limit of water is defined by the potential

when the oxygen generation starts on the anode according to reaction ½ O2 + 2H+ +2e- =

H2O. The relation between potential and pH is E = 1.299 – 0.0591 pH. The lower stability

limit of water is defined by potential where hydrogen gas (H+ + e- = ½ H2) is evolved and at this
[16]
condition the corelation between potential and pH is E = 0.059 pH . The actual overall

boundaries of the Pourbiax diagram is described by the above stability field of water.

Figure 1.3. Redox potential and stable oxidation states of actinides

1.5.3. Complexation, hydrolysis, and polymerization: Because of the electropositive and

hard Lewis nature, the actinide-ligands bonds are mainly ionic, kinetically labile and non-

9
directional and show preferences to binds with hard Lewis bases such as fluoride and

oxygen. The presence of two oxo group in the linear in the actinyl ions provide a steric limitation

on the number of donor groups for binding with these ions. The oxo group oriented in axial

position and coming ligands will binds through equatorial position in actinyl ions. In absence of

steric constraints, the strength of actinide-ligand complexation depends on the electrostatic

attraction, i.e., ionic potential (Z/r; Z= effective charge on the ion and r= ion size) and its order

for actinides in different oxidation state usually increases as AnO2+<An3+≤AnO22+<An4+.

This order is so because the -yl oxygen atoms of actinyl ion contain partial negative charge

and the effective charge on AnO22+ (An= U, Np and Pu) was found to be in between +3 to 3.3

while for AnO2+ viz., NpO2+ was estimated as 2.2±0.1 [13-14]

. For a given oxidation state, the

complexation tendency rises with increasing atomic number due to increasing charge density

of actinide ions. Unlike lanthanides, actinides show preferences for soft donors also and

display covalent bonding behaviour with ligands containing soft donor atoms N, and S, which

govern the common basis for Ln/Ac separation. Actinide ions can form inner sphere (bonding

involve direct contact between cation and ligand) and outer sphere (ligand does not arrive the

primary coordination sphere and separated by minimum one solvent molecule) complexes

depending on the basicity of ligand. The outer sphere results into an exothermic and negative

entropy change while the inner sphere shows the endothermic and positive entropy change

during complexation of actinides. Actinides form complexes with π bonding ligands such as

alkyl phosphines and thiourea. In case of inorganic oxoanion ligands the stability of actinide

complexes varies in the order OH-, CO32- > F-, ΗΡΟ42- , SO42- > CI-, ΝO3- due to increasing

charge and basicity of the ligands. The actinides, because of their high positive charge, easily

hydrolysed via polarizing the water molecule sufficiently to release protons. For the actinides

in the +3, +4 and +6 oxidation states, the hydrolysis reaction occur in weakly acidic to

alkaline solution whereas in pentavalent actinides it takes place at pH ≥ 8. The early actinides

10
in +5 and +6 oxidation states exist as partially hydrolyzed actinyl ions, viz., MO2+ and

MO22+. Depending on the ionic potential and considering hydrolysis reaction akin to

hydroxide complexation, the strength of hydrolysis of actinides follows the order as

AnO2+<An3+≤AnO22+<An4+. The actinides, in tetravalent state, exhibit hydrolysis even in

acidic solutions with pH ≥ 0. The hydrolysis of actinyl cation decreases as UO22+> NpO22+>

PuO22+. Prior to complete hydrolysis, the actinides in hydroxo complexes tend to form

polynuclear species in which metal ions are allied through hydroxo (M-OH-M) and oxo (M-

O-M) bridges. The Pu4+ easily hydrolysed and form polymeric/colloid species (colloidal size=

1-1000 nm; M.w. 1010), which affects its migration in environment.

1.5.4. Aqueous Speciation: The speciation of an actinyl ion is dominated either (i) by

hydrolysis, or (iii) by carbonate complexation depending about pH and the carbonate content
[16-17]
of the solution and also in some cases by both . Usually, the hydrolysis dominates the

speciation at the low pH values but above neutral pH, the carbonate (CO32-) present in the

solution works as a dominant ligand. The U-shaped solubility curves are observed due to the

development of negatively charged species, carbonate, and hydroxide, which increase the

solubility of actinyl as the pH increases above the neutral region. Even though hydroxo and

carbonato complexes dominate the actinyl speciation in many scenarios, however, there is

possibility that other inorganic or organic ligands can compete for the formation of actinyl

complexes. In presence of aqueous soluble ligand, the speciation of actinyl-ligand complex

can overcome that by hydroxy or carbonate species. The dominancy of actinyl-ligand

complex in pH range primarily deepens on its logβ value. Higher the value of logβ, larger

will be the pH range in which the actinyl-ligand complex can dominate over hydroxy or

carbonate. With the knowledge of a complete set of formation constants of all type of

possible species of actinyl ions in aqueous solution such as actinyl-ligand, actinyl-carbonate,

and actinyl-hydroxy species, the speciation of actinyl ion can be described in a speciation

11
plot, which shows the proportion of each species as a function of pH, carbonate

concentration, or any other parameter. Fig. 1.4 illustrates the main complexes of uranyl that

form in an air-equilibrated solution (CO2(g) partial pressure = 0.00035 atm) as a function of

pH in absence of any complexing ligand. The stoichiometries and thermodynamic stabilities

of hydroxy and carbonate species of uranyl and neptunyl are described in Table S1.1. The

ligands which possess oxygenated moieties like carboxylates, polycarboxylates and

phenolates, phosphonates have a higher affinity for actinides and can consequently affect

their solubility and thus speciation. The complex formation (other than hydroxo complexes),

depends on the presence of complexing agents and on their concentration.

Figure 1.4. Aqueous species distribution of Uranyl in (a) absence (b) presence of carbonate

1.5.5. Molecular-orbital diagram: The actinide have unique feature of the linear ‘‘yl”‐ions

(AnO2n+; n= 1, 2) in aqueous solution. The U(VI)-Oyl bond distance is short approximately

1.75 Å, which implies a strong multiple uranium-oxygen bonding. The orbital involved in

uranium-yl oxygen bonds formation is given in following molecular orbital (MO) diagram of

uranyl [Fig. 1.5], which shows that the bonding orbitals have mainly O 2p character and

turanyl(VI)-oxygen bond contains one σ and two π character thus it can be represented as

12
O2–≡U6+≡O2–. The bonding molecular

orbitals are σg2 σu2 πg4 πg4 with 5fδ and

5fφ as the lowest unoccupied orbitals.

The nonbonding and antibonding orbitals

have 5f and 6d character and the order of

bonding is πg < πu < σg << σu, where σu is

the highest occupied orbital.

1.6. Speciation definition and its roles in actinide chemistry

Speciation in chemistry refers to the distribution of an element among defined

chemical species, i.e., among specific forms of an element defined as to electronic or

oxidation state, complex or molecular structure and/or isotopic composition. ‘Speciation,’ a

word borrowed from the biological sciences, has become a concept in analytical chemistry.

The biologist Orator F. Cook was the first to coin the term 'speciation' for the splitting of
[18]
lineages . The IUPAC has defined speciation as “species distribution based on their

oxidation states or stoichiometries” and given some terminology as following:

(i) Chemical species: Chemical element: specific form of an element defined as to isotopic

composition, electronic or oxidation state, and/or complex or molecular structure.

(ii) Speciation analysis: Analytical chemistry: analytical activities of identifying and/or

measuring the quantities of one or more individual chemical species in a sample.

(iii) Speciation of an element: speciation. Distribution of an element amongst defined

chemical species in a system.

13
(iv) Fractionation: Process of classification of an analyte or a group of analytes from a

certain sample according to physical (e.g., size, solubility) or chemical (e.g., bonding,

reactivity) properties.

Speciation of a radionuclide generally refers to separation of species primarily dependent on

its source, and its later fate is influenced by the physical and chemical properties of its

environment. The total element concentration may be static, the species may be highly

dynamic. In speciation studies, a lot of attention must be paid to the stability.

Metrical knowledge about metal ion’s speciation of the early actinides (U, Np, Pu and

Am) in aqueous (Aq) and non-aqueous (Non-Aq) solutions are of vital importance and

interesting to the nuclear industry in order to understand their solubility, stability, and

reactivity. One of the important features of early actinides is the formation of actinyl ions

(AnO2n+; n= 1, 2). Actinyl ions are the important species in the nuclear fuel cycle because of
[16, 19-21]
their multifaceted and highly characteristic chemical behavior . These ions have

dynamics behaviour in Aq solution and can form stable complexes and nanoclusters with

various organic and inorganic ligands in Aq and Non-Aq solutions. The chemical behaviour

i.e., speciation of actinyl ions, such as complex formation, dissolution, solubility, sorption,

precipitation, and immobilization, depend on several key factors of solutions chemistry such

as hydration, hydrolysis, solubility product, coordination modes, redox potentials, pH and

[16, 19-21]
stability constants . Acquiring knowledge about these factors of actinyl ions are the

first critical step for holistic understanding of early actinides, particularly actinyl ions, in

solutions. Metrical knowledge about the speciation of a metal ion under complexing medium

with varying physicochemical conditions (such as pH) can be broadly classified as below:

(i) Molecular speciation: It is the quest about stoichiometry, structure, chemical and stability

constant (logβ values) and thermodynamic parameters (enthalpy, entropy, and Gibbs free

energy) and coordination modes of a metal ion in complexing medium [Fig. 1.6].

14
(ii) Redox speciation: It deals with acquiring the information about the oxidation state

stability, redox energetic (peak potential and formal potential), trend towards reversibility,

transport property (diffusion coefficient (D0), heterogenous electron transfer kinetic

parameters (αn and k0), electron transfer mechanism (ET; redox-mechanism) and

electrochemical phase diagram, i.e., Pourbiax diagram (Eh-pH plot) [Fig. 1.6].

Figure 1.6. Schematic diagram of Metrical speciation in complexing medium.

The oxidation state stability, Metal-ligand complex formation and ET-mechanism of

actinides mostly depend on pH. For an example, in case of actinides, ET-mechanism may be

either step-wise or direct. It is also possible that ET coupled with some chemical reaction.

Speciation of actinides in solution is a daunting task and are highly challenging. This

is because (1) unlike most elements of the periodic table, there is absence of geologic

precedent, (2) their diverse chemistries, including rich redox behavior, radioactivity, and
[16, 19-21]
susceptibility towards hydrolysis and condensation reactions , and (3) the relative

stabilities of the actinide oxidation states and the types of complexes formed with the actinide

cations in these states vary for Aq and Non-Aq solutions. In addition, speciation of actinides

is very mobile and the effect of pH on their speciation is still couched. Based on aforesaid

reasons, the independent knowledge of chemical behaviour of early actinides is critical in

determining a robust description of solution speciation. Attempts should be made to provide

cohesive database on their redox and molecular speciation. Therefore, novel research with the

15
aim of probing direct metrical information about molecular and redox speciation of actinyl

ions as a function of physicochemical conditions are quintessential requirement for

describing in-depth solution chemistry of early actinides and to mitigate challenges of NFC.

Speciation is a cornerstone of different facets of NFC as described below [Fig. 1.7]:

(i) Actinide environmental aspects for fate and transport of actinides (aqueous chemistry)

(ii) Dissolution, analysis, and recovery in non-aqueous medium (ILs and DESs)

(iii) Stability of unusual (or rare) oxidation state in aqueous and non-aqueous medium

(iv) Separation schemes advancement (oxidation states based or designing novel ligands)

Figure 1.7. Importance of speciation nuclear fuel cycle.

1.6.1. Environmental aspects of Actinide chemistry

1.6.1.1. Pathways of Radioactive Substances in the Environment: The sources of

radioactive contamination are nuclear weapons testing and production, processes associated

with the nuclear fuel cycle, accidental release of radioactive material used in medicine and

industry, mining and mineral processing, and the use of depleted uranium in weapons.

Besides the natural abundance in lithosphere (in Earth’s crust: U, 2−4 ppm; Th, 10−15 ppm)

and hydrosphere (2-4 ppm and 3 ppb, respectively), the light actinides (Th, Pa, U, Np, Pu,

16
Am, and Cm) are important environmental contaminants associated with anthropogenic

activities as discussed above. In the atmosphere, nearly 2х1020 Bq of radioactivity have been
[17]
released due to nuclear weapons tests . Accidental and other releases of radioactive

nuclides from nuclear reactors amount to 0.3% of this total. The primary releases consist of

residual fissionable nuclides in the weapon viz., uranium and plutonium and those which are
137 90
produced from the nuclear explosions (fission products, e.g., Cs, Sr etc. and nuclei

formed by nuclear reactions, beta decay, etc.). In the world’s aquatic systems, the nuclear test

explosions and reactor wastes have deposited an estimated 16х1015 Bq of plutonium [17].

1.6.1.2. Risks associated with actinides in environment: The spread of the actinides (or
[22]
their decay product) through aquatic pathways and physicochemical and geological-

mineralogical processes leads to significant environmental media (e.g., surface and ground

water resources and soil) contaminants, both in the immediate locality of the contaminated

sites and at a sufficiently long distance away from it. Their combined radioactivity (with a

longer half-life) and chemotoxicity are globally a serious concern for environmental chemists

since they pose chronic threats to human health (e.g., cell damage, kidney disease and lung

cancer) and environmental bio-diversity. In addition, the dissolved actinide ions are
[22]
potentially harmful to the aquatic ecosystem . Therefore, understanding the fate and

transport (i.e., migration) of actinides in environment is essential.

1.6.1.3 Chemical Interaction of Actinides in the Environment

Aqueous speciation of actinides serves as the basis for (i) assessing actinides’ release

and transport rates i.e., mobility in the environment, (ii) long term safety assessment of deep

geological repositories, (iii) design methods for clean-up of contaminated site, and (iv)

chelation therapy for the development of formulations for the detoxication and excretion of
[16-17, 19-20]
actinides . This is because of the oxidation state and predominance of aqueous

complexes which govern their chemical behaviour and the interactions with the surrounding

17
geologic media in the environment. In addition, several important factors of solution

chemistry such as the solubility (hydration, hydrolysis, and solubility product), transport

properties, toxicity, bioavailability, redox potential, coordination modes, sorption, and

thermodynamic stability of actinides are strong dependent on their speciation viz.,

composition, oxidation state, molecular-level structure, and nature of the phase in which the

element or molecule occurs. Thus, aqueous speciation of actinides is crucial to understand

about the chemistry which controls the interactions of actinides under environmental
[23]
conditions . The speciation of actinides critically depends on physicochemical conditions:

pH, Eh, metal and ligands concentration, nature of site-specific minerals and temperature, and

their complexation with organic moieties/chelators and microorganism.

Figure 1.8. Overview of actinide behaviour in the environment.

The overview of various geochemical processes that affects the chemical behaviour

and interactions of actinides in the environment are illustrates in Fig. 1.8. As evident from
[16-17]
figure, the important processes that may occur with actinides cations are (i)

precipitation, (ii) complexation reaction, (iii) redox process, (iv) sorption, and (v) colloid

formation, which are briefly discussed below. The dynamic interplay between these factors

18
affects partitioning of actinides between the solid and solution phases and retard or enhance

their migration in environment. An accurate understanding of these processes and dynamic

interaction between the actinides and environment fortifies for accurately assessing the

feasibility of storing nuclear waste in geological repositories.

(i) Precipitation: It can limit solubility and have a retarding effect on release and migration

rates of actinides. Thus, it is providing an important immobilization mechanism for actinides.

(ii) Sorption: It is the process through which actinides may sorbs on mineral or rock surfaces

in contact with the aqueous phase. Like the precipitation process, this process tends to retard

migration and reduce the amount of actinides ion in solution.

(iii) Colloidal formation: Actinides have a tendency to form or become associated with

colloidal size particle. In colloidal form, the actinides exhibit the dissimilar behaviour and

different migration than a dissolved species. This process can enhance or retard migration of

actinides depending on the nature of colloids and the solution conditions.

(iv) Redox process: The significant role of oxidation state and redox chemistry on the

migration of actinides in the environment is beyond dispute. The primary factor and the

single most important property of actinide ion determining the mobility of actinides ion is
[16-17, 20]
their oxidation state because (i) it can have wide range of values in aqueous phase

depending on the environmental redox conditions, and (ii) the tendency of geochemical

processes (e.g., precipitation, complexation, sorption, and colloidal formation) considerably

depends on oxidation state and differ from one oxidation state to another. However, for

actinides in the same oxidation state these processes tend to be similar. An interesting feature

of actinides is that their oxidation states can coexist in solution due to very small differences

in Gibbs energy between their oxidation states. It makes actinide redox distributions rather

difficult to predict. Since the chemical behavior of actinides depends mostly on the oxidation

state, actinide redox processes are of direct environmental relevance. Redox chemistry of

19
actinide under environment is reliant on the geochemical boundary conditions, where the

predominant actinide oxidation states and actinide species in aqueous solution can be
[16]
envisaged in diagram plotting the redox potential (Eh) versus the pH of solution . The

diagram is called as Pourbaix diagrams, which implies the expected dominant actinide

species as a function of fundamental thermodynamic properties, define intrinsic ‘redox

borders’ for aqueous systems and represent upper and lower limits for thermodynamically

stable aqueous solutions. The ability to predict actinide migration is directly linked to the

ability to establish the nature, stability, and mobility of dissolved species formed within the

bounds of the prevailing redox conditions. The environmental chemistry of actinides is vastly

dependent on their oxidation state distribution and associated redox conditions. The

surroundings near the nuclear waste repository are determined by the absence of oxygen (i.e.,

anoxic) in deep underground and presence of strong reducing condition. This type of redox

situation is mainly established by coupled direct and indirect microbial activity, geochemical

reactions with the host rock, and the presence of organic chelators, Fe(II) and S2- [24-25]. The

redox processes which influence the actinides oxidation states distribution in environment

can be broadly classified as below:

(a) Abiotic: Reductants and oxidants: The anoxic environments contain a suite of potential

reductant Fe(II) species, S2- species and reduced natural organic matter (NOM) from which

oxidized species of actinide can accept electrons. The O2, Mn(III, IV) and Fe(III) species are

most abundant potential oxidants to whom reduced form of actinide can transfer electrons.

Radiolysis: The radiolysis of actinides in aqueous solution may also generate very reactive

species such as e-aq, H•, OH•, and H2O2, which can change the actinide oxidation state.

Redox effect of organic chelating agents with actinides: Organic chelators present in

environment from both natural and anthropogenic sources can directly affect the oxidation

state of dissolved actinide in two ways: (i) they can stabilize an oxidation towards

20
precipitation reduction by forming complexes and (ii) many organic chelators tend to reduce

or facilitate the reduction of multivalent actinides.

[24-25]
(b) Biotic: Actinides can be reduced or oxidized by microbial processes . The presence

of microbes in environment plays an important role in defining the predominant oxidation

state of the actinide and thus their speciation. Microorganisms mostly have an impact on the

redox behaviour of actinides in two important ways: (1) indirectly, by providing reducing

conditions in environment via the reduction of oxygen and by generating reducing agents (2)

directly, by enzymatic reduction. Microbial reduction occur by Fe(III) or sulfate reducing

bacteria DIRB and DSRB, respectively whereas microbial oxidation happen through

Acidithiobacillus ferrooxidans and nitrate dependent oxidation by G. metallireducens.

(c) Coupled abiotic-biotic redox processes: The microbial activity can produce a suite of

reductants/oxidants that can provide redox conditions for an example as reduction of Fe(III)

by DIRB yield Fe(II).

Actinides in oxic environment generally exists in higher oxidation states (e.g., UO22+, NpO22+

etc.) which are more soluble and mobile than their reduced or lower oxidation state species

(e.g., UO2 and NpO2 etc.). Lower oxidation state of actinide also exhibits enhanced tendency

to sorb on mineral surfaces. Thus, conversion from an oxidized/potentially mobile from to a

more reduced/potentially less mobile form is an attractive approach for in situ immobilization

of actinide [24]. This kind of redox conversion can be obtained through above redox processes.

Therefore, an understanding of these redox processes and their synergisms, is essential to

establish environmental fate of actinide. Redox behavior and thus above redox processes of

actinides can also be strongly influenced by electron transfer (ET) kinetics. In case of

actinides, the various possible ways of ET and their relevant nature of ET kinetics are

depicted in Fig. 1.9. As evident from figure, the redox reactions usually proceed fast which

involving only electron transfer (e.g., 1and 2) and no structural change. On other side, the

21
redox reaction requiring a molecular rearrangement either forming or breaking the actinyl

structure or coupling of chemical reaction with ET step are known to be slow and kinetically

hindered (e.g., 4 and 5).

Figure 1.9. Possibilities of electron transfer process and associated kinetic behaviour.

(v) Complexation reaction

Complexation reactions with relevant ubiquitous (hydroxide, carbonate, humic and

fulvic acids) or anthropogenic ligands (carboxylate or phosphonate based) (i) influence the

stability of redox forms and the solubility of actinides, and the actinide sorption processes (ii)

modifies their concentrations in aqueous solution and typically increases the actinide

concentrations unless it helps adsorption on mineral surfaces or precipitation of an actinide

solid phase, (iii) define the chemical form (speciation) of the actinides in solution, and (iv)
[16-17, 19-20]
control their presence in the environment . Thus, deep knowledge of the main

complexation reactions of actinides is required for calculating the actinide solubility,

assessing sorption effects and modeling transport properties. Organic chelators, both naturally
[26-27]
occurring and anthropogenic act as “shuttles” for transporting actinides in the

22
 [23, 26-27]
environment, play a pivotal role in determining their environmental behaviour .

Generally, the natural or anthropogenic organic chelators present near repository or mining

area have important role in the sorption/diffusion competition of actinides and can affect

sorption via redox and hydrolysis and diffusion via complexation with them. Both type of

organic chelators significantly influences the migration of actinide ion through strong

chemical interaction by forming aqueous soluble complexes and altering their redox energetic

and kinetics as a function of changes in denticity and coordination [20, 23, 28-29]. The migration

of actinide in the environment can be significantly retarded by removal/immobilization of

actinide ion through several environmental or synthetic processes, such as the formation of

adsorption/sorption complexes and precipitation by organic chelators [20, 23, 28-29], reduction of

higher oxidation state of actinide to their lower state, and microbial reduction process [20, 23, 28-
29]
. Actinide ion form strong bonds with organic chelators and its complexation process with

chelators tends to increase the stability of dissolved actinide species and slow down its

electron transfer processes. Therefore, actinide-organic chelator interactions are vital in

accessing the dependency of molecular and redox parameters on solution variables and for a

thorough comprehension of environmentally relevant processes of actinide and in

determining the fate of actinides in the environment. Research about exploring new organic

molecules that could provide an additional binding site to obtain selectivity and to prevent

actinide desorption for its efficient removal/immobilization is also important [30-31].

1.6.2. Dissolution and analysis

Uranium and Plutonium are primarily utilized as a fuel source for nuclear power

production. Nuclear fuel used in power reactors consists of UO2 or mixed oxide (U, Pu)O2

(MOX). Once discharged from the reactor, the spent nuclear fuel contains unreacted U/Pu
[32-33]
oxide, fission products, and transuranic (TRU) elements . For a standard PWR with a

burn up of 33 GW/t, the spent nuclear fuel typically consists of about 95.5% UO2 matrix,

23
 [32-33]
3.6% fission products, and 0.9% transuranium elements . The increasing demand of U

and Pu as fuel materials in the nuclear reactor and also for the sustainable development of

nuclear energy, the processing and reprocessing of these metals from naturally occurring ores

and spent nuclear fuel (SNF) is of great importance. Current approaches of reprocessing fall

into two major categories, aqueous based hydrometallurgical and pyrochemical processes [34].

In hydrometallurgical reprocessing spent nuclear fuel such as the Plutonium Uranium

Reduction Extraction (PUREX) process, the spent nuclear fuel will be dissolved first with

high concentration HNO3 and then solvent extraction carry out for the separation of U and

Pu. This step results in a large volume of high-level radioactive liquid waste with most of the

fission products and minor actinides. The long-lived fission products and minor actinides

pose potential long-term risk to the environment. Further, the principal disadvantage of

PUREX is in the area of proliferation resistance [33-35], as this process permits the isolation of

a pure plutonium product. In pyrochemical reprocessing method the actinides are separated
[35]
from the high temperature molten salt media through electrochemical means . However,

the requirement of high temperature and the strongly corrosive nature of the molten salt

media have been opposed critically for its application in reprocessing. Further, both the

processes have poor atom and energy efficiency. Thus, complexities of both processes and

resulting technical challenges, demands the development of alternative method.

International Atomic Energy Agency (IAEA) safeguard policy is based on the robust

nuclear materials accounting (NMAC) which ensure no misuse of nuclear materials (NMs) or
[36]
technology for nuclear weapons . The environmental swipe samples at a declared facility

are collected and transported to analytical laboratories for dissolution and estimation of NMs

for proper implementation of safeguard. Furthermore, for quality assurance of reactor fuels

and nuclear forensics studies, the U and Pu samples (including swipe samples) were routinely

dissolved in various worldwide laboratories. However, the main problem in sample

24
preparation is time consuming and hazardous dissolution procedures, which uses corrosive

inorganic acids (e.g. HNO3, HF, HClO4, and/or H2SO4) [37-38]. For operator and environmental

safety considerations, such corrosive chemicals should be avoided because it generates large

volume of harmful NO and NO2 gases and increases neutron and γ-ray background due to (α,

nγ) reactions on 19F nuclei. Based on above issues, for advancement of NFC, it is necessary

to develop an innovative, environmentally safe, and economical low-waste technology for

fast dissolution of actinides using less hazardous chemicals.

1.6.2.1. Ionometallurgy: Dissolution through Non-aqueous route

Dissolution of metals or their oxide/salt is an important and challenging issue for the

development of alternative route in the nuclear field. The direct dissolution of metal oxides

has the added advantage of complete mitigation of the aqueous processing of SNF. If a green

dissolution is possible, it will be worthwhile to replace inorganic acids in reprocessing of the

present and advanced fuels as well as in routine sample dissolution at laboratory scale. It will

be meritorious if some energy-intensive alternate routes of non-aqueous processes using ionic

liquids (ILs) or novel solvents such as deep eutectic solvents (DESs) are developed, which
[33, 39-43]
can work at room temperature itself . Non-aqueous routes are talented new

technologies for NFC since it has several advantages such as minimal volumes of waste

generation, less time consuming, low criticality concern and feasibility to reprocess the high

burn-up, short cooled fuels compact infrastructure, radiolytic stability of the process reagents

and ease of recovery of the metals by electrochemical means etc. If ionic solvents such as ILs

or DESs are involved to process metals or their oxides/salts then the term “ionometallurgy”

can be used. In ionometallurgy, an innovative and more efficient ways of processing and/or

reprocessing and the subsequent production of metals can be achieved via simple two-step

process of dissolution and recovery (either by chemical precipitation/downstream chemistry

or electrowining process) without generating hazardous wastes [39] [Fig. 1.10]. Dissolution of

25
metal oxides depends on many factors, such as temperature, mixing time, lattice energy,

crystal structure, acidity or basicity of the metal oxides, stability of the metal ion complex
[43]
formed after dissolution or by the presence of chloride ion in ionometallurgy . For a

complete dissolution, the lattice of the solute particles is required to be broken to become

solvated by the solvent molecules. For this, the attractive force among dissimilar particles

(solute-solvent) should be higher than the attractive force between similar particles (solute–
[33]
solute and solvent–solvent). Fan et al. proposed a correlation (U/x) between the lattice

energy (U) of a metal oxide (MxOy) and its solubility in the IL medium. A good solubility of

metal oxides was found if U/x < 7000 kJ mol-1 whereas if U/x >10 000 kJ mol-1 metal oxides

is insoluble. In viscous ionic liquids the dissolution process of metal oxides is slow due to

slow mass transfer. Room temperature ionic liquids (RTILs) were put forth for the purpose of
[39-43]
nuclear fuel reprocessing and other related campaigns . However, their potential was

never realized due to issues such as cost, toxicity, and non-biodegradability. In addition, ILs
[39, 44]
(and molecular solvents) have poor solubility for metal oxides because of (1) high

strength of metal oxide bond, (2) the inability of the oxygen anion of a metal oxide to exist in

a free form in ILs, (3) the absence of the oxide-binding reagents in ILs medium to react with

the metal oxide, and (4) weak coordinating ability of constituting anions and cations.

Figure 1.10. Scheme of the general idea of metal oxide processing in non-aqueous medium.

26
 Task-specific ionic liquids (TSILs), which are ionic liquids with a functional group

covalently tethered to the cationic or anionic part, are developed to overcome the problems of
[44]
poor solubility of metal oxides . However, the main drawback of TSILs is that they are

often only accessible after a difficult and time-consuming multistep synthetic procedure
[44]
which restricts their use in large-scale industrial applications . Meanwhile, deep eutectic

solvents are the newest entries to the current world of chemical media with unique

physicochemical and tuneable properties. It is innovative that DES can be explored for the

dissolution and recovery of actinides from their primary, secondary sources, spent fuels or

high-level nuclear wastes.

1.6.2.2. Speciation of Actinides in non-aqueous medium (ILs or DESs): One of the key

chemical aspects when considering the reactivity of a metal during ionometallurgy is the

species that form upon dissolution [45-49]. The speciation of metals in ILs or DESs solution is

extremely pertinent in the area of metal salts/oxides dissolution and it basically controls their

reactivity. A species dissolved in these solvents will experience a very strong ionic

atmosphere since both consist only of ions. It will be quite interesting to understand how the

chemistry of metal ions behaves under such an extraordinary condition. Speciation is known

to regulate key features of metal processing and electrochemical behaviour, such as solubility

and redox potentials. In aqueous solvents, the chemistry of H+ and OH- dominate the species

formed in solution, the redox properties, and the solubility of metals whereas in ILs and

DESs the speciation is mainly governed by the anionic component of the liquid. Metal ion

interacts with whatever ligands (L) are available in ILs or DESs (equation 1.1). The species

present and the equilibrium constant are depending upon the concentration of salt in solution

and the relative Lewis or Brønsted acidity [45].

 
 +  +  ↔ [  ] (1.1)

27
The solvent species which dominates complexation is the anion because it has a significant

Lewis basicity and it is generally present in higher concentration (5-10 mol dm−3). It means

that even strong ligands can be displaced.

For foreseeing the application of ILs or DESs as media to the reprocessing and waste

treatment processes in nuclear fuel cycles requires the comprehensive understanding of

primitive redox and molecular speciation. Knowledge including mechanistic information

about the both kind of speciation of actinides in ILs or DESs is essential to better understand

the chemistry that is occurring starting from their dissolution to subsequent selective recovery

in chemical/electrochemical processing and to quantitatively differentiate ILs/DESs from

[45-49]
other ordinary solvents . Furthermore, probing the speciation (redox and molecular) of

dissolved actinide metal ions is imperative (1) to benchmark the redox thermodynamics and

kinetics of redox-sensitive actinide ions and their dependency on solvation and equatorial

coordination, (2) to describe the coordination environment around the actinide ion, (3) to

reveal the coordination competition between the anionic/hydrogen bond donor ions of ILs or

DESs toward equatorial coordination of actinide ions, (4) to provide the optimized redox

conditions for actinide ions analysis and electrocatalytic recovery, (5) to understand the

activity of actinide ion in ILs/DESs solution which is crucial for utilizing the full potential of

a reactive species, and (6) to understand the actinide oxides/salts dissolution phenomenon

such as rate, kinetics and mechanism. The objective of the redox speciation of actinides in

ILs/DESs is to establish the baseline thermodynamic and kinetic data for these systems which

will be helpful to critically evaluate the ability to use electrochemical methods and ILs/DESs

systems for controlled, potential mediated, separation of actinides by electroplating on

electrodes surfaces [49]. Redox speciation studies will examine the interfacial electron transfer

processes of actinides and their potential dependent deposition at electrode surfaces. The

disparity of redox physicochemical parameters of actinides in ILs/DESs from the aqueous

28
medium is expected due to difference in speciation of the metals in the two solvent systems.

The solvation plays an important role in determining the complexation and coordination

behaviour of metal ions in ionic liquids or DESs medium and provides direct information
[45-48]
about the speciation , which will be helpful to reveal the mechanism involved in

dissolution process, to better understand the corresponding leaching (during dissolution)

behaviour, and to know about the feasibility of cation-cation interactions between homo or

hetero actinyl ions. The solvation of actinide ions in these solvents is different from what is

observed in conventional organic solvents and water since the poorly solvating behaviour of

ILs/DESs can provide the formation of coordination compounds with low coordination

numbers. It is of great importance to study the solvation of metal ions and their molecular

speciation through the determination of complexation behaviour (stoichiometries) and the

thermodynamic parameters such as stability constant, enthalpy, and entropy of actinides. All

these thermodynamic parameters are very helpful to energetically understand the

complexation and interaction behaviour of actinides in ILs/DESs during dissolution.

1.6.2.3. Analytical aspects in nuclear fuel cycle

(i) Why determination of NMs is important?

SNF reprocessing media is quite a challenging analyte due to its high radioactivity

and strong acidity, from the analytical chemistry point of view. Speciation characterization of

the actinide elements extracted and their relative concentration determination is crucial for

the monitoring the performance at each step of the reprocessing and chemical quality control

of nuclear fuels, ensuring security of the nuclear fission processes, and measuring the nuclear

wastes. In addition, in order to implement full scope of lAEA Safeguards under an agreement

between the nuclear non-proliferation treaty signatory state and the IAEA (INFCIRC/153;

IAEA Safeguards Glossary [36, 50]), robust nuclear materials accounting and control (NMAC)

and nuclear forensic are essential for (i) precise and accurate determination of nuclear

29
materials (NMs) and (ii) analysing swipe samples at both bulk and trace/ultratrace level

concentration to detect and deter any unauthorized activities and to verify the identity of

smuggled or discovered nuclear materials [50]. It is generally accepted that trafficking of metal

ions/metal complexes depend greatly on their actual chemical and physical forms, oxidation

state, etc., and not merely on their concentrations. Thus, it is necessary to determine not only

the total content of the element but also its individual chemical and physical form or the

oxidation state, i.e., speciation information, which can be attained through extensive

destructive analysis of NMs.

(ii) Comparison between DA and NDA methods and drawbacks of conventional

methods

Destructive assay (DA) provides a more accurate quantifiable measurement than non-

destructive assay (NDA) techniques and can be used to determine if a small fraction of a
[51]
material is present . In most cases, the precision of DA techniques is better because the

effect of the sample matrix can be eliminated or corrected for. Detection limit of DA

techniques is generally lower than NDA techniques since the measurement approaches

involve counting of atoms versus activity counting. Moreover, an often-downplayed role of

DA techniques is the characterization of samples needed for the calibration of NDA

analytical instrumentation. DA methods currently in use for actinides/NMs quantification are

mainly inductively coupled plasma atomic emission spectrometry (ICP-AES) and mass

spectrometry (ICP-MS). These methods are rather time-consuming and can barely be

implemented in on-line mode. The results of such analyses are usually available only several

hours after sampling. Other optical spectroscopy tools suffer from the incapability to deal

with non-transparent and highly scattering media and also cannot ensure sufficiently low

detection limits for NMs. Conventional electrometric redox titrimetry using endpoint

detection through biamperometric, coulometric, and potentiometric methods are routinely

30
used for analysis of actinides/NMs. However, these conventional methods have several

disadvantages, viz., generation of hazardous acid waste, the involvement of various metallic

impurities (Cr, Fe, Ti, Ag, etc.) due to the addition of redox titrants during the analysis, time-

consuming hazardous acid dissolution, and the laborious recovery of actinides/NMs from
[52]
analytical waste . Coulometry is an absolute electroanalytical method, but the total period

of analysis for a sample is effectively long. Several studies were further devoted to

modification of electrode surfaces for NMs analysis as an alternative but its preparation

involves a complex procedure and is expensive, tedious, and time-consuming, which restricts
[53]
its application in routine sample analysis at bulk concentration . Side effects of using

conventional analytical methodologies in routine chemical analysis may involve serious risks

for operators and damage to the environment due to used toxic reagents. Therefore, new

analytical methodology which consider the use of less toxic reagents and minimizes wastes

generated need to be developed in order to determine NMs with good precision and accuracy.

(iii) Importance of Voltammetry technique and DES in analysis

Among the analytical techniques, electroanalytical presents many advantages for the

speciation characterization and quantification of metal ions. Voltammetry is one of the

simple, cost effective and rapid electroanalytical techniques capable for fast, precise, and

accurate destructive determination of concentrations of the analyte [54]. It has twin advantages

as the possibility to work at larger concentration ranges (from milli to micro molar) and the

inherent sensitivity towards oxidation states of the elements. It also enhances the possibility

of on-site analysis, ability to design the facilities to significantly lower the radiation exposure

to the work personnel and equipment and is inexpensive, enabling its wider application. The

technique involves minimal sample handling, thereby reducing the potential sources of

contamination. Because of its wide concentration range, it is applicable for (1) analysis

methodology advancement at bulk and (2) sensor development at trace/ultratrace level

31
concentration for actinides/NMs. The electrochemical sensing of actinides/NMs appears to be

an attractive approach, as it can provide the quantification of very low concentrations of

target analytes and allows measuring in turbid liquids. The measurement of the redox

speciation and quantification of actinide elements at conventional electrodes (Au, Pt, or

glassy carbon is complicated by (1) poisoning of Pt and Au working electrode surfaces

through the formation of Pt-O and Au-O bond [55], (2) side reactions such as water oxidation,

metal oxide formation, hydrogen evolution at negative potentials etc., and (3) much narrow

cathodic potential window of Pt and Au. In most cases, the reduction potential of actinides is

significantly more negative than the potential associated with the hydrogen evolution side
[56]
reaction is ~ -0.2 V . Because of these factors, the analysis, especially the simultaneous

determination of NMs (mainly U and Pu) and systematically examination of electrochemical

parameters of actinides are highly challenging. Compared to aqueous, non-aqueous medium

has wider potential window, thus analytical activity such as simultaneous determination of
[57]
NMs is quite feasible in non-aqueous medium. Literature reports indicate that DESs can

be use as designer solvents for green analytical chemistry because the intermolecular

interactions exist between supramolecular structure of DES and target analytes. DESs

behaves like liquid crystals in which the solute molecules are fixed in crystals, therefore,

analytical detection enhancement is possible when target analytes are part of DES (a

phenomenon like micellar-enhanced spectrometry detection generated by surfactants) [57].

1.6.3. Stability of unusual oxidation state in solution

Uranium (U) is known to exist in various oxidation states as III, IV, V and VI. Among

them pentavalent uranium (i.e., UVO2+) has historically been reported as unusual (rare)

oxidation state of uranium in aqueous solution by J. Selbin et al. in “Chemistry of uranium

(V)." Chemical Reviews 1969, 69, 5, 657–671 [58]. It remains comparatively unstable and rare

due to (1) its propensity to disproportionate to thermodynamically favoured U(IV) and U(VI)

32
products in aqueous solution according to following equation 1.2 and (2) its extreme air and

water sensitivity and its easy conversion/oxidation to hexavalent uranium in the presence of

trace amounts of oxygen or water.

[ ()] +   → [ ()] +  () +   (1.2)

Figure 1.11. Geometry of Pentavalent uranium (UO2+) in cation-cation interaction (CCI).

Unlike NpO2+ and PuO2+, which are stable under a wide range of conditions,

pentavalent uranyl can be stabilized in concentrated carbonate media or at low pH (pH 2-3)
[59-60]
, where in each environment it exhibits a considerably longer half-life [2], but otherwise

it readily disproportionate in aqueous phase. The UO2+ disproportionation mechanism is quite

obscure. Recent kinetic and theoretical studies suggest that the redox disproportionation

reaction proceeds through the interaction of the “yl” oxo group of UO2+ with an adjacent

pentavalent uranyl, forming cation-cation complexes (CCIs) that facilitate electron transfer

and yield UO22+ and U(IV) species after protonation of the uranyl oxygen atoms. The CCI

complex mainly contains two mutually coordinated UO2+ groups in which -O of one UO2+

moiety coordinated to U of second UO2+, as shown in Fig. 1.11. Its formation (or interaction

33
between two pentavalent uranyl moiety) is expected to favoured by the increased Lewis

basicity of oxo group (U=O) in pentavalent uranium (UO2+) than to that of hexavalent uranyl

(UO22+). Previous studies [59-60] reported that CCI complex mainly exist in two forms either in

T-shaped tetranuclear (tetramer) or diamond-shaped dinuclear (dimer) [Fig. 1.11]. In

centrosymmetric dimer structure of ([UO2(dbm)2K(18C6)]2; dmb= dibenzoylmethanate), two

units are assembled through a diamond shaped via two mutually coordinated monodentate

UO2+ group. The value of the U=O distances are 1.941 and 1.850 Å while the O(1U)-U(1)-

O(2U) and O(1U)-U(1)-O(2U) angles are 175.80º and 101.6º, respectively. The structure of

the cation ([UO2(dbm)2]4[K6Py10])2+ consists of a centrosymmetric tetramer of UO2+’s

coordinated to each other in a monodentate fashion to form a square plane. Each UO2+

coordinates two adjacent uranyl groups and is involved in two T-shaped cation-cation

interactions (two linear UO2+ groups arranged perpendicular to each other). The distances of

U=O bonds in structure of above complex are mentioned in Fig. 1.11 while the angle are as

O(14)-U(1)-O(11)= 179.0(4)º and O(12)-U(2)-O(13) = 178.9(4)º. Because of its instability,

the study on solution chemistry of pentavalent uranium is difficult. Thus, gaining information

about aqueous speciation of pentavalent uranium is highly challenging, resulting in its elusive

aqueous chemistry and a knowledge gap related to the comprehensive understanding of its

stability and structure in the aqueous solution. The aqueous speciation of pentavalent uranium

plays a crucial role in the solubility and mobility of uranium in the environment and in

investigating the mechanism of biotic and abiotic reduction of uranyl species in the

environment. Despite of its huge instability, the pentavalent uranium can be stabilized against

disproportionation under specific conditions by careful choice of ligands and chemical media,

which prevents the formation of CCI, such as equatorial complexation or uranyl oxo binding

by (1) sterically bulky organic ligands/chelators viz., shiff base ligands (salophen) or

counterions such as cation K+ or iron, which provides the steric protection along the O=U=O

34
 [59-60]
axis , and (2) anaerobic environment and non-aqueous solvents. Due to rapid

disproportionation of UVO2+ species, the voltammetric method is appropriate to understand

the aqueous speciation of UVO2+ species in comparison to other techniques since it allows for

a semi-quantitative determination of redox processes parameters on a very short timescale

and minute concentration change.

1.6.4. Separation schemes advancement (oxidation states or designing novel ligands)

Separations of actinides are a critical aspect to reprocess the spent fuel for subsequent

safe disposal and for nuclear waste management. This can be achieved either by (a) control

and determination of actinide oxidation states or (b) designing novel ligands for complexation

of actinide species.

(a) Oxidation states play a considerable role in actinide separation especially in case of early

actinides (U, Np, Pu and Am) since these exist in more than one oxidation states and every

oxidation state has different chemical behavior in solution. Separation techniques/methods

i.e., PUREX and SESAME (SElective Separation of AMericium by Electrochemical means)

[61]
exploit the distinct variation in the chemical makeup and behavior of different oxidation

of actinides in solution and thus it is feasible to easily partition/separate one state from

another. (b) In actinide separation chemistry, designing novel ligands for selective

complexation of actinides is an important task. This research area has gained significant

attention due to their potential applications in nuclear waste management. The newly

designing ligands should be talented to enhance the binding affinity, specificity and

selectivity towards a particular actinide as compared to others. In this context, the

preorganized macrocyclic ligands (e.g., Cucurbituril CB[n], and cyclodextrin) and chelating

ligands with stereognostic coordination platform are appropriate choice. Preorganization of

several ligating unit on a molecular platform provide a specific fit to the target metal, which

results in a better extractant with higher metal selectivity. The chelating ligand with

35
stereognostic coordination platform has a tendency to form an intramolecular hydrogen bond

(IMHB) with the oxo group of the actinyl ions and imparts specificity towards actinyl ions

binding [30-31], which helps in molecular recognition and selective separation of actinyl ions in

presence of other interfering ions. To develop and optimize new separations chemistries,

speciation of early actinides is essential.

1.7. Choice of Complexing medium (chelating ligands and novel solvents)

The principles about choice of chelating ligands, chemical media, and ligand

designing should be depending on their relevant application and important role in mind so

that new research activities can assist in actinides’ separation, geosphere migration

predication, dissolution and analysis, redox control, and actinyl-oxo bond (i.e., O=U=O)

activation. Keeping these in mind, in the present dissertation, the chelating ligands and

chemicals media, as discussed below [Fig. 1.12], have been prudently chosen to cover all

speciation aspects discussed under title (i) to (iv) and their respective “redox and molecular

speciation” data with “actinyl ions” were generated. The details about the aqueous based

ligands and DES media, used in present thesis, are given below. Phosphorus oxo anion and

carboxylate-based ligands were selected due to their high aqueous solubility and high

ionization at physiological pH.

(i) Citrate: Citric acid is a naturally occurring a-hydroxy polycarboxylic acid. It is capable to

form strong water-soluble complexes with actinides over a wide range of pH.

(ii) Phenylphosphonic acid: It contain doubly ionizable phosphonate groups (-PO3H2),

which shows stronger complexation tendency towards the metal ions than the isostructural

carboxylic acid. It is more probable towards deprotonation compared to carboxylic acid

therefore metal ion can more effectively compete with H+ for truly anionic ligand binding

sites in acidic solutions.

36
Figure 1.12. Choice of complexing agents

(iii) Phosphonocarboxylic acid: It is a phosphorus oxoanion and heterobifunctional

phosphonate ligand [HOOC-(CH2)n-PO3H2; where n= 0, 1, 2], where one of the phosphonate

moiety has been changed by a carboxylate group. It has high complexing strength for metal

ion in aqueous solution through its multiple coordination sites.

(iv) Deep Eutectic Solvents (DESs): DES, a new class of ionic liquid first introduced by
[62]
Abbott et al. in 2001 , constitute a

prominent addition to the repertoire of

non-aqueous media. It appears to be

very interesting “green and

sustainable” solvent and promising

alternative to non-aqueous media such

as conventional organic solvents and

room temperature ionic liquids (ILs) in

the 21st century. DES is generally composed of two or three cheap and safe components,

generally one component as hydrogen bond acceptor (HBA) and other as hydrogen bond

37
donor (HBD), which are capable of associating with each other through hydrogen bond

interactions to form a eutectic mixture with a significant depression in freezing point than that
[63-64]
of each individual [Fig. 1.13] . The term DES used to differentiate it from ionic liquids

which contain primarily one type of discrete anion and cation. In contrast to ILs, the DES

contains a variety of anionic and/or cationic or neutral species. DESs that are made of

primary metabolites such as organic acids, amino acids, sugars, polyols, and choline

derivatives are entitled as Natural Deep Eutectic Solvents (NADES). NADES fully represent

green chemistry principle. DESs have the general formula as Cat+X-zY, where Cat+ is in

principle refers to quaternary salt of any ammonium, phosphonium, or sulphonium

whereas X is a Lewis base (usually a halide ion). Y is the Lewis or Bronsted acid and z is

number of Y molecule which can interact with anion X- and form complex anionic species
[45]
. The classification of DES is represented in Table 1.2 and some examples of HBA and

HBD for DES synthesis are summarized in Fig. 1.14 [45].

Table 1.2. Classification of DESs

Type General Formula Terms

type I Cat+X-zMClx M= Zn, Sn, Fe, Al, Ga, In

type II Cat+X-zMClx.yH2O M= Cr, Co, Cu, Ni, Fe

type III Cat+X-zRZ Z= CONH2, COOH, OH

type IV MClx + RZ = MClx-1+.RZ + MClx+1 M= Al, Zn and Z= CONH2, OH

type V Non-ionic DES Composed only of molecular

substances

The physicochemical properties, advantages, and applications of DESs are described below:

38
Figure 1.14. Structures for several HBAs and HBDs for DES synthesis.

(i) Phase diagram: The word “eutectic” comes from the Ancient Greek εὔτηκτος
τηκτος or eútēktos

which
ich implies easy melting. DESs are not pure compounds but mixtures of two or more pure

compounds. Therefore, their formation should be represented by a solid-

solid-liquid phase
[62-64]
diagram. Abbott et al. proposed that the depression in freezing point of the mixture

(∆Tf) is the difference between the ideal eutectic temperature of the composition of a binary

mixture of A + B and the linear combination of the melting points of the pure components A

and B, as shown in Fig. 1.15,, and further stated that the magnitude
magnitude of ∆T
∆ f is directly

proportional to the strength of interaction between A and B (larger the interaction the larger
[65-66]
will be the ∆Tf). However, some recent studies indicate defining a DES is still

controversial subject and more appropriate classi

classification
fication should be present to distinguish
[65]
DESs from other eutectic mixtures. Martins et al. in recent times defined DESs as “a

mixture of two or more pure compounds for which the eutectic point temperature is below

39
that of an ideal liquid mixture, presenting significant negative deviations from ideality

(∆T2>0)”, where ∆T2 stands for depression in the temperature which is the difference

between the ideal and the real eutectic point [Fig. 1.15]. Furthermore, they suggested that a

DES should be liquid at operating temperature even if this needs a different composition than

the eutectic one. The above definition by Martin et al. provides the appropriate meaning of

word “deep” in DES as “huge depression in freezing point” and covers the mixtures with a

melting point lower than the ideal eutectic temperature. The magnitude of the freezing point

depression, ∆T2, is defined as Tf(real) – Tf(ideal), where Tf(real) is the measured freezing point of a

mixture at the eutectic composition and Tf(ideal) is the theoretically predicted freezing point for

an ideal mixture. In DESs formation, the significant melting point depression of a eutectic

mixture compared to that of the pure materials is because of charge delocalization from the

halide anion (HBA) to the HBD through hydrogen bonding.

Figure 1.15. Phase diagram of a two-component mixture representing the eutectic point

(ii) Freezing Point (Tf): DES generally has a lower freezing point than that of individual

components. The significant depression of the freezing point is because of stronger

interaction between the anion of HBA and the HBD component. Abbott et al. suggested that

that the freezing point of HBD-salt eutectic mixtures mainly dependent on (1) the lattice

40
energies of DESs, (2) the mode how the couple anion-HBD interacts, and (3) the change in

entropy due to the formation of a liquid phase. The selection of HBA and HBD is the key

factor which decides the lower freezing points. For a chlorine salt-derived DES, the freezing

point decreases in the order F- > NO3-> Cl- > BF4-. The molar ratio of HBA and HBD has also

a noteworthy impact on the freezing point of DESs. In carboxylic acid based DESs, in order

to form eutectic mixture, two carboxylic acid molecules are required to complex each

chloride anion of choline. In the case of diacids, the eutectic is formed at its 50 mol% (i.e.,

1:1). In addition, the carboxylic acid with the lowest molecular weight shows the largest

depression in the freezing point. The freezing points for all reported DESs are below 150°C

and the DESs with a freezing point < 50°C are more applicable for various field.

3. Density: The majority of DESs show higher densities than water with the value ranging

from 1 to 1.3 g/cm3 at 25°C for most of the DESs while metal based DESs have densities in

the 1.3-1.6 g/cm3 range. The difference in the density of DESs might be due to a different

molecular organization or packing. DESs are basically composed of holes or empty

vacancies. During the DES formation, the average holes radius was decreased which results

in a slight increase of the DES density compared to that of neat HBD. The mole ratio of

HBA/HBD, and the nature of salt (HBA) and the HBD have an important effect on the

densities of DES. Density of DESs show a temperature-dependent behavior and decreases

linearity with the increasing temperature. Lower densities than water are obtained for

hydrophobic DESs.

4. Viscosity: Most of the reported DESs exhibit relatively high viscosity (>100 cP) at room

temperature except choline chloride (ChCl)-ethylene glycol which has low viscosity as 37 cP.

Sugars or carboxylic acids based DESs shows extremely large viscosity (12730 cP for 1:1

ChCl: sorbitol) and even high viscosities were reported for metal salts based DESs (85000 cP
[67]
for 1:2 ChCl:Zinc Chloride) . The low viscosity is observed only in hydrophobic kind of

41
DESs. The viscosity of DESs is mainly governed by (i) forces such as hydrogen bonds,

vander waals and electrostatic interactions, (ii) the chemical nature of DES components

(HBA and HBD), (iii) the mole ratio of HBA and HBD and (iv) the temperature and water

content. The high viscosity of DESs is mainly due to extensive hydrogen bond network

between each component, which consequences in lower mobility of free species within the

DES. In addition, the large ion size and very small void volume of the DESs give the high

viscosity. Viscosity of most eutectic mixtures significantly depends on the temperature. As

the temperature increases, the viscosity decreases.

5. Ionic conductivity: The majority of the reported DESs have low ionic conductivity

compared to high temperature molten salt (7.61 mS/cm in ethaline compared to 350 mS/cm

in BiCl3 at 200°C). However, their conductivity is comparable and/or higher than drinking

water (0.2 to 0.8 mS/cm) and deionized water (0.05 µS/cm), respectively. With raise in

temperature, the conductivities of DESs generally increase significantly owing to a decrease

of the DES viscosity. The conductivity of DESs is also depends on the HBA/HBD mole ratio,

the nature of the organic salt and the hydrogen bond donor as well as the salt’s anion, and the

addition of water.

6. Acidity and alkalinity: The chemical nature of HBDs has a strong effect on acid and basic

strength of the DESs. The Hammett function (H_) is used to evaluate the acidity and basicity

of non-aqueous solvents. The H_ value of Reline is 10.86, which suggest that this DES is

weakly basic. The Maline (1:1) is acidic DES with pH 1.67 and its acidity varies with

addition of water such as for Maline:0.22 H2O, the pH lies in the range 1.28-0.41.

7. Effect of Water: When water is added to the DES, at a low water content, it integrating

into the deep eutectic solvent’s network and strengthening the hydrogen bonds taking place
[66]
between the HBA and the HBD . Further dilution of DES will result into hydration of all

42
the species; however, it is anticipated that the anion will be preferentially hydrated. Water

addition in DES decreases its viscosity.

8. Advantages of DES and Major Applications: DESs are environmental benign and have

low ecological footprint due to their several advantages such as non-volatile, non-toxicity,

sustainable, biodegradability, biocompatible, recyclability, inflammability and chemical

inertness with water. DESs are less expensive and chemically tuneable and their synthesis

procedure adds to green chemistry as it is easy to handle, 100% atom economic, no

purification is required, and

no waste production. DESs

have many prospective

applications in diverse field

such as electrochemistry,

metal/metal oxides

processing, catalysis,

extraction/separation, carbon
[45]
dioxide adsorption, cleanup of heavy metal and nanotechnology . The foremost

applications for DESs include the incorporation of metal ions in solution. DESs are talented

of donating or accepting electrons or protons which confers them excellent metal ion

hijacker [Fig. 1.16], especially Maline, due to high solvating potential for metal oxides/salts.

DESs have wider potential windows than aqueous solutions and high electrical conductivity,

therefore, in electrochemistry, DESs are used as promising electrolytes for electrodeposition

of metal, electrochemistry reaction, recovery, and electropolishing (metal dissolution).

1.8. Green and Sustainable Chemistry:

According to IUPAC Green chemistry is “the design chemical products and processes that

particularly eliminate the use or generation of substances hazardous to humans, animals,

43
 [68]
plants, and the environment” . Green chemistry basically is based on twelve principles

which are described in Fig 1.17.

The OECD in 1990 define the term Sustainable chemistry as “a scientific concept that seeks

to improve the efficiency with which natural resources are used to meet human needs for
[68] [69]
chemical products and services” . In 1999, Hutzinger et. al provided a fundamental

difference between these two concepts of chemistry and suggested that the green chemistry

denotes to the “design, manufacture, and use of chemicals and chemical processes that have

little or no pollution potential or environmental risk,” whereas sustainable chemistry implies

the “maintenance and continuation of an ecologically-sound development”. However, the

keywords (e.g., safe, clean,

efficient, biodegradable etc.)

which are related to the

concept of sustainable

chemistry are also employed

to describe the merits of

green chemistry. Therefore,

it is always better attempt to

refer the “Green and

Sustainable chemistry”

instead to differentiate both

terms. The essentials of Green and sustainable chemistry are (i) Holistic approach and long-

term positive development, (ii) validation of 12 principles of green chemistry, (iii) address

social, environmental, scientific, and economical aspects, and (iv) substances and process

with the least adverse effects.

1.9. Motivation of the work

44
 Speciation of uranyl in citrate is very mobile and shows complex behavior about pH-

dependent changes in stoichiometry and coordination environment in the aqueous medium.

Despite the extensive spectroscopic studies, no organized study has been carried out on the

speciation of UO22+ in citrate medium considering its redox behavior. In addition, despite

decades long research as many discrepancies among published data exist and knowledge gaps

remain. In aqueous solution, the speciation of uranyl with PPA is unknown in literature due

to precipitation at higher concentration of uranyl (>10-4 M). Therefore, there is need of

sensitive technique which can work at trace level concentration of uranyl. In this context,

electroanalytical techniques are better choice. Np speciation is very complex, resulting in

knowledge gap due to lack of comprehensive understanding of its behaviour. The

complexation studies on Np have been reported with inorganic ligands (CO32-, ClO4-, NO32-

and SO42-) and some other organic chelating ligands including carboxylic acids, amides, and

hydroxamic acids. However, no reports in the literature have been found on aqueous solution

chemistry of Np in presence of PPA as chelating agent. In literature, crystal synthesis of

homometallic and heterobimetallic uranyl with phosphonoacetic acid,

carboxyphenylphosphonate, and diphosphonoterephthalic acid were reported. Nevertheless,

no studies have been reported on aqueous complexation, redox speciation, and coordination

modes of UO22+ with heterobifunctional chelating ligands such as phosphonocarboxylic acids

viz., PFA, PAA and 3-PPA. Literature survey implies the unavailability of redox

thermodynamics and kinetics parameters of uranyl and Np with citrate, PPA and

phosphonocarboxylates. These facts motivate us to present the systematic study on the

speciation of UO22+ with varying physicochemical conditions in aqueous citrate, PPA and
[39, 70]
phosphonocarboxylates and Np in PPA. Previous studies reported the use of additive

viz. water, aqueous hazardous acids and Fe/Al-salt during ionometallurgical processing of

uranium (U) matrices. Literature survey implies the lack of direct sequestration of uranium

45
(U) from its solid matrices and the greening analysis methodology for U. Electrochemical

studies on d-block metal ions [Fe(II)/Fe(III)] and Cu2+/Cu+ in Reline and Ethaline were

reported but literature is scarce on electrochemical studies on f-block elements in DES.

Compared to the aqueous media, there is a paucity of knowledge regarding speciation of

actinides in DESs. In addition, the important aspect that how DES interact with uranium is

missing in literature. Use of DES as co-solvent for Am separation [71] is available in literature

but no studies have been reported on the speciation of Am in DES.

1.10. Scope of the Thesis

Metrical speciation of actinides in aqueous and non-aqueous solutions is an important

fundamental chemical aspect (1) to understand their behaviour such as redox potential and

solubility, (2) to predictive their migration in the aquatic environment and associated risk

assessment for nuclear waste disposal, and (3) for advancement of new analysis, separation

and recovery schemes based on non-aqueous methods. The migration of actinides within the

environment is dictated by speciation, which depends on complexation with organic

chelators, redox reactions, and physiochemical conditions (Eh and pH). Aqueous soluble

organic chelators, both naturally occurring and anthropogenic in the environment, play a

pivotal role in determining the migration behaviour of actinides. Carbon and phosphorous are

two most important elements in the bio-geosphere as they are omnipresent in both biotic and

abiotic medium. Phosphonate and carboxylate are constituents of the cellular wall of bacteria

and considered as building blocks of glyphosate and humic substances. These are the main

driving functionalities for most of the chemical interactions associated with the actinides in

the aquatic environment. Deep eutectic solvents with tuneable chelating functional groups are

a suitable sort of “green and sustainable” non-aqueous media and works as a “designer

solvent” in analytical chemistry. It can provide high solvating potential for actinides solid

matrices to leach their ions from oxides, salts, or alloy host core. DES, especially type III,

46
provides a new variety of organic complexing moiety, which is different from organic

complexing ligands in aqueous solution. The malonic acid-based DES such as Maline, which

contains dicarboxylic acid functional group, is strongly acidic and its solvating potential for

metal oxides is correlated well with that in aqueous HCl. The imidazolium cation is quite

stable to radiolytic degradation and its density, surface tension, refractive index, etc. are not

notably affected upon irradiation. The present dissertation aims to acquire comprehensive

redox and molecular speciation of early actinides with aqueous and deep eutectic solvents

based complexing agents. To accomplish the aims, the present thesis has mainly two

categories of investigations as discussed below.

(a) Aqueous based studies using complexing ligands: Speciation of actinides in presence of

aqueous soluble carboxylate and phosphonate based chelating ligands. In this context, citrate,

phenylphosphonic acid and three heterobifunctional phosphonocarboxylates were chosen to

studies the aqueous speciation of U and Np with varying physicochemical conditions.

(b) Deep eutectic solvents-based studies (Dissolution, speciation and analysis of

actinides): In the present studies, Maline and imidazolium cation based DESs were preferred

for sequestration of uranium matrices and development of its analysis methodology.

Speciation on dissolved solution of uranium matrices in these DESs was probed to

understand the mechanistic of dissolution process, interaction of uranium with DES and

analysis parameters.

Attempts have been made to obtain the redox potentials (peak and formal potentials),

Pourbiax diagram (Eh-pH plot), transport property (i.e., diffusion coefficient), electron

transfer (ET) mechanism, heterogeneous electron-transfer kinetic parameters (k0 and αn),

stoichiometries, stability constant (logβ), coordination modes, and thermodynamic energetics

of the complexes in aqueous and DESs systems by multi-technique approach.

Electroanalytical methods viz., cyclic voltammetry, differential pulse voltammetry, square

47
wave voltammetry, chronoamperometry and chronopotentiometry were employed to probe in

details (1) the redox speciation of actinides with varying pH in aqueous and DESs, (2) to

inspect the coupled chemical reaction with electron transfer steps, and (3) to obtain the

calibration plot for analysis of uranium and the stability constant value by Deford-Hume

methods. In-situ spectroelectrochemical studies were performed to corroborate the finding of

coupled chemical reaction, ET-mechanism, and stability of pentavalent uranium (UO2+) and

to acquire its electronic absorption spectra. UV-visible absorption studies were carried out to

obtain the stoichiometries and their respective stability constant values. The fitting of

absorption titration data was carried out with Hyperquad software. Potentiometry studies

were undertaken to know the protonation of phosphonocarboxylates ligands. Using

isothermal titration calorimetry, the thermodynamic energetics parameters of

complexation/interaction processes were determined. ESI-MS studies were employed as the

characterization techniques to provide the physical evidence of the dominant species in

aqueous. The coordination modes of the complexes were analyzed by EXAFS. MINTEQA2

and HySS software were used to obtain the speciation diagram as a function of pH. Physical

properties, such as density, viscosity, and melting point of imidazolium-based DESs were

determined. Karl-Fischer titration was used to determine the water content in DESs.

Theoretical calculations viz., molecular dynamics (MD) and density functional theory (DFT)

were performed to (1) authenticate the experimental results, (2) optimize the geometries of

the dominant species, and (3) derive the bond distances, partial charges, and molecular orbital

(MO) diagram for the optimized geometries. The studies in present thesis do not cover the

isolation of pentavalent uranium. Herein, the speciation studies of actinides are limited to

aqueous and DES solutions. The solid-state characterization of actinide complexes and

speciation of actinides in other non-aqueous media such as ionic liquid are not within the

scope of the thesis.

48
1.11. Chapters’ distribution Present dissertation has been divided in six chapters as

indicated in Fig. 1.18.

Figure 1.18. Pictorial representation of chapter distribution in present dissertation.

49
 Chapter-2

Experimental and Instrumentations

AIM: Gaining comprehensive information about redox and molecular speciation of actinyl

ions in aqueous and non-aqueous solutions cannot be feasible simply through a single

technique, thus, multi-techniques approach is required. In this chapter, brief discussions

about the various techniques used for speciation studies and sample solutions preparation of

actinyl ions, organic ligands, dissolution process of actinide matrices and synthesis of deep

eutectic solvents are provided.

50
2.1 Introduction: The studies in the present dissertation are mainly focused on

understanding the speciation of actinyl ions with aqueous soluble chelators and deep eutectic

solvents. The acquiring speciation information of actinyl ions in aqueous and deep eutectic

solvents is possible through following major steps:

(i) Preparation of metal ions and organic chelator solutions in aqueous solution and

their pH optimization: Under metal ions, the preparation of uranium and neptunium

solutions is described. The organic chelators employed are citric acid, phenylphosphonic acid

and three phosphonocarboxylic acids. The preparation of above organic chelators in aqueous

solution is also discussed.

(ii) Synthesis of deep eutectic solvents and dissolution procedure of actinide matrices:

The synthesis of Maline, two imidazolium based DESs, Choline dihydrogen citrate-Malonic

acid DES are described. Further, the dissolution procedure of uranium matrices (oxides, salts,

metal powder and alloy) and americium oxide are given.

(iii) Probing of speciation through various techniques: Multitude of techniques, as

indicated below [Fig.

2.1], is employed for in-

depth understanding of

speciation. The basic

principles and main role

of each technique are

discussed.

(iv) The relevant data

analysis: To obtain redox and thermodynamic parameters and coordination modes.

2.2. Sample preparation:

51
(i) Aqueous media: AR grade sodium perchlorate, PPA, Citrate and three

phosphonocarboxylates (PFA, PAA and 3-PPA) were used to carry out the experiment. The

stock solution of uranyl nitrate (0.1 M), prepared by dissolving the solid U3O8 in 1-2 M

HNO3, and was standardized using Davies and Gray’s method. Samples were prepared by

mixing stock solutions of UO2 (NO3)2, NaClO4, and ligands to obtain solutions with required

concentration for electrochemical experiments. The pH of samples was adjusted by HClO4 or

NH3 using PICO+ pH meter which is based on a combination pH electrode (glass membrane

electrode and a reference electrode) with a glass electrode (Lab india, Mumbai, India). The

pH meter was calibrated using standard buffer solutions (Merck) of pH 7, 4 and 9. All

solutions were prepared using milliQ water having resistivity 18 MΩ·cm. ESI-MS

measurement was done in 100 % Methanol. Supporting electrolyte was used as 0.1 M

NaClO4 in the electrochemical experiment. Np(V) Stock Solution: Np-237 stock solution in

our laboratory was used for the present studies. It was purified from Pa-233 and other cations
[72]
using anion exchange (Dowex 1X4) 57 resin in nitrate form . The acidity of the Np stock

solution was adjusted to 7.5 M (HNO3) for loading on the anion exchange resin (Dowex

1X4). To this solution, ferrous sulphamate and hydrazine solutions were added to ensure that

all Np(VI) and Np(V) is reduced to Np(IV). This feed solution was loaded on the column and

after three column volume washings of the resin with 7.5 M HNO3, the solution was eluted

with 0.35 M HNO3 to collect the purified Np solution. The purity of neptunium was checked

by alpha spectrometry. The concentration of purified neptunium was estimated by alpha

spectrometry and by UV-VIS-NIR spectrophotometry [73].

(ii) DES media: (a) Maline and Choline-Dihydrogen Citrate-Malonic acid DES

synthesis: Choline chloride (≥98%) (CC) and Malonic acid (99%) (MA) were purchased

from Sigma-Aldrich. Both solids were taken in 1:1 molar ratio and mixed well and kept for

heating at 60oC for four hours till the homogenous Maline deep eutectic solvent formation.

52
METALAB oven was used for heating the solid samples. The karl-fischer titration was used

to determine the water content in prepared MALINE, providing nearly 1% of water content.

(b) Imidazolium based DESs: 1-decyl-3-methyl imidazolium bromide, C10mimBr, not a

clear liquid at room temperature (RT) but appears as gel-type was prepared following the
[74]
procedure given in the previous literature report . Malonic acid (MA) and diglycolic acid

(DGA) both solids at RT were

procured from Fluka as AR grade

and were used as such. C10mimBr

was mixed with 1:1 and 1:2 molar

proportions with MA and DGA

respectively and stirred

continuously with a glass rod until a

clear single viscous phase was obtained [Fig. 2.2]. Hereafter, the DES C10mimBr with MA is

referred to as DES 1 and that with DGA is referred to as DES 2. The amount of water content

with drying both DES 1 and 2 were found to be ~ 8% and 6.7%, respectively.

(c) Source of Uranium matrices and their Dissolution procedure in Maline and

Imidazolium based DESs: Eight solid U matrices namely UO3, Uranyl nitrate (UN)

UO2(NO3)2, UO2, U3O8, Rb2U(SO4)3, U-metal, (U, Pu)O2 and U3Si2 and one PuO2 were

dissolved in Maline (Table S2.1). The dissolution process of solid matrices of UO3, Uranyl

nitrate (UN) UO2(NO3)2, UO2, U3O8 in Maline was carried out by ultrasonication nearly 3

hours afterwards heating at 60°C about 1 to 2 hour in METALAB oven. The dissolution of

Rb2U(SO4)3, U-metal and U3Si2 matrices were also carried out by ultrasonication and heating

steps. The ultrasonication of solid matrices Rb2U(SO4)3, U-metal and U3Si2 in Maline were

performed nearly 3 to 5 hours and the heating step was done at 60°C for 2 to 3 hours. The

dissolution of PuO2 and (U, Pu)O2 matrices were carried out in the radioactive glove box

53
using IR lamp. IR heating (~100 °C) of PuO2 and (U, Pu)O2 matrices were performed in the

repetitive stepwise manner of heating and cooling such as 10 to 15 minutes heating and half

an hour cooling. The repetitive heating and cooling were done for 3 to 4 hours till the

complete dissolution of solid matrices. The number of samples taken and their corresponding

concentration was reported in Table S2.1. Weighed amounts of uranium oxides (UO3 and

UO2) were added to the DES 1 and DES 2 separately and were sonicated (~ 3-4 hours) till the

entire solid was dissolved. In the case of UO2, in addition to sonication, heating at 700C for 1

hour was also carried out for complete dissolution. The concentration of dissolved uranium

oxides in DES 1 and 2 was mentioned in Table S2.2.

2.3 Summary of used Techniques: The brief discussion about the various techniques

employed in present thesis is given below:

2.3.1 Electrochemical methods, experimental set-up, and parameters: Voltammetry is a

transient electrochemical technique where the applied potential (E) on the electrode is

changed with time and current (i) flowing through the electrode is measured as a function of

E. The resultant “i versus E” plot is known as “voltammogram”. The current is proportional

to the concentration of the analyte. These techniques are inexpensive and strictly analytical

(i.e., can determine the low levels of metals in different matrices) and can be classified into

three categories, which are sweep techniques, pulse techniques and hydrodynamic

techniques. For investigation of the general electrochemical behaviour of the analyte in

solution the sweep techniques are preferred while quantitative information about the analyte

can be obtain by pulse techniques. In voltammetry, the main instrument used is a potentiostat

which provides a potential to the electrochemical cell and the resulting current is then

measured. Modern potentiostat contains a built-in sweep and/or pulse generator, and those

which are interfaced to a computer to generate the desired waveform. Potentiostat use a three-

electrode configuration, which is connected to the working, reference, and auxiliary

54
 [75-77]
electrodes. The voltammetric techniques are based on Fick’s and Faraday’s Laws .A

simple electrode reaction Ox + ne- ↔ R proceeds through a series of steps as discussed below

and depicted in Fig. 2.3.

Figure 2.3. Pictorial representation of series of steps during electrodic reaction

1. Movement of analyte from bulk solution to the electrode (Mass transport)

2. Electron transfer between the metallic electrode surface and the analyte (Electron Transfer)

3. Movement of the product away from the electrode surface to the bulk solution

4. Coupling of different chemical reactions preceding or following the electron transfer (e.g.,

protonation, dimerization, catalytic decomposition etc.) and other surface reaction (e.g.,

adsorption, desorption etc.)

The mass transport of redox species towards electrode can be taken place through any of the

following processes:

1. Migration: The transport of charged species under potential gradient due to electrostatic

force between the charged electrode and the analyte ions. The migration of analyte can be

avoided by using excess of swamping or damping electrolyte.

55
2. Diffusion: The movement of anayte towards working electrode under concentration

gradient.

3. Convection: The transport of analyte due to the mechanical motion of the solution by

stirring of the solution, rotating electrode or vibration of the solution or electrode. It is usually

eliminated by keeping the experimental set up under quiet and stable condition.

Cyclic Voltammetry: Cyclic voltammetry (CV) is a very important electrochemical

technique for acquiring qualitative information about the electrochemical reactions of an

analyte in the solution. The power of CV lies in its capability to quickly provide information

on the thermodynamics of redox processes, on the kinetics of heterogenous electron-transfer

reactions, and on coupled chemical reactions or adsorption processes of an analyte. In CV,

the potential of a stationary working electrode is scanned linearly versus time from Ei

(starting potential) to Ef (switching potential) and reversing back to Ei, using a triangular

potential-time (E-t) waveform [Fig. 2.4]. Single or multiple cycles can be used depending on

the requirement of information. The potentiostat records the current resulting from the

applied potential during the potential sweep and the associated plot of current versus

potential, thus obtained, is known as a cyclic voltammograms. The scan rate (ν) of CV is the

rate at which the potential of the WE vary with time. Figure 2.4, shows the characteristics CV

response of a reversible electron transfer process of analyte during a single potential scan. For

an analyte, the redox parameters such as anodic peak current (Ipa), cathodic peak current (Ipc),

anodic peak potential (Epa), cathodic peak potential (Epc) and half wave potential (Ep/2,

potential corresponding to half of peak current) can be attained from CV. There are mainly

two primitive types of behaviour, as discussed below, which controls the peak current of an

analyte during redox process:

Redox process:  + !" # ⇋ %"& (2.1)

Behaviour: (i) Mass Transport:  ('()* +, -./ 0+)(-1+2) →  (/)/3-4+5/ 0(4,63/)

56
Figure 2.4. E-T curve and cyclic voltammetry plot with varying concentration profiles 1 to 7.

In presence of potential at electrode, surface concentration of an analyte reduces, which

results in the concentration gradient between the bulk solution and the electrode. Therefore,

diffusion of analyte occurs towards the electrode. The observed current depends on the

concentration gradient, as shown below:

=>
7 = !9:; <= ? (2.2)
@A

Where I is the current (A), A is the area (cm2), D is diffusion coefficient (cm2 sec-1),

(BC/Bx)x=0 is the concentration gradient (mol cm-1) at the electrode surface, C is the

concentration of the analyte (mol cm-3) and x is the distance from the electrode to the bulk

(cm). In presence of applied cathodic potential, an analyte starts to reduce and current flow.

Beyond the formal reduction potential, the surface concentration of an analyte becomes

nearly to zero and the mass transfer to the surface reaches a maximum rate (current

approaches its maxima, Ipc) and afterwards it declines due to the depletion effects

57
[(BC/Bx)x=0) decreases]. Therefore, a peaked current potential curve is obtained. Mass

transport of analyte occurs through three different modes as:

(ii) Electron Transfer:

kred
#
 (/)/3-4+5/ 0(4,63/) + !" ⇌  (/)/3-4+5/ 0(4,63/) (2.3)
koxi
The rate constants of the electron transfers vary with the electrode potential as shown below:

F2G
E4/5 = E A (K L K , ) (2.4)
* H / IJ

(M#F)2G
E+ 1 = EA (K L K , ) (2.5)
* H / IJ

Where, k0 = standard rate constant, α = transfer coefficient (0< α< 1) and n is the number of

electrons transferred. The heterogeneous standard rate constant k0 measures the intrinsic

ability of a species (say, Ox) to exchange electrons with the electrode in order to convert to

its redox partner (say, Red). A large k0 implies that a species will convert to its redox partner

on a short time scale while the same phenomenon

occurs on a long-time scale in case of a small k0. The current-potential relationship which is

known as Butler-volmer equation is described in following equation

QRS <TUTV? (WUQ)RS (TUTV)

7 = !9:E A [C+ (0, P)" # IJ L C4/5 (0, P)" IJ ] (2.6)

The transfer coefficient (α) is

generally an index indicative

of the symmetry of the

energy barrier for a redox

half-reaction.

Types of electron transfer:

Relative to the rate of mass

transport, the analyte ET-

processes can be reversible,

58
irreversible, and quasi-reversible depending on the electron transfer rate. The shape of CV

changes accordingly, as shown in Fig. 2.5. Compared to the rate of the mass transport, if the

rate of the electron transfer is higher, the process is defined as electrochemically reversible

(both kred and kox are large and greater than the rate constant of the mass transport). In another

condition, where the rate of the electron transfer is lower than the rate of the mass transport,

the process is defined as electrochemically irreversible. The diagnostic criteria for reversible,

irreversible, and quasi-reversible ET process are provided in Table 2.1.

Table 2.1: Diagnostic criteria for ET-processes in terms of various redox parameters

S.N. Reversible Irreversible Quasi-reversible

0.059
)V
XKY = ZKY3 L KY6 Z Ep shifts with ν and shift is
2.303 %\
XKY > (
1. of about 30/αn mV for a n
=
!9 tenfold increase of ν XKY i!dm"gf"f hiPℎ k
0.059
=( ) V at 25°C
n
XKY de!fPg!P hiPℎ k
(KY3 + KY6 )
K, =
2.
2
3. Ep is independent of scan Ep shifts with ν and shift is
rate (ν) of about 30/αn mV for a
tenfold increase of ν
7Y6 7Y6
=1 = 1 e!o ip q = 0.5
4. No current ratio (Ipa/Ipc)
7Y3 exists 7Y3
Otherwise
7Y6
< 1; q > 0.5
7Y3
7Y6
> 1; q < 0.5
7Y3
5. 7Y ∝ k M/ 7Y ∝ k M/ Current-function
vw
Current-function Current-function z W { |i}ℎP !eP ~"
vw vw
(xW/y ) if de!fPg!P hiPℎ k (xW/y) if de!fPg!P hiPℎ k xy
de!fPg!P hiPℎ k

6. Ep-Ep/2 = 0.0565/n at 25°C Ep-Ep/2 = 47.7/αn mV at

25°C

59
Pulse Voltammetry: The pulse voltammetric techniques lowers the detection limits of

voltammetric measurements down to the 10-8 M concentration level by substantially

increasing the ratio between the faradic and non-faradic currents. The difference between the

various pulse voltametric techniques is the excitation waveform and the current sampling

regime. For speciation studies, more sensitivity pulse techniques are differential pulse

voltammetry and square wave voltammetry which are discussed in detail as below.

Differential pulse voltammetry (DPV): It is extremely useful and sensitive technique for

measuring analyte at trace level. In DPV, fixed magnitude pulses superimposed in a linear

potential ramp are applied to on working electrode and the current is sampled twice just

before the pulse application [i(t1)] and at end of the pulse [i(t2)]. The current difference [∆i =

i(t2)-i(t1)] is plotted versus the applied potential and the resulting peak shaped curve is called

differential pulse voltammograms [Fig. 2.6]. This procedure effectively reduces the

background current and thus this procedure results in a Faradaic current free of most

capacitive current. The major advantage of DPV is low capacitive current, which leads to

high sensitivity. The peak current (ip) is directly proportional to the concentration of the

analyte by following equation

2G€ W/y > M#ƒ

XiY = (-‚ )W/y
(Mƒ) (2.7)

Where σ = exp [(nF/RT)(∆E/2)] (∆E is the pulse amplitude). The width of the peak (at half

height; W1/2) is related to the electron stoichiometry as W1/2= 3.52RT/nF.

Figure 2.6. (a) The waveform of DPV and (b) the differential pulse voltammogram.

60
In DPV, the irreversible redox system results in lower and broader peak current with inferior

sensitivity and resolution compared to reversible systems.

Square wave voltammetry: It is a large amplitude differential technique in which a

waveform composed of as symmetrical square wave is superimposed on a bare staircase

potential and is applied to the working electrode. The current is sampled twice during each

square wave cycle, first at the end of the forward pulse (at t1) and second at the end of the

reverse pulse (at t2). The difference between the two measurements is plotted versus the base

staircase potential [Fig. 2.7]. In SWV, the frequency (fsw) and scan rate (ν) is correlated to the

pulse width (tp) according to following equations

M †‡
p0„ = (2.8) and k= = p0„ XK0 (2.9)
-w -w

where XK0 is the staircase shifts at the beginning of each cycle. The equation for actual peak

current (∆ip) in SWV is as below:

W/y ∗
2G€H >H
XKY = W/y W/y X‰Y (2.10)
 -w

Where, ∆Ψp is the dimensionless peak current and depends on n (number of electrons), ∆Ep

(pulse height) and ∆Es. It gauges the peak height in SWV.

Figure 2.7. (a) Potential modulation (b) Single potential cycle in square-wave voltammetry

(c) typical square-wave voltammogram.

61
The SWV has several advantages such as excellent sensitivity because the net current is

larger than both the forward or reverse components and the rejection of background currents.

The SWV is 4 and 3.3 times higher for reversible and irreversible systems, respectively, than

the analogues DPV. Major advantages of SWV are its speed and increases in the signal to-

noise ratio. It is useful the study of electrode kinetics to and determination of some analyte at

trace level (~ 10-8 M).

Chronoamperometry (CA): In CA, a fixed potential is applied to the working electrode and

the current produce is measure with time. It generally involves stepping of potential at the

working from a value at which no faradic reaction occurs to a final potential at which the

surface concentration of the electroactive species is effectively zero [Fig. 2.8]. The resulting

current-time response is called as chronoamperogram. During CA measurement, a stationary

working electrode and unstirred solution are used and under these conditions the mass

transport happen mainly by diffusion, therefore, chronoamperogram shows the change in the

concentration gradient in the vicinity of the surface. With progress of time, the slope of the

concentration profile of analyte is decreased due to gradual expansion of the diffusion layer

associated with the depletion of the analyte. Consequently, the current decays with time

according to the following Cottrell equation:

2G>€ W/y
i (P) = = EP #M/ (2.11)
 W/y - W/y

CA is frequently used for measuring the diffusion coefficient of analyte, surface area of the

working electrode and mechanism of the electrode processes, especially the ECE type. In

addition, CA help in the precise determination of concentration of analyte due to negligible

contribution of charging current.

62
Figure 2.8. (a) Potential-time waveform (b) change of concentration profile with time (c)

typical current-time response

Chronopotentiometry (CP): In CP, the current is held constant and the potential becomes

the dependent variable, which is measured as a function of time. The steady current (i) is

applied to the working electrode through which causes analyte (Ox) to be reduced at a

constant rate. The potential of the electrode moves to values characteristic of the Ox/Red

couple and varies with time as the Ox/Red concentration ratio changes at the electrode by the

continuous flux of the electrons. This consequences in a E-T curve like the that obtained in

potentiometric titration [Fig. 2.9]. After the concentration of Ox drops to zero at the electrode

surface, the flux of Ox to the surface is insufficient to accept all of the electrons being force

across the electrode-solution interface. The potential of the electrode will then rapidly shift

toward more negative values until a new, second reduction process can start. The time after

application of the constant current when this potential transition occurs is called the transition

time (τ), which is related to the concentration and the diffusion coefficient of analyte

according to following equation (Sand equation):

W/y W/y ∗
2G€H  >H
iŠ M/ = 
(2.12)

The shape and location of the E-t curve is governed by the reversibility, or the heterogeneous

rate constant, of the electrode reaction. The CP is useful for mechanism and heterogenous

ET-rate constant for stepwise electron transfer reaction, ET with coupled chemical reactions

and multi-components systems.

63
Figure 2.9. (a) Current-time waveform (b) typical potential-time response

In-situ spectroelectrochemistry: First, Spectroelectrochemical (SEC) experiment was

[78]
carried out by T. Kuwana in 1964 . SEC deals with the marriage between spectroscopic

and electrochemistry i.e., combination of reaction-oriented electrochemistry with species-

focused spectroscopy. It is coupled method which have the advantages of both the

electrochemistry and spectroscopic measurements to describe the redox reaction at the

electrode surface [Fig. 2.10]. Principally, any form of spectroscopy such as IR, UV-Visible,

Raman, EPR, NMR etc., can be used to follow the progress of an electrode reaction.

Typically, spectroscopic response is monitored in situ while electrochemical reaction is

carried out under controlled conditions.

Figure 2.10. Spectroelectrochemistry principle and set-up

A light beam passes through the electrode surface to measure the absorbance changes

resulting from species produced or consumed in the electrode process. Therefore, optically

transparent electrodes (OTEs), which enable light to passed through their surface and the

64
adjacent solution, are the prerequisite in SEC experiments. OTEs may be (i) thin film (100-

5000 Å) of a semiconductor e.g., SnO2 or In2O3 or a metal e.g., Au or Pt deposited on a glass,

quartz, or plastic substrate or (ii) fine wire metal micromesh “minigrids” containing small

(10-30 µm) holes, which can provide good optical transmission (> 50%) and electrical

conductivity. For a general redox process: O + ne- ⟷ R, the change in absorbance is related

to concentration and optical path length. The absorbance change can be described by

considering a segment of solution of thickness dx and if R is the only absorbing species, the

differential absorbance upon passage of the light is dA = εRCR(x, t)dx, where εR is the molar

absorptivity of R. The total absorbance is then : = ‹Œ ∫A CŒ (Ž, P)&Ž, which is total amount
∞

of R and is equal to Q/nFA (Q= is the charge passed in electrolysis). Since Q is related to

integrated Cottrell equation, thus, the absorbance will be as below:

W/y W/y
I >H∗ €H -
:=  W/y
(2.13)

The above equation implies that absorbance is linearly dependent on t1/2 (and respective A-t

curve is called as chronoabsorptometry) and useful to determine the diffusion coefficient and

εR.

Applications: SEC is very useful for (i) the elucidation of reaction mechanism, and for the

explanation of kinetic and thermodynamic parameters, (ii) measuring the formal redox

potential and number of electrons transferred during redox conversion, (iii) the mechanism

diagnosis and kinetic characterization of coupled chemical reactions. In addition, SEC

enhances the overall selectivity of different sensing and detection applications.

Practical consideration in electrochemistry: In electrochemistry experiments, the

necessities include a cell (with 3 or 4-electrode system), a voltammetric analyzed (consisting

of a potentiostatic circuitry and a voltage ramp generator) and a recorder (i-E-t). Some basic

details are described below:

65
1. Electrochemical cells and electrodes: The electrochemical cell is generally an enclosed

beaker of 2-50 mL volume, which contains the three electrodes namely as working, reference

and auxiliary. These electrodes are immersed in the analyte solution. The electrode at which

the reaction of interest occurs is known as working electrode (WE) while the electrode that

provides a stable and reproducible potential and against which the potential of the WE is

compared is termed as reference electrode (RE). The RE is insulated through an intermediate

bridge to avoid the contamination of the analyte solution. A current carrying electrode of

inert conducting material such as platinum wire or graphite rod is employed as auxiliary

electrode (AE). The relative position of these electrodes and their proper connections to the

electrochemical analyzer is important.

Working Electrode: The characteristics of WE should be such that it should provide high

signal-to-noise ratio, reproducible response, chemical inertness with analyte, low cost, non-

toxicity, and high potential window, electrical conductivity, surface reproducibility,

mechanical properties. The mercury, carbon, noble metals such as platinum, silver and gold

are used as WE.

Reference Electrode: An ideally non-polarizable electrode whose potential is constant for a

long period of time is better for RE. The normal hydrogen electrode/Standard hydrogen

electrode (E0=0 V), saturated calomel electrode (SCE: Hg/Hg2Cl2/KCl [saturated], E0= 0.242

V vs. NHE) and silver-silver chloride electrode (Ag/AgCl/KCl [saturated], E0= 0.197 V vs.

NHE) are some commonly used aqueous based REs. For the non-aqueous media non-aqueous

REs are used such as a Ag wire in contact with AgNO3.

Counter Electrode: The area of the CE must be larger than that of WE so that its area does

not control the limiting current. Also, CE should not get dissolved in or react with the

experimental solution and the reaction product during redox reaction at the CE should not

react with WE. Pt-wire or glassy carbon are frequently used as CEs.

66
2. Solvents and supporting electrolyte: The choice of the solvent is governed by the

solubility of the analyte and its redox activity, and by the solvent properties such as the

electrical conductivity, electrochemical activity, no chemical reactivity with analyte or

products, and the wider potential range without any side reactions in presence of potential. In

electrochemical experiments, the frequently used solvents are water and some non-aqueous

such dimethylformamide, dimethylsulfoxide, methanol etc. The supporting electrolyte (SE) is

required to decrease the resistant of the solution, to maintain constant ionic strength,

swamping out the effect of the variable amount of naturally occurring electrolyte, and to

eliminate the electromigration effect i.e., The SEs, generally, are inorganic salts, a mineral

acid, or buffers. An excess of unreactive ionic salts (often termed as “swamping electrolyte”),

about 100 times greater than the concentration of analyte, is required for purely diffusion-

controlled transport of analyte towards electrode and to avoids its migration from bulk.

3. Inert gas purging: The electrochemical reduction of oxygen usually proceeds via two

well-separated two-electron steps as below:

O + 2H  + 2e# → H O  (2.14); E1/2 = -0.1 V (Versus Sat. calomel

electrode)

  + 2 + 2" # → 2  (2.15); E1/2 = -0.9 V (Versus Sat. calomel

electrode)

The large background current accruing from above redox reaction of oxygen interferes with

the reduction process of analyte and the products of oxygen reduction can also affect the

electrochemical process of interest. Therefore, for gaining information about the true redox

peaks of analyte, the oxygen removal from the solution is utmost task. Commonly, the

purging with an inert gas, such as high purity nitrogen gas, for 5-10 minutes prior to

recording of the voltammogram is used to remove the dissolved oxygen.

67
4. Electrochemical analyzer: The schematic diagram of a three-electrode potentiostat is

given in Fig. 2.11. Basically, the electrochemical analyzer instrument contains two circuits as

(i) a polarizing circuit which applies potential to the cell, and (ii) a measuring circuit which

monitors the cell current. The analyzer cares the potentiostatic control of the working

electrode and minimizes errors from cell resistance (R). The applied potential (Eapp) is related

to ohmic potential drop (iR) as Eapp = EWE-ERE-iR. The ohmic potential drop results in poorly

defined voltammograms with lower current response and shifted and broadened redox peaks.

Under potentiostatic control, compensation of major fraction of the cell resistance is achieved

using a three-electrode system and a combination of operational amplifiers and feedback

loops. In addition, the reference electrode is placed closer to the working electrode and is

connected to the instrument through a high resistance circuit that draws ultimately no current

from it. A current carrying auxiliary electrode is placed in the solution for completion of

current path and current flow through the solution between the WE and AE. Therefore, no

current passes through the RE and due to it specific position (as close as possible to WE), the

potential drop caused by the cell resistance (iR) is minimized. The closeness of RE with the

Weis accomplish using a Luggin probe, which is as specially designed bridge of the RE. In a

scenario, when the potential sensed by the RE is lesser than the desired value, the operational

amplifier provides a corrective potential value, Further, in presence of operational amplifier

current to voltage converter (called as “current follower”) to the WE, it if feasible to measure

the current without disturbing controlled parameters. With a ramp generator in instrument,

production of various regularly changing potential waveform is possible. The Ru is the

uncompensated solution resistance between RE and WE and due it some fraction of potential

drop called as iRu is still be included in the measured potential. This fraction is large when

resistive non-aqueous media are used. However, using appropriate positive feedback, this

68
fraction of drop can be automatically compensated from the potential signal. Bi- and multi-

potentiostat offers simultaneous control of more than one WE.

Instrumentation of electrochemical methods: For uranyl with Citrate, PPA and PCs ligands,

the cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square wave

voltammetry (SWV) and Chronopotentiometry (CP)/amperometry (CA) measurements were

undertaken with an AUTOLAB PGSTAT100 electrochemical analyzer with three-electrode

systems consisting of SMDE as working electrode (sensitive for speciation analysis [79]), Ag-

AgCl/(sat. KCl) as a reference and glassy carbon as an auxiliary electrode. For Np-PPA

system, the glassy carbon electrode (GC) was used as working electrode while other

electrodes remain same as above. In case of studies in DES media, the CV, DPV, and in-situ

spectroelectrochemical measurements were undertaken with a CHI (760 E model)

electrochemical analyzer with three-electrode systems consisting of glassy carbon (GC) as

working electrode, Ag-AgCl/sat.KCl as a reference and Pt wire as an auxiliary electrode.

Before use, the GC working electrode was polished with graded 5µM alumina powder and

rinsed with doubly distilled water + methanol.

Figure 2.11. (a) Three electrode set-up (b) schematic diagram of a three electrode

potentiostat (c) Potentiostats used in the present studies.

69
High purity N2 gas was used to purge the solution for at least 10 minutes prior to each

experiment. Spectroelectrochemical experiments were carried out by coupling the

potentiostat with Ocean optics spectrophotometer with QE 65000 detector. UV-visible

absorption Cuvette with the Teflon top was used as a spectroelectrochemical cell. ITO plate

was used as the working electrode with Ag/AgCl (sat. KCl) as the reference electrode and Pt

wire as auxiliary electrode.

2.3.2 UV-Visible absorption spectroscopy: The UV-visible absorption spectroscopy is the

elementary tool to get qualitative information about the functional group of organic moieties

and oxidation state of metal ion in solution. In addition, it is one of the direct techniques for

quantitative analysis of soluble species since the spectra obtained are the representative and

reflection of structure of a specific species. UV-Visible absorption spectroscopy is mainly

based on the principle of Lambert-Beer law which is discussed below

—
“ = ”•–( ˜ ) = ™š› (2.16)
—

Where, A is the absorbance, I0 and I are the intensity of incident and transmitted light, ε is the

molar extinction/absorption coefficient (characteristics of species and it is not dependent on

the concentration and path length), c is the molar concentration of the absorbing species and l

is the path length. The species (metal ion, ligand and complex) present in the solution absorb

the incident photon and exhibit the transition from ground state to excited state. The

wavelength at which maximum absorption occur is denoted as λmax and is used for

spectroscopic analysis such as concentration and stability constant determination.

Instrumentation of UV-Visible absorption spectrophotometer: All the spectrophotometric

measurements were performed using a JASCO V530 model spectrophotometer. The V-530 is

a double beam spectrophotometer which contains the light sources as a deuterium (D2) lamp

(190 to 350 nm) for the UV region and a halogen (WI) lamp (340 to 1100 nm) for the Vis-

NIR region. It measures the absorbance of a species in the wavelengths range 190 to 1100 nm

70
with a wavelength resolution and accuracy of 1 nm and ± 0.5 nm, respectively. The half-

neutralized ligand solution is added in increments to a fixed volume (2.0 mL) of actinyl ions

solution present in quartz cuvette. The spectra are recorded for each addition of ligand

solution to the metal solution and enough time (300 s) was given for equilibration (though the

reaction was instantaneous) after each addition before recording the spectra. All the titration

data was analyzed using the Hyperquad computer programming [80] to determine the stability

constants and molar absorbencies.

2.3.3 EXAFS: The X-ray Absorption Fine-Structure (XAFS) is the modulation of the x-ray

absorption coefficient at energies near and above an x-ray absorption edge. The XAFS

spectroscopy has been widely employed for studying the local structure around a metal ion at

molecular scale. The term “XAFS” is a broad one that comprises mainly XANES (X-ray

Absorption Near Edge Structure) and EXAFS (Extended X-ray Absorption Fine Structure)

[Fig. 2.12]. The physical quantity that is measured in XAFS is the X-ray absorption

coefficient µ(E), which describes how strongly X-rays are absorbed as a function of X-ray

energy. XAFS is based on the X-ray photoelectric effect, in which an X-ray photon incident

on an atom within a sample is absorbed and liberates an electron from an inner atomic orbital

(e.g., 1s). The “photoelectron” wave scatters from the atoms around the X-ray absorbing

atom, creating interferences between the outgoing and scattered parts of the photoelectron

wavefunction. These quantum interference effects cause an energy-dependent variation in the

X-ray absorption probability, which is proportional to the X-ray absorption coefficient. The

XAS measurements have been carried out at the Energy-Scanning EXAFS beamline (BL-9)

at Indus-2 Synchrotron Source (2.5 GeV, 100 mA) at Raja Ramanna Centre for Advanced
[81]
Technology (RRCAT), Indore, India . This beamline operates in the energy range of 4

KeV to 25 KeV. The beamline optics consists of a Rh/Pt coated collimating meridional

cylindrical mirror and the collimated beam reflected by the mirror is monochromatized by a

71
Si(111) (2d=6.2709 Å) based double crystal monochromator (DCM). The second crystal of

DCM is a sagittal cylinder used for horizontal focusing while a Rh/Pt coated bendable post

mirror facing down is used for vertical focusing of the beam at the sample position. Rejection

of the higher harmonics content in the X-ray beam is performed by detuning the second

crystal of DCM. In the present case, XAS measurements have been performed in both

transmission mode and fluorescent mode. For the transmission measurement, the absorption

coefficient µ is obtained using the relation:

− µx
I = I e
T 0 (2.16)

where, x is the thickness of the absorber. The EXAFS spectra of all samples at U L3-edge

were recorded in the energy ranges of (17050-17900) eV. In order to take care of the

oscillations in the absorption spectra µ (E ) has been converted to absorption function χ (E )

defined as follows:

µ (E ) − µ0(E ) (2.17)
χ (E ) =
∆µ0(E0)

where, E0 is absorption edge energy, µ 0 ( E0 ) is the bare atom background and ∆µ 0 ( E0 ) is the

step in µ ( E ) value at the absorption edge. The energy dependent absorption coefficient

χ ( E ) has been converted to the wave number dependent absorption coefficient χ (k ) using

the relation,

2m( E − E0 )
K= (2.18)
h2

where, m is the electron mass. χ (k ) is weighted by k2 to amplify the oscillation at high k and

the χ(k)k2 functions are fourier transformed in R space to generate the χ ( R ) versus R spectra

in terms of the real distances from the center of the absorbing atom. The set of EXAFS data
[82]
analysis programme available within Demeter software package have been used for

EXAFS data analysis. This includes background reduction and Fourier transform to derive

72
 [82]
the χ ( R ) versus R spectra from the absorption spectra using ATHENA software and

finally fitting of experimental data with the theoretical spectra using ARTEMIS3 software.

The data has been fitted from 1-3.2 Å in R space and the goodness of fit has been

R factor
determined by the value of the defined by:

[Im( χ dat ( ri ) − χ th (ri )]2 + [Re( χ dat ( ri ) − χ th ( ri )]2

R factor = ∑
[Im( χ dat (ri )]2 + [Re( χ dat ( ri )]2
(2.19)

where, χ dat and χ th refer to the experimental and theoretical χ (r ) values respectively and Im

and Re refer to the imaginary and real parts of the respective quantities.

XANES: band structure; long range order;

hybridization
µ(E)

Edge: Oxidation state

Energy (eV)

Figure 2.12. The representative XAFS spectra showing various regions of XAFS (XANES,

EXAFS etc.) and information obtained from them.

2.3.4 Calorimetry: Isothermal titration calorimetry (ITC) is a technique used to study the

thermodynamics of a chemical or physical processes. It measures the energetics (heat

released or absorbed) of a chemical reaction at constant temperature. The reaction is triggered

by changing the chemical composition of the sample by titration of a required reactant. The

heat associated with the reaction is the direct thermodynamic observable (related to both the

enthalpy and extent of reaction). The foundation of this technique is based on the

measurement of heat, q. Because of the relationship between the change in enthalpy and the

73
change in internal energy (∆E) of a system, the heat (q) absorbed or released is equal to ∆H

when the system is at constant pressure (P)

∆H = ∆E + P∆V (2.20)

∆E = q+w=q – P∆V (2.21)

∆H = qp- P∆V + P∆V (2.22)

Where ∆V = change in volume and w = work

Instrumentation for ITC: An isothermal titration calorimeter (Nanocalorimeter TAM-III,

Thermometric AB, Sweden) was used to carry out all the calorimetric experiments. It is a

twin thermopile heat conduction type calorimeter and differential power signal measured is

dynamically corrected for the thermal inertia of the system. The titration assembly consists of

4 ml reaction vessel and a reference vessel. The heat capacity of reaction vessel and reference

vessel is balanced by keeping the same volume of solutions in both sides in order to minimize

the short-term noise. The titrant is delivered in the reaction vessel through a stainless-steel

injection needle (length 1 m and internal diameter 1.5 х 10-4 m) connected to the Hamilton

syringe containing the titrant. The syringe is driven by Lund Syringe pump. The temperature

of the bath was maintained at 298.0000 (±0.0001) K.

Determination of Enthalpy of Formation by ITC: The enthalpy of protonation of ligand

can be obtained by either titrating the protonated ligand solution with base or by titrating

deprotonated ligand anion with acid solution. In the present study, the later procedure was

employed to determine the enthalpy of formation of protonated species of ligands. All the

titrations were carried out in 1.0 M NaClO4 ionic medium at 298 K temperature. At each step

of titration, the reaction heat (QiP) solely of protonation, was calculated using the equation.

QiP = QiT - QiD (2.23)

Where QiD is the heat change during dilution titration, QiT - the sum of heat changes due to

both the protonation and dilution. The heat change during the formation of protonated ligand

74
is related to ∆HP (enthalpy of protonation) and ∆Hn (enthalpy of neutralization) by following

relation

QiP = ∆HP1 (viHL – vi-1HL) + (∆HP1 + ∆HP2) (viH2L - vi-1H2L) + ∆Hn ∆vHn0 (2.24)
X
where vi - the number of moles of species ‘X’ in the cup after ith injection which were

calculated using Hyperquad Simulation and Speciation software (HySS 2006). For the

calorimetric titration of complexation studies, the metal ion solution at the desired pH and

ionic strength was taken in the reaction vessel and was titrated with the ligand solution. The

heat released due to complexation only (Qi C) at any injection i can be given by

Qi C = Qi T - Qi D - Qi P (2.25)
T D
where Qi is the heat released in titration of ligand with metal atom and Qi is the heat

released due to dilution and Qi P is the heat of protonation of the ligand. Using Hess's law of

constant heat summation, the enthalpy of formation for each complex (for example: the

formation of ML4) can be related to Qi C.

2.3.5 Electro-spray ionization mass spectrometry (ESI-MS): The electro-spray ionization

(ESI) is a soft ionization technique extensively used for production of gas phase ions without

fragmentation of thermally labile molecules. Therefore, ESI-MS is applicable for molecular

speciation (basically the stoichiometry of metal-ligand complex) of metal ions in solution [83].

The basic architecture of the ESI-MS composed of three basic components as ion source,

mass analyzer, and detector. The intact molecular ions are produced in the ionization

chamber where the ion source is kept, and then they are transferred in the mass analyzer

region via several ion optics, which are basically kept to focus the ion stream to maintain a

stable trajectory of the ions. The mass analyzer sorts and separates the ions according to their

mass to charge ratio (m/z value). The separated ions are then passed to the detector systems to

measure their concentration, and the results are displayed on a chart called a mass spectrum.

Since the ions in the gas phase are very reactive and often short lived, their formation and

75
manipulation should be conducted in high vacuum. For this reason, the ion optics, analyzer,

and also the detectors are kept at very high vacuum (typically from 10-3 torr to 10-6 torr

pressure). A dilute analyte solution is injected by a mechanical syringe pump through a

hypodermic needle or stainless-steel capillary. A very high voltage (2-6 kV) is applied to the

tip of the metal capillary relative to the surrounding source-sampling cone. Because of this,

the dispersion of the sample solution into an aerosol of highly charged electro-spray (ES)

droplets occurs. The ions derived by ES process are multiply charged, and the analyte

remains intact (no fragmentation). In positive ion mode the charging generally occurs via

protonation (sometimes metalation also), but in negative ion mode charging occurs via

deprotonation of the analyte. During transfer of an analyte from solution to the gas phase via

ESI, the analyte

solution undergoes

three major processes:

(a) production of the

charged droplets from

the high-voltage

capillary tip where the

analyte solution is

injected, (b) repeated

solvent evaporation

(from the charged droplet) and droplet disintegration, resulting a very small charged droplet,

which is able to produce the charged analyte, and (c) finally a mechanism by which the gas-

phase ion is formed.

Instrumentation of ESI-MS: Mass Spectrometric studies were carried out with the

electrospray ionization ion source equipped with the Quadruple-Time-of-Flight mass

76
analyzer (model micrOTOFQ-II, Bruker Daltonics GmbH). Data analysis was carried out

with Bruker Compass Data Analysis software (supplied by Bruker Daltonics GmbH). The

solution was infused into the mass spectrometric system with the help of 100 µL syringe

(Hamilton) using a syringe pump (NEMESYS, Cetrol GmbH). The capillary voltage of -4500

V and +3800 V were applied for the measurement in the positive ion mode and negative ion

mode, respectively. Nitrogen was used as both dry gas and nebulizer gas at a flow rate of 4

Lmin-1 and the pressure 0.3 bar, respectively.

2.3.6 Theoretical calculations: Theoretical calculations including the density functional

theory (DFT) and molecular dynamics simulation (MD) are the important methods (i) to

understand the coordination modes of ligand with actinyl ions, (ii) to get the optimized

structure with minimum energy of species with ligand in aqueous medium and DES media

(iii) to know the hydrogen bonding interaction in DES formation using HBA and HBD,

number of hydrogen bonds with dilution of DES with water and the possibility of formation

of stereognostic intramolecular hydrogen bond (IMHB) interaction, and (iv) to authenticates

the experiment results via calculating the diffusion coefficient, bond distances, partial charges

and Gibbs free energy.

DFT calculations for aqueous system: The structure of three CPs and their complexes with

UO22+ ion were optimized without any symmetry restriction using B3LYP functional with

triple valence plus polarization (TZVP) basis set as implemented in Turbomole package.

Relativistic effective core potential (ECP) was used for U where 60 electrons are kept in the

core of U. The energies were calculated at the same level of theory. Due to the inclusion of

non-local HF contribution in the exchange functional, the B3LYP functional works well in

predicting the energetics. The frequency calculations were carried at the same level which is

used for geometry optimization. The gas-phase free energy, ∆Gg was computed at

T=298.15K and P=1atm. The solvent effects were considered using the Conductor like

77
Screening Model (COSMO) solvation model. The default COSMO radii were used for all the

elements. The dielectric constant, ε of water was taken as 78.4. The gas-phase minimum

energy structures were used for the calculation of single-point energy in the COSMO phase.

MD and DFT in DES media: For the simulation of UO22+ ion in the solution of choline-

malonic-water, first the geometries of choline and malonic were first optimized using M06-

2X functional [84] and TZVP basis set [85] as implemented in Turbomole suite of package [86].

Then a simulation box was created with 500 choline, 500 chloride, 1000 malonic acid (MA)

(for pure DES as well water-saturated DES), 5 uranyl (UO22+) ions and 10 Cl- molecules.

Percentage of water was kept 5%, 10 and 20% by placing water molecules in the box.

(dimensions of approximately 6.5 × 6.5 × 6.5 nm3). Initial configurations of the system were
[87]
built with the PACKMOL package , ensuring a random distribution of molecules. In the
[88]
present study, all the simulations were performed using GROMACS (VERSION 5.1.2)

molecular dynamics simulation package employing all-atom optimized potentials for liquid

simulations (OPLS–AA) for bond stretching, bond angle bending and dihedral angle torsion.

For, UO22+, we have used the potential parameters from our earlier study [89]
and for water,

SPC water model was adopted. The systems were first energy minimized using the conjugate

gradient method and then the steepest descent method of minimization. All ions were

represented by charged 12-6 Lennard-Jones sites bound together by harmonic bond distance,

bond bending (angular), and dihedral potentials. Lorenz-Berthelot rules were used throughout

for the mixed Lennard-Jones terms and the long-range electrostatic interactions were

incorporated using the particle mesh Ewald techniques. The systems were simulated for 100

ps and 1ns of equilibration in NVT and NPT ensemble respectively using Noose-Hoover

thermostat and Parrinello-Rahman barostat for pressure coupling with a time step of 1fs.

Further, the data was collected after the production run of 50 ns using NPT ensemble. The

78
simulation trajectories were visualized using VMD graphical package using data of 1ns run

after 50ns production run.

2.4 Other supporting techniques (only instrumentation is discussed)

(i) Thermogravimetry analysis (TGA): The loss in weight as a function of temperature for

pure DES and uranium matrices dissolved DESs was recorded in thermogravimetry and

differential scanning calorimetry (TG-DSC). TG-DSC of model DSC-2 supplied by M/s

Mettler Toledo Pvt Ltd, Switzerland was used. Commonly the loss in weight occurs as a

result of the breaking of bonds and liberation of various molecules. The weaker bond breaks

at a lower temperature and stronger at a higher temperature. Prior to the actual measurements,

the instrument was calibrated for temperature and heat flow rate using high purity standards

like In, Pb and Zn. 40 mg of each sample were loaded in the sample crucibles of capacity 150

uL and run at a heating rate of 10 Kmin-1 with an argon flow of 50 ml min-1 from 25oC to

450oC. A blank run was carried out with the same experimental conditions to subtract

atmospheric and instrumental effect by keeping two empty alumina crucibles of capacity 150

uL in reference and sample holders. The melting point of pure components and DESs were

measured using DSC (DSC823e supplied by M/s Mettler Toledo Pvt Ltd, Switzerland) with a

heating rate of 5 Kmin-1 and in argon gas flow of 50 mlmin-1. The temperature and heat flow

calibration were carried out following a similar procedure as mentioned above for the TG-

DSC system.

(ii) D.C. Arc AES and EDXRF: The D.C. Arc atomic emission spectrometric (D.C.Arc

AES) technique was carried out using Spectro-Arcos Atomic Emission Spectrometer

procured from Spectro-Arcos, Germany. The array of capacitively coupled device (CCD) was

used as a detector system instead of a photomultiplier tube. The resolution of the instrument

was recommended as 0.02 nm for the wavelength range 450-800 nm. The optical design

corresponds to Paschen Runge mounting. The spectrometer has holographic grating with

79
maximum groove density 3600 grooves/nm. The focal length of the optical arrangement is

750 mm. Using this instrument, the maximum wavelength covered was 130-800 nm. In D.C.

Arc AES, standard graphite electrode, ASTM designation E-130-66 type S-2 on a type S-1

pedestal were used as the anode. ASTM designation E-130-66 type C-1 was used as a pointed

cathode. A Jordan Valley EX-3600 M EDXRF spectrometer was used for XRF analysis. The

system is equipped with a Si(Li) detector, which is having a 12.5 mm thick beryllium

window. The nEXt system software provided by the manufacturer was used for acquisition

and analysis of the spectrum. The detector used in the present case was having a resolution of

139 eV at Mn-Kα (5.9 keV). The wavelength range under investigation is 1–40 keV. 30 kV

high voltage and 200 µA emission current was utilized for data acquisition. The cross-

sectional area for the aperture of the X-ray beam at the sampling site is circular in nature with

8 mm diameter. The 1 mL of standards/samples in solution form was placed in the sample

holder having a polyvinyl chloride tubular guide with 13 mm internal diameter.

(iii) FT-IR spectra: FT-IR spectra were recorded using the Platinum attenuated total

reflection (ATR) technique (ALPHA FTIR spectrophotometer). All spectra were obtained

using a resolution of 4 cm-1 (wavenumber) and equal measurement conditions (3900–450 cm-
1
) and 40 scans. (Scan means 16 repetitions of a single FT-IR measurement).

(iv) Karl-Fischer titrations (KF): The water content in DESs were determined by Karl-

Fischer titration using a single batch of KF reagent procured from Merck by Titrando-905

(Metrohm AG) auto-titrator. The instrument was calibrated by titrating a known weight of

water in methanol using the KF reagent and deriving a multiplying factor F with units of mg

of water /volume of KF in mL. Known weights of DESs were similarly titrated and

corresponding water content was calculated using the calibration above.

(v) Speciation modelling: In the present studies, speciation modelling of actinyl ions in

presence of ligands were carried out using two software namely, Hyperquad simulation and

80
speciation (HySS) software [90] and MINTEQA2 [91]. HySS is a computer program written for

the Windows operating system on personal computers which provides (a) a system for

simulating titration curves and (b) a system for providing speciation diagrams. MINTEQA2
[92]
is an equilibrium speciation model which uses the Newton-Raphson approximation

method and includes the implementation of a competitive Gaussian model for computing the

complexation of metals.

2.5 Details about the equations

(i) Equation for evaluation of thermodynamics complexation:

The heat change (Qir) at each addition of ligand to the metal solution is the summation of heat

due to metal-ligand complexation (Qic), ligand protonation (Qip) and the dilution (Qid)

processes. The heats due to solely complexation can be deduced by following relation.

Qic = Qir - Qip - Qid (2.26)

(ii) Equations Used in the electrochemical study:

(a) The number of protons associated with electron transfer step in both region A & B was

accounted from following equations with using their corresponding slope values.

dE/dpH = -0.059p/αn for irreversible reduction (2.27)

dEp/dpH = - 0.059 P/n for reversible reduction (2.28)

Where p and n is the number of protons and electrons respectively involved in ET step, α is

the transfer coefficient.

(b) With the assumption of coupled chemical reaction, the slope of the linear portion of Ecom

vs. logν plot can be represented as below:

dEcom/dlogν = 0.059/2αn (2.29)

(c) Laviron equation

Following the Laviron equation indicates the linear dependency of Ep on the logarithm of

Scan rates (logν) for irreversible redox peak.

81
 .žAžŸ Ÿ ¦H .žAžŸ
E = E A + < (α¡)¢
? log < (α¡)¢ ? + < (α¡)¢
? logν (2.30)

(d) Randles-Sevcik equation

ip = (2.99x105) n (αn)1/2AC0*D1/2 √ν (2.31)

ip = (2.69x105) n3/2 AC0*D1/2 ν1/2 (2.32)

where A is the electrode area, F the Faraday, icom the reductive peak current, C0* the bulk

concentration of complex, and n = 1 is the number of electrons transferred.

(e) In Chronopotentiometry (CP), for diffusion-controlled irreversible reduction of an

electroactive species, the potential of the working electrode at any time (t) can be

expressed by following equation.

RT nFAC 0 k 0 f , h RT t (2.33)
E (t ) = log[ ]+ log[1 − ( ) 1 / 2 ]
α nF i α nF τ

Where, kof, h is the heterogeneous forward rate constant and E(t) is the potential at time

t and τ is the transition time for reduction wave.

(f) An expression for ip in terms of Ep can be described by the following equation:

F2G
iY = 0.227 !9:CA∗ E A exp [− Œª
«KY − K , ¬] (2.34)

If Ef is known and Ep occur beyond Ef, a plot of lnip versus (Ep-Ef) would give a straight line

with a slope of (αnF/RT) and intercept of ln (0.227 nFAC0*k0). The value of αn and k0 were

evaluated from slope and intercept of the straight line of lnip versus (Ep-Ef) plot respectively.

Where Ep is the peak potential, Ef is the formal redox potential, k0 is the standard

heterogeneous rate constant, α is the electron transfer coefficient, n is the number of

electrons, F is the Faraday constant, ν is the scan rate (V/sec), R is gas constant (8.314 J K−1

mol−1) and T is the temperature in Kelvin.

(g) The linear relationship between Ep and log ν according to the following equation:
º º
°± ¹˜ ²³´½ 
­® = ­ − ¯
[˜. µ¶ + . ·˜· ”•– ¸ ˜ ¼ + . ·˜· ”•– < ? ] (2.35)
²³´ » °±

82
Where k0 is the standard heterogeneous rate constant and all other notations have the usual

meanings.

(h) In those cases where the calculation of Ef is not so simple, it is derived from the literature
[92]
that equation 2.36 can also be used, eliminating the Ef, for the calculation of k0.

#º/
(¾˜ )¿℃ = º. ºº Á˜ «Âà L ÂÃ/ ¬ ĺ/ (2.36)

Where the notations have their usual meanings, knowing values of Ep-Ep/2 at a

particular scan rate and with the knowledge of D0, equation 2.36 can be used to

calculate k0.

(iii) Equation used in Molecular dynamics and DFT simulation: It is very important and

necessary to understand the microscopic structure of the molecular system and thus the pair

correlation functions (PCF) have been evaluated to examine the bulk structures of molecular

systems and is expressed as:

Å Å ÅÈ
}1* (m) = Æ Å Å 〈∑1 Ç ∑1Ì* Ë (m L m1* )〉 (2.37)
Ç È

Here, N, r and ρ indicate the total number of molecules, distance and number density

respectively. Ni and Nk denote the number of molecule i and molecule k respectively and rik is

the distance between the centre of masses of molecule i and k.

Self-diffusion coefficient: The self-diffusion coefficient is a highly important dynamical

quantity to build up an understanding of the mobility of solute particles and is calculated

from Einstein’s equation using the mean square displacement (MSD) profile as:

lim-→∞ < (m(P) L m( PA )) > = 6;P (2.38)

Where r(t) and r(0) are positions of atom at any time t and at t=0 respectively. The left part of

the equation indicates the ensemble average of squared displacement i.e., MSD. The

diffusivity, D is then computed from the slope of MSD.

2.6 Determination of stability constant of complex: The methods used in present studies

are discussed below

83
(i) Electrochemical method: The voltametric studies of stabilities of metal complexes,

involve the determination of shifts in potential in the presence of increasing amounts of

complexing ligands. The shift increases with increasing ligand concentration. Out of a

number of possible methods for mathematical analysis of shift in potential, the Deford-Hume

method has been applied here owing to the possibility of successive complex formation with

increasing ligand concentration. In this case the peak potential was found to shift with

varying ligand concentration at fixed metal ion concentration or varying metal ion

concentration at fixed ligand concentration. The stability constants can be determined by the

following relations initially proposed by Deford-Hume [93].

F0(X) = Σ βn [X]n (2.39)

= β0 + β1[X] + β2[X]2 +……..βn [X]n (2.40)

Where, F0(X) is a polynomial function representing the sum of the βn[X]n for all complexes,

βn is the cumulative stability constant of the nth complex, [X] is the analytical or total

concentration of the added species (PPA in this case), and β0=1 for the zeroth complex. F0(X)

is related to the current and potential data by equation (2.41),

F0(X) = antilog {[0.434nF/RT] [∆Ep] + [log (Ip)s /(Ip)c]} (2.41)

Where, ∆Ep = (Ep)s-(Ep)c, that is, the shift in potential; n and Ip are number of transferred

electrons and peak current, respectively. The subscripts c and s indicate complexed and free

anion respectively. The evaluation of other functions from F0(X) is described elsewhere in

detail [93] and they are mentioned briefly here for convenience:

F1(X) = [F0(X)-1]/[X]; (2.42)

F2(X) = [F1(X)-β1]/[X]; (2.43)

Fn(X) = [Fn-1(X)-βn-1]/[X] (2.44)

84
At constant ionic strength and pH, the shifts in potential with increasing ligand or metal ion

concentration have been measured and used to evaluate the F0(X). From the plot of F0[X.] vs.

[ligand Conc.] the logβ value can be calculated.

(ii) Spectrophotometry method: The formation constant of a complex can be evaluated by

taking known concentration of a metal ion and a ligand, and experimentally monitoring the

optical densities of the metal, ligand & metal-ligand mixture separately. Metal-Ligand

complex stoichiometry can be obtained by the Job's method of continuous variation, method
[94-95]
of mole ratio, method of slope ratio, method of isosbestic point . The absorbance of the

solution at any point of time is an additive contribution of the absorbance of all individual

species present such as metal, ML, ML2…MLn in the solution as shown below,

AT = AM +AML +AML2 +AML3……. + AMLn (2.45)

AT = εM CM l+ εML CML l + εML2CML2 l + εML3CML3 l…….. + εMLnCMLn l (2.46)

: ª = o Σ21@A ‹ÑÒ1 CÑÒ1 (2.47)

Where εMLi is the molar absorption coefficient of species MLi, CMLi is the concentration of

species MLi. Each incremental addition of ligand solution to metal solution consequences in

an above equation for all the wavelengths and results in a matrix of the form A (N, λ).

Herein, N is the number of titration point and λ is the wavelength of consideration. During

titration, the solution of this matrix in combination with mass balance equations are used to

determine the molar absorption coefficients and stability constants of the species formed. The

spectroscopic data was analyzed using Hyperquad software [80]

[96]
2.7 Green Chemistry Matrices: A basic understanding of green metrics is necessary to

assessing greenness of the process or methodology.

The knowledge about the appropriate green metrics is a prerequisite for a meaningful

comparison with old methods. The metrics are:

85
(a) E-Factor: It is the quantity of waste that is produced for a given mass of product. It also

exposes the relative wastefulness of different steps of chemical process/methodology.

ª+-6) Ó600 +, „60-/

K 9gdPem = (2.48)
Ñ600 +, ,126) Y4+5(3-
(b) Atom economy: It is a calculation of how much of the reactants remain in the final

product. Final product in this context applies to a single chemical transformation, a series of

chemical transformations in a single stage of a multistage synthetic route, or to the entire

route to a final product.

× 100
Ñ+)/3()64 „/1Õ.- +, Y4+5(3-
:Pe| Kde!e| (%) = (2.49)
Σ Ñ+)/3()64 „/1Õ.- +, 4/63-62-0
(c) Mass intensity: It considers the yield, stoichiometry, the solvent, and the reagent used in

the reaction mixture, and expresses on a weight/weight basis rather than a percentage

ª+-6) Ó600 (0/5 12 6 Y4+3/00

gff 7!P"!fiP = Ñ600 +, Y4+5(3-
(2.50)
(d) Reaction mass efficiency (RME): When calculating reaction mass efficiency, atom

economy (AE), yield and the stoichiometry of reactants are included. RME is the percentage

of the mass of the reactants that remain in the product.

Ñ600 +, Y4+5(3-
%"gdPie! |gff "ppidi"!d (%K )(%) = Σ Ñ600 +, 4/63-62-0
× 100 (2.51)

2.8. Detection limit of various technique and advantages of electrochemistry for

speciation: Electroanalytical techniques better technique for speciation of actinides because

(1) provides information about different oxidation states of metal ion in solution (ii) low

detection limit (Table 2.2) and low cost (iii) has large linear range and ability to speciate

based on complex eciatlability (iv) low energy excitation technique and species selective

rather than element selective (v) equally suitable for analyzing inorganic, organometallic and

organic compounds.

86
Table 2.2 Detection limit of various techniques for speciation of actinides

Technique Approximate detection

limits
NMR 10-1–10-4 M
X-ray Absorption 10-1–10-4 M
Spectroscopy
UV-Visible Absorption >10-5 M
Spectroscopy
LIPAS 10-5–10-9 M
Laser-Induced Thermal 10-5–10-9 M
Lensing Spectroscopy
TRLFS 10-5–10-9 M
Electroanalytical 1-10-10 M

87
 Chapter 3

Redox Speciation of Uranyl with Citrate and Phenylphosphonic acid

(carboxylate and phosphonate based organic chelators)

AIM: Studies on speciation of uranium with carboxylate and organophosphorous ligands in

aqueous solution are important from

point of view of mobility of uranium

in the environment. In this chapter,

the speciation of uranyl (UO22+) with

(1) citrate and (2) phenylphosphonic

acid (PPA) were investigated on the

basis of its redox behaviour with

varying physiochemical conditions

using electrochemical methods. ESI-

MS studies on solutions of varying UO22+ to ligands ratios and pH were used to confirm

complex stoichiometries.

88
3.1 Introduction:

Speciation studies on Uranium have been of considerable interest for quite some time
[16-17. 19-20, 97]
with an objective to predict its distribution and fate in the environment . This

becomes important as anthropogenic activities, such as, milling and mining, may create
[20]
situations of higher concentrations of uranium in the geosphere than that naturally

abundant in soil and water (2-4 ppm and 3 ppb respectively). Its radiological and

toxicological effects have been the subject of interest to environmentalists. Hence, knowledge

of the speciation of uranium and its complexes is one of the interesting subjects, with regard

to understanding its migration behavior in an aquifer [16-17, 20, 27] and to evaluate its impact on

the living organisms. Uranium mobility and transportation in the environment is strongly

dependent on its oxidation states, and hence, there has been renewed interest in redox

chemistry of uranium and its complexes in the recent past. Uranium is a redox-sensitive
[20, 98]
element and its redox chemistry is exceptionally rich and diverse due to readily

accessible oxidation states ranging from III to VI and the sensitivity of the redox potential to
[98]
the coordination environment around the metal ion . Investigation of the redox properties

of uranium in presence of chelating agents [20, 26, 29] is important from the point of view of its

effect on Uranium speciation involving the solubility, complexation, sorption, precipitation,

bioavailability, and toxicity, which are remarkably dependent on the oxidation states and

physiochemical conditions, viz., Eh, pH, etc. [20]

Citric acid (C3H5O(COOH)3): It is a naturally occurring α-hydroxy polycarboxylic acid

forming strong water-soluble complexes with both U(VI) and U(IV) over a wide range of pH
[99]
. It is a versatile chelating agent, and is a common constituent of domestic, industrial as

well as nuclear wastes. With proper steric arrangement it forms small chelate rings in the

equatorial plane of the uranyl ion giving highly stable uranyl chelates. It exhibits relatively

consistent removal efficiency which has been extensively used for decontaminating the

89
contaminated sites in nuclear facilities. Uranyl ion complexation with citrate in

environmental systems provides higher solubility, increased mobility and enhanced

availability for microbial and phytocoenosis groups [100-101]. Citric acid is preferred over other

organic ligands for removal of uranium due to the formation of bio- or photo-degradable
[100]
complexes of uranium thereby controlling its mobility in the environment . Citric acid

increases uranium accumulation in plants, thereby facilitating phyto-remediation strategies

[102]
of contaminated soils. Moreover, speciation studies on the Uranyl Citrate complexes are

also important in chelation therapy towards the development of formulations for detoxication

and excretion of uranium [20]. The pka values of citric acid are given in scheme 3.1.

Phenylphosphonic acid (PPA): Recently, metal phosphonates have received increasing

attention because of their potential applications in ion exchange, catalysis, sorption, and

intercalation chemistry. Doubly ionizable phosphonate groups (-PO3H2) have many

properties, which are unique, and promise more efficient separation processes for waste

clean-up and environmental restoration [103-104]. Organic and inorganic phosphorus containing

ligands which are pervasive in soil systems are known to form strong complexes with

uranium. High proportion of phosphorus exists in organic forms, as derivatives of

phospholipids, phosphonic acids, phosphoric mono- and diesters in soils rich in organic
[105]
matter . Though relatively low content of P (800−1500 mg/kg) is found in humic

substances, organic compounds containing P=O and P−OH functionalities show excellent
[106]
complexing tendencies towards metal centre and are presumed to play a remarkable role

in binding of uranyl ion by HS. The complexation tendency of phenylphosphonic acid (PPA)
[104]
for uranyl ion is stronger than that reported for the isostructural carboxylic acid . Higher

stability of the phosphonate complexes of the uranyl ion with regard to the corresponding

carboxylate is due to differences in net electrostatic charge and basicity between the

phosphonate and the carboxylate ligands [107] as well as an entropic effect of the phosphonate

90
unit having more potentially binding oxygen atoms than that in carboxylates [108]. Further, the

complexation of uranium (VI) by P-containing ligands is highly pertinent to biogeochemical

cycle of uranium in soils, its dissemination in surface waters and the mobility in phosphate-

rich soil systems [103-104, 109]. The pka values of PPA are given in scheme 3.1.

Scheme 3.1. The Pka values of (a) Citrate (b) Phenylphosphonic acid (PPA)

Earlier investigation on the Uranyl Citrate complexes have been reported in the literature

using different experimental techniques such as UV-Visible and IR spectroscopy, ionic

13
exchange, 1H and C NMR, electro-spray ionization mass spectrometry (ESI-MS) and
[110-113]
extended X-ray absorption fine structure (EXAFS) . Uranyl Citrate system shows

complex behavior with regard to pH-dependent changes in stoichiometry and UO22+

coordination environment in the aqueous medium. Therefore UO22+ speciation in Citrate is

very mobile, sensitive to the solution conditions, and arduous to accurately characterize,

resulting in the lack of comprehensive understanding of its behavior despite decades long

research as many discrepancies among published data exist and knowledge gaps remain. Of

particular concern is the lack of incomplete understanding of UO22+ redox reactions in

presence of ligand. Moreover, despite the extensive spectroscopic studies mentioned above,

91
no systematic study has been carried out on the speciation of UO22+ in Citrate medium

considering its redox behavior. With PPA ligand, the redox speciation of uranyl is

unavailable in literature. These facts motivate us to develop an analytical methodology (i.e.,

electrochemical method) to present the systematic study on the speciation and redox

behaviour of UO22+ with varying physicochemical conditions in aqueous Citrate and PPA

medium. The present study signify its important for providing a new direction in analytical

methodology to gain about the metrical knowledge viz. speciation, in presence of chelating

agents at low concentration [Herein 10-5 M] of metal ion. The present work involves study of

redox speciation of Uranyl in presence of Citrate and PPA by Voltammetry, with emphasis

on speciation and redox property characterization of different Uranyl complexes at varying

metal ligand ratios. Attempts have been made to obtain the stoichiometry of the complexes,

their stability constant, redox potential, and heterogeneous electron-transfer kinetic

parameters as a function of pH, Uranyl to ligands ratio and concentration of UO22+.

3.2. Experimental and Instrumentations: Discussed in chapter 2.

3.3. Results and Discussions: The experimental results and related descriptions are provided

in following two parts:

Ist: Uranyl with Citrate and IInd: Uranyl with PPA

Ist Uranyl with Citrate

3.3.1. Speciation with varying pH: Cyclic voltammograms recorded as a function of

uranyl ion concentration and pH in presence of citric acid is given in Fig. 3.1 a-b. The

plots show a significant shift in peak potential of U(VI) in presence of Citrate with

respect to that in absence of Citrate recorded at same metal ion concentration,

indicating complexation of U(VI) by Citrate. In order to corroborate these

observations, the speciation diagram for Uranyl Citrate system at lower (10-5M) and

higher (10-3M) concentration of UO22+ was calculated using the geochemical code,

92
MinteqA2 [91]. The speciation diagrams [Fig. S3.1a-b] show that monomeric [UO2Cit]-

species dominates the speciation over other species in the pH range of 2.5 to 8 at lower

UO22+ concentration (10-5M) while in the same pH region the dimeric [(UO2)2Cit2]2−

species dominates the speciation over other species at higher UO22+ concentration (10-3

M). Furthermore, to validate the results of cyclic voltammmetry, ESI-MS experiments

were carried out at both UO22+ concentrations. The mass spectra acquired for the

Uranyl Citrate system as a function of pH and UO22+ and Citrate concentration are

given in Fig. S3.2 a-e. The intense peak at m/z value 459 [Fig. S3.2 a-b], corresponds

to monomeric [UO2Cit]- species. In gas phase the dimer can be singly or doubly

charged anionic or neutral depending on the protonation state of the two free carboxyl

groups. The intense peak at m/z= 919 in Fig. S3.2 c-d corresponding to

[(UO2)2(Cit)2+H+]-, confirms the existence of dimeric [(UO2)2Cit2]2− species at higher

UO22+ concentration. Based on the speciation diagram and the ESI-MS spectra, the

cyclic voltammograms [Fig. 3.1a] obtained at lower UO22+ concentration [10-5M] can

be explained as due to reduction of monomeric [UO2Cit]- species while the same [Fig.

3.1b] obtained at higher UO22+ concentration [10-3 M] can be attributed to reduction of

dimeric [(UO2)2Cit2]2− species. These conclusions are in agreement with the report by
29
Ohyoshi et.al. (1975) that at lower UO22+ concentration (≤10-5M) polymerization of

uranyl ion is diminished and monomeric species, namely, [UO2Cit]− predominates the

speciation. The conclusion about the dominance of dimeric species [(UO2)2Cit2]2− over

monomeric species at higher UO22+ concentration (≥10-3 M), is also in agreement with
[110-113]
the literature reports based on spectroscopic techniques . It has been observed

that at [U(VI)] ≥ 10-3 M and pH ≥ 8, there is no well-defined reduction peak in CV.

[112, 114-115]
Some researchers reported the existence of polymeric species, namely,

93
[(UO2)3Cit3]3− and (UO2)3Cit2. However, under these conditions, reductions of

polymeric species are arduous to explain.

In order to obtain better understanding about redox behavior of both the species, the

reduction pattern was investigated with varying pH. As shown in Fig. 3.1a-b both the

species show a pattern representing two irreversible reduction peaks at pH ≤ 5, above

which the two peaks get merged and finally single reduction peak appears at pH ≥ 6.

This indicates the change in the redox behavior of the monomeric and dimeric Uranyl

Citrate complexes with pH. Referring to the speciation diagram in Fig. S3.1 a-b it can

be inferred that there is no significant variation in speciation at pH values below and

above 5 and the monomeric and dimeric species dominate the speciation upto pH 8.

The ESI-MS spectra [Fig. S3.2 a-b] show that the intense peak at m/z= 459 remains

constant at both pH values (4 and 6.5). Further, the intense peak at m/z= 919 also

remains constant at pH 4 and 6.4 [Fig. S3.2c-d], indicating no significant change in

m/z values with pH. Thus, the reduction patterns obtained at pH 4 and 6.5 in Fig. 3.1

(a) and (b) can be attributed to reduction of monomeric and dimeric species

respectively. The different redox behavior of same species with varying pH could be

due to the difference in the electrochemical reduction processes. The electrochemistry

of uranium in aqueous solutions has been widely studied earlier [116-120] and it has been

reported that in acidic medium the first reduction peak is due to reduction of U(VI) to
[119]
U(V). Suzuki et.al reported slow dispropotionation of U(V) in acidic pH (2-5),

thereby explaining slight stability of U(V) in this pH region, while at pH >5, the

disproportionation reaction becomes very fast resulting in disappearance of U(V).

Accordingly in Fig. 3.1 a-b at pH 4, peak I is assigned to the reduction of U(VI) to

U(V). Since Citrate can stabilize U(V), the second reduction peak (peak II) can be

attributed to the reduction of U(V) to U(IV). At pH ≥ 6 a single reduction peak is

94
obtained, which can be explained in terms of the fast disproportionation of U(V), and

hence the reduction of U(VI) directly to U(IV).

The redox potential (Eh) vs. pH plots for monomer and dimer obtained from CV are

given in Fig. 3.2 (a) & (b), respectively. Change in the peak potential with varying pH

indicates the involvement of protons during the reduction process. For both the species

plot I is the variation of first reduction peak [U(VI) to U(V)] potential upto pH 5.5 and

the two electrons reduction peak [U(VI) to U(IV)] potential at pH ≥ 6, while plot II

shows the variation of second reduction peak [U(V) to U(IV)] potential with pH up to

5. Plot I show two linear regions with discontinuity at pH 5.5, while plot II shows a

single linear region upto pH 5. The discontinuity at pH 5.5 in peak I observed in both

the species could be due to change in redox mechanism as discussed earlier. The slope

of linear portion of Eh-pH plot is related to the number of protons involved during

reduction and is given by the equation 2.27 for irreversible reduction at pH ≤ 5 and

equation 2.28 for reversible at pH ≥ 6. The observed value of slope of linear region A

and B and corresponding number of protons calculated for both species are given in

Table 3.1, which shows that for both species, no proton is involved during first

reduction step [U(VI) to U(V)] at pH ≤ 5, while one proton is involved during second

reduction step [U(V) to U(IV)] upto pH 5. The number of protons during [U(VI) to

U(IV)] reduction is calculated to be 4 at pH ≥ 6.

For both the species at pH 4, the plot of peak potential (Ep) vs. logarithm of scan

rate (logν) for first reduction peak [U(VI) to U(V)] are given in Fig. 3.3 (a) & (b). The

Ep values were found to vary linearly with logν in case of both the species, which,

along with the absence of oxidation peak in reverse direction of applied potential [Fig.

3.1a-b], confirms the irreversibility of reduction process. The value of αn can be easily

calculated from the slope of Ep vs. logν plot. Assuming the first step as

95
electrochemical reduction coupled with a chemical reaction (described later), the slope

of linear portion of Ep vs. logν plot can be given by equation 2.29. The value of αn

calculated from the observed slopes for monomer (-0.0568) and dimer (-0.0588) using

equation 2.29 are 0.519 and 0.501, respectively. Assuming α as 0.5, the value of n was

calculated as 1 for both the species, thus corroborating the first reduction peak as due

to U(VI) to U(V) conversion. For monomeric and dimeric species, the ip vs √ν plot at

pH 4 (first reduction peak) and pH 6.5 [Fig. 3.3(b)] depicts the linear relationship

between ip and √ν, indicating diffusion control reduction process of both the species at

both pH values. The diffusion coefficient (D0) of [UO2Cit]- and [(UO2)2Cit2]2− were

evaluated at both pH values using the Randles-Sevcik equation 2.31 (used at pH 4)

and 2.32 (used at pH 6.5) [121-122] and are given in Table 3.2.

The Square wave voltammograms recorded at three pH values, namely, 1.5, 2.5 and

3.5 for UO22+ concentration of 10-3 M and Uranyl to Citrate ratio of 1:1 are shown in

Fig. 3.1c. The figures indicate a single reduction peak at pH 1.5 and three reduction

peaks at pH 2.5 and 3.5. Peak I (Ep= -0.152) is due to the reduction of free UO22+

species as it conforms to the known reduction potential (Ep= -0.150) of UO22+ in

absence of any ligand. However, it is not clear if the reduction peaks II and III

obtained at pH 2.5 and 3.5 are due to reduction of monomeric or dimeric species. The

Eh-pH diagrams for peak II and III, shown in Fig. 3.2 (c) and (d), respectively, help in

understanding the reduction behaviour of Uranyl Citrate system with varying pH

values. The Eh-pH plot for peak II shows two linear regions A (Slope = -0.046) and B

(Slope = -0.048) with discontinuity at pH 3. Both the linear regions have nearly the

same slope which is comparable with the slope of Eh-pH plot for the first reduction

peak of monomer and dimer species at pH ≤ 5 (Table 3.1). Therefore, peak II at pH 2.5

and 3.5 can be attributed to U(VI) to U(V) reduction with the discontinuity due to

96
change in nature of species above and below pH 3. The speciation diagram [Fig.

S3.1c] at same UO22+ concentration and Uranyl to Citrate ratio implies that the three

species UO22+, [UO2Cit]- and [(UO2)2Cit2]2− have comparable concentration in the pH

range 1.5 to 3.5. The Fig. S3.1c also shows that below pH 3 monomeric species

dominates the speciation while at pH>3, the speciation is dominated by the dimeric

species. The ESI-MS spectrum in Fig. S3.2e indicates the existence of both the

monomer (m/z = 459) and dimer (m/z = 919). Therefore, it can be inferred that the

reduction of monomer and dimer dominate the reduction process at pH <3 and pH>3

respectively. The Eh-pH plot for peak III is shown in Fig. 3.2d. The slope of linear

region C was found to be -0.110 and nearly equal to that of second reduction peak of

monomer and dimer at pH ≤ 5 (Table 3.1), indicating that it corresponds to reduction

of U(V) to U(IV).

3.3.2. Kinetic study of U(VI)Citrate system: The cyclic voltammetry,

chronopotentiometry (CP) and chronoamperometry (CA) techniques have been used to

explore the kinetic behavior of reduction for Uranyl Citrate species. Herein the

reduction follows the ECE mechanism for both Uranyl Citrate species. In cyclic

voltammograms over a wide range of potential scan rates, no anodic currents are

observed in case of monomer and dimer at pH ≤ 5, indicating both the reduction steps

to be irreversible and coupled with the chemical process (an ICI mechanism). The

consideration of data in Fig. 3.3c-d with increasing scan rates and small currents

permits some qualitative features of the coupled chemical reaction to be deduced. The

effect of varying scan rates on the value of peak current functions (i/√ν) for the first

reduction peak for both monomer and dimer have been summarized in Fig. 3.3 (c),

respectively. For diffusion controlled, reversible or irreversible electron-transfer

[123]
reaction the peak current function should be independent of scan rate . Instead, a

97
decrease in the same is observed indicating complex kinetics for both the Uranyl

Citrate species. The decrease in current function with increasing scan rate differentiate

the observed reduction mechanism of the present case from that involving only multi

step charge transfer and no chemical reaction between charge transfer steps, as for the
[75-76]
latter case the peak current functions (i/√ν) should be invariant with scan rate .

Thus, present observation indicates the existence of chemical reaction between charge

transfer steps.

For first reduction peak [U(VI) to U(V)], the plots of chronopotentiometric constant

(iτ1/2, where τ is the transition time for reduction wave) vs. applied currents for a series

of pH values for both 1:1 and 2:2 Uranyl Citrate species are summarized in Fig. 3.3 (d)

respectively. Under controlled current, the reduction behavior of [UO2Cit]- and

[(UO2)2Cit2]2− appears to be significantly dependent upon the pH of the test solution

and the amount of applied current (i). iτ1/2, for a diffusion-controlled electron transfer

process, is quantified using Sand equation (equation 3.1) [75-76].

i√τ= (√π nFA√D C)/2 (3.1)

Thus, iτ1/2 should be independent of the magnitude of applied current. However, Fig.

3.3d shows that iτ1/2 is not constant and varies inversely with applied current and

approaches a constant value at high applied current. This suggests the involvement of

complex kinetics in the first reduction step with iτ1/2 varying with actual concentration
[124-125]
of the electroactive species . The potential of the working electrode at any time

(t) for diffusion-controlled irreversible reduction of an electroactive species is given

by equation 2.33. A plot of E(t) vs. log [l - (t /τ)½] will be a straight line with slope of

59/αn mV and an intercept that gives the value of kof, h. The graph for both 1:1 and 2:2

Uranyl Citrate species have been plotted in Fig. 3.4 (a), respectively. Curve A in Fig.

3.4 (a) has been obtained from data at low current densities [in the kinetic region

98
shown in [Fig. 3.3d] and reveals appreciable deviation from theory as t approaches τ.

While, curve B in Fig. 3.4 (a) results from data in the region of constant iτ1/2 [Fig.

3.3d, current-limiting value] and deviates from linearity for both large and small

values of t. The value of αn and kof, h calculated from slope and intercept of the linear

portion of the curves are given in Table 3.3. The values of E(t=0) have been evaluated

by extrapolation of the straight-line portion of the E(t) vs log [1 –(t/τ)1/2] to t=0. The

graph of E(t=0) vs. log i for monomer species is shown in Fig. 3.4d. The plots

indicates that at high applied current, where iτ1/2 is constant, E(t = 0) is a linear

function of log i but at the lower current (kinetic) region a systematic deviation from

linearity takes place. The same behavior is also observed in E(t=0) vs. log i plot for

dimeric species. The E(t=0) shifts cathodically with increasing current, which also

supports irreversibility of first reduction step. The possibility of disproportionation

process is ruled out as the voltammetric wave for a disproportionation process would

exhibit an anodic shift of about 30/αn mV per tenfold increase in the potential scan
51
rate whereas in the present case, exactly opposite effect, that is, a cathodic shift has

been observed [Fig. 3.3 (a)] with nearly 30/αn mV per tenfold increase in scan rate,
[126]
which is characteristic of an ECE mechanism . The chronopotentiometric constant

(iτ1/2) and peak current function (i/√ν) at constant current density and constant scan

rate respectively, initially increase up to pH 3.5 and subsequently decrease for both the

Uranyl Citrate species [Fig. 3.4b-c]. These two quantities (iτ1/2 & i/√ν) are function of

concentration of electroactive species, and hence the initial increase in iτ1/2 and i/√ν up

to pH 3.5, can be attributed to the enhancement in the concentration of the monomeric

and dimeric species, which follow the same pattern in the speciation diagram [Fig.

S3.1a-b]. However, the same argument does not hold for the pH region 3.5-5, wherein

the concentrations of the momoner and dimer remain constant, but the functions, iτ1/2

99
and i/√ν have a decreasing trend, indicating a decrease in the amount of the electro-

active species generated by the chemical reaction with decreasing hydrogen ion

concentration. This suggests that the chemical reaction step appears to involve

protonation of the product of the first reduction step [123-124] as given below,

[UVO2Cit]2- + 3H+ ↔ [HUVOCit]+ + H2O

thereby forming the second electro-active species [HUVOCit]+.

3.3.3. Reduction Mechanism: The citrate ligand does not produce any

electrochemical redox peak in the experimental potential region (0 to -1 V), therefore

the issue due to the free citrate ligand on the overall electrochemical reduction

mechanism has no major significance. The effect of change in Citrate concentration at

fixed UO22+ (10-5 M) was also examined on the redox behaviour of UO22+-Citrate

complex. Shift in peak potential and change in redox behaviour were not observed

with changing concentration of Citrate from 10-5 M to 5x10-3 M. This confirms that

the reduction of UO22+-Citrate complexes is invariant with the concentration of

Citrate. As evident from Fig. 3.1 (a) & (b), no change in redox pattern was observed

with change in the UO22+ concentration indicating the conversion of dimeric species,

firstly into monomer in the electrode surface region followed by the same reduction

pattern as monomer. On the basis of above discussions the plausible reduction

mechanism of [UO2Cit]− and [(UO2)2Cit2]2− can be summarized as follows.

At pH ≤ 5.5

[(UO2)2Cit2]2− 2[UVIO2Cit]−

[UVIO2Cit]− + e- [UVO2Cit]2- (Electrochemical: irreversible)

[UVO2Cit]2-+ 3H+ ↔ [HUVOCit]++ H2O (Chemical Reaction)

[HUVOCit]++H++e- [UIVCit]++ H2O (Electrochemical: Irreversible)

At pH ≥ 6

100
[(UO2)2Cit2]2− 2[UVIO2Cit]−

[UVIO2Cit]− + 4 H+ + 2e- [UIVCit]++ 2H2O

The reduction mechanism observed in Uranyl Citrate complexes is ICI, which is

important in predicting the formation of species after electrochemical reduction and to

understand the redox behaviour of other Uranyl complexes. Herein, mono oxo Uranyl

moiety viz. [HUVOCit]+ is formed by electrochemical reduction of [UVIO2Cit]− to

[UVO2Cit]2- followed by a chemical reaction. The existence of mono oxo Uranyl

moiety was validated by Musikas et. al. [127]

3.3.4. Chronoamperometry: Fig. 3.5a shows chronoamperograms recorded at pH 1.5

and 6.5, where no kinetic complication is observed and the system follows 1e- and 2e-

reduction, respectively. When the same experiment is carried out at pH 3.1, the

chronoamperogram shows the typical pattern characteristic of the ICI reduction

mechanism. The observed current is intermediate between 1e- and 2e- reduction, since

the reduction of [HUVOCit]+ to [UIVCit]+ is controlled by the rate of chemical

reaction of [UVO2Cit]2- to generate [HUVOCit]+. Fig. 3.5b displays the data in terms

of normalized i vs. t-1/2. The shape of the ICI curve can be understood from i vs. t-1/2

plot in terms of the time taken for the chemical reaction involving [UVO2Cit]2-. At

shorter times (larger t-1/2) the ICI curve approaches the 1e- Cottrell plot [i= nFAC0*

√D0 ⁄√πt] due to insufficient time for formation of [HUVOCit]+ from [UVO2Cit]2-.

Hence the mechanism is essentially 1e- reduction of [UVIO2Cit]- to [UVO2Cit]2-. At

longer times (small t-1/2), there is adequate time for the formation of [HUVOCit]+

which is then reduced to [UIVCit]+. Consequently, the mechanism is indistinguishable

from a simple 2e- reduction of [UVIO2Cit]- directly to [UIVCit]+. The transition

between these two extremes during the chronoamperometry experiment reveals

coupling of chemical reaction between two charge transfer steps [128].

101
3.3.5. In Situ Spectroelectrochemical study: With a view to corroborate the ICI

reduction mechanism, as proposed based on electrochemical investigation, in situ

spectroelectrochemical measurements were carried out. Herein, the reduction

processes of Uranyl Citrate species were followed spectroelectrochemically by using

an optically transparent cell. The absorption spectra were measured at each applied

potential in the range from -0.01 to -1V with varying time of electrolysis. The results

are shown in Fig. 3.6. The spectra recorded after 25 min. electrolysis with varying

potential from -0.01 to -1V are shown in Fig. 3.6a. As seen from Fig. 3.6b no clear

isosbestic points are observed from the present spectroelectrochemical measurements,

indicating absence of redox equilibrium. Hence it might be considered that the

[129]
reduction of U(VI)Citrate species is followed by chemical reaction . The decrease

in iτ1/2 with increasing pH in the chronopotentiometry measurements implies

protonation of the species produced during the first reduction step. Furthermore,

during electrolysis the absorption bands at 487, 504, 560 and 663 nm, which are

consistent with absorption peaks of U(IV) in Citrate, become intense with time and

with decrease in applied potential as shown in Fig. 3.6a. The reduction of U(VI) is also

evident from the decrease in intensity of absorption bands of U(VI) in Citrate at 422,

436 and 447 nm. Above observations suggest that the reduction of U(VI)Citrate

species proceeds through two steps reduction process: the first reduction step

involving U(VI) to U(V) conversion, followed by a chemical reaction involving

protonation of the species generated during first reduction step. This chemical reaction

generates the electrochemically active species which undergo further reduction in

second step and produce the U(IV)Citrate species. Thus, spectroelectrochemical

measurements validate the ICI reduction mechanism proposed based on

electrochemical measurements. Since the reduction from U(VI) to U(IV) proceeds

102
through U(V), one might expect the existence of the U(V) species in the Citrate

medium. However, the literature reports on the signature of U(V) complexes are

scarcely available. Furthermore, owing to the instability of U(V) due to

[130-
disproportionation and lower value of molar absorptivity (ε) in aqueous medium
131]
the detection of absorption bands of U(V) is quite a scientific challenge; hence

their assignments are still uncertain. The present spectroelectrochemical measurements

show the presence of new U(V) species in aqueous Citrate medium, namely,

[UVO2Cit]2-. We observed the appearance of the absorption bands at 732, 743, 774,

785, 798 and 982.8 nm associated with the reduction of U(VI)Citrate to U(V)Citrate as

shown in Fig. 3.6c-d. The intensity of absorption bands increases with time from 0 to

25 minute at fixed potential (-0.01V) and the trend continues with decrease in potential

from -0.01V to -0.3V up to 1 minute after which the intensity starts to decrease with

further increase in reduction time as well as decrease in applied potential from -0.3V

to -1V [Fig. 3.6c-d]. This type of variation in intensity of absorption bands with

reduction time (at fixed -0.01 V) and varying (-0.01V to -0.3 V up to 1 minute)

potential is reminiscent of U(V)Citrate formation and absence of second reduction step

[U(V)Citrate to U(IV)Citrate] in the initial stage of electrolysis, but with increase in

reduction time from 1 to 35 minute at -0.3V the second reduction step initiates

reduction of U(V)Citrate U(IV)Citrate. The kinetics of second reduction step becomes

faster with decrease in potential from -0.3 to -1V, resulting in decrease in the intensity

of U(V)Citrate after 1 minute at -0.3V as well as decrease in applied potential from -

0.3 to -1V. Literature reports on absorption bands of U(V) in visible and near-infrared
[132-133]
regions, show peaks at 765 and 980 nm in K2CO3 aqueous solution .

Furthermore, the characteristic absorption bands of U(VI) [422, 436 and 447 nm] and

U(IV) species [487, 500, 560 and 663 nm] occur at wavelengths well below 700 nm.

103
Therefore, the absorption bands at 732, 743, 774, 785, 798 and 982.8 nm, obtained in

the present study have been attributed to [UVO2Cit]2-, which arise due to f-f transitions

in the 5f1 configuration [131]

. The change in nature of absorption bands in the case of

Citrate complex compared to that in case of Carbonate could be due to change in

nature of complexing agent.

3.3.6. Determination of stability constant: Voltammetric studies does not show any

significant shift in peak potential with varying ligand concentration from 10-5 to 10-2

M at fixed UO22+ concentration (10-5 M). This suggests absence of dissociation of

Citrate from UO22+ with no change in the nature of the species with increasing ligand

concentration. The stability constant of Uranyl Citrate complexes was determined

following the voltammetric measurements at varying UO22+ concentration and fixed

Citrate concentration. Citrate concentration was fixed at 10-2 M, while UO22+

concentration was varied from 10-6 to 10-3 M at pH 4. The plot of first reduction

[U(VI)-U(V)] peak potential (Ep) vs. logCM is given in Fig. 3.7a, which shows two

linear regions A and B having different slopes. This result further confirms the

existence of two different species with varying UO22+ concentration. Region A [≤

2x10-4 M], corresponding to lower metal ion concentration could be assigned to

reduction of monomer [UO2Cit]- and the region B [≥ 3x10-4 M] could be assigned to

the reduction of dimeric species. The stability constant of [UO2Cit]− was determined
[93]
following the Deford-Hume formalism . At constant ionic strength I=0.1 M and pH

4 the shifts in potential with increasing UO22+ concentration have been measured. The

plot of F0[UO22+ Conc.] vs. [UO22+ Conc.] (equation 2.41) is given in Fig. 3.7b, which

represents a straight-line having slope = 6.3x106. The logβ value of monomer was
31
deduced as 6.8±0.11, which is in excellent agreement with the literature data . The

first reduction step in the redox process is expressed by the following equation:

104
[UVIO2Cit]− + e- [UVO2Cit]2− (3.2)

The formal redox potential of (Ef) is expressed as

RT β V (3.3)
E f = E0 + ln
αnF β VI

Where, E0 is the standard redox potential, while βV and βVI represent the stability

constants of [UVO2Cit]2− and [UVIO2Cit]− respectively. By substituting Ef, E0, and

logβVI = (6.80) into equation 3.3, logβV was obtained as 6.10±0.12.

(II) Uranyl with PPA

Literature reports [107-108, 134] indicate that UO22+ in PPA medium exists mainly in three

types of U(VI)-phenylphosphonate complexes. Two complexes with a metal-to-ligand

stoichiometry of 1:1 as mono-protonated UO2(HPhPO3)+ and non-protonated UO2PhPO3

forms exist in solutions at pH 3-7 while a 1:2 UO2(HPhPO3)2 complex is formed additionally

at relatively high ligand-to-metal ratio. The cyclic voltammograms recorded at 10-5 M

concentration of UO22+ and 10−3 M concentration of PPA at pH 4 and pH 5 are given in Fig.

3.8 (i-ii). The figures show a significant shift in peak potential of U(VI) in presence of PPA

with respect to that in absence of PPA recorded at same metal ion concentration, indicating

complexation of U(VI) by PPA. At pH 4 the difference between potential of peak I and that

of U(VI) in absence of PPA is observed to be (∆Ep)I = 0.102 V while the same for peak II is

found to be (∆Ep)II = 0.197 V. At pH 5 this difference is found to be ∆Ep = 0.167 V. In order

to corroborate this observation, the speciation diagram for U(VI)-PPA system was calculated
[91]
using the geochemical code, MinteqA2, . The speciation diagram (Fig. S3.3) shows that

1:1 U(VI)-PPA complex dominates the speciation over other possible species in the pH range

of 2 to 7, thereby indicating that the CV in Fig. 3.8 is due to reduction of UO2PhPO3 (1:1)

complex.

105
3.3.7. Redox behavior with pH: Variation in redox behavior of UO2PhPO3 (1:1) species has

been observed with change in pH values. As shown in Fig. 3.8 (iii-iv) in 3D plots similar

changes have been observed in CV and DPV with variation in pH values. Upto pH 4 two

reduction peaks are obtained with intensity of second reduction peak being higher than first

one. The electrochemistry of uranium has widely been studied in aqueous solutions earlier
[115-120]
and it was reported that in acidic medium the first reduction peak is due to reduction

of U(VI) to U(V). Accordingly, in Fig. 3.8(iii-iv), peaks I and II can be assigned to reduction

of U(VI) to U(V) and that of U(V) to U(IV), respectively. Higher intensity of peak II than

that of peak I at pH 4 can be explained in terms of the stabilization of U(IV) by PPA

compared to that of U(V). However, at pH 4.5 a drastic change in redox behavior has been

observed with the intensity of peak I being higher than that of peak II, indicating that at pH >

4 PPA has a tendency to stabilize U(V) oxidation state over U(IV). The disproportionation
[135] [58, 135]
of U(V) to U(IV) and U(VI) described by the following reactions may be

responsible for this drastic change in redox pattern.

UVO2+ + H+ UVOOH2+ (3.4)

UVO2+ + UVOOH2+ HOUVIO2+ + UIVO2+ (3.5)

UIVO2+ + 2H+ U(IV) + H2 O (3.6)

HOUVIO2+ UVIO22+ + OH- (3.7)

[119]
Suzuki et al. reported slow dispropotionation of U(V) in acidic pH (2–4), thereby

explaining slight stability of U(V) in this pH region, while beyond pH 4 the

disproportionation reaction becomes fast resulting in disappearance of U(V). The present

study indicates that in the presence of PPA, the slow disproportionation of U(V) continues as
[119]
expected upto pH 4 but beyond pH 4 the fast disproportionation, as proposed earlier ,

does not occur in this case. This suggests that in presence of PPA at pH > 4 U(V) will be

stable with respect to disproportionation. Therefore, two reduction peaks upto pH 4 could be

106
explained in terms of slow disproportionation and less stability of U(V), while the single

reduction peak at higher pH could be explained in terms of the absence of disproportionation

and more stability of U(V). This further explains why the peak intensity of U(VI) to U(V)

reduction become higher while that of U(V) to U(IV) lower at pH 4.5 and this reduction peak

[U(V) to U(IV)] totally vanishes after pH 4.5 as can be seen in Fig. 3.8 (ii). Redox behavior

of 1:1 species at three pH conditions viz., acidic, neutral, and alkaline are given in 3D plots of

CV and DPV [Fig. 3.8 (v-vi)]. Two reduction peaks at acidic condition and single reduction

peak both at neutral and alkaline condition are evident from figure.

3.3.8. The Eh-pH plot: The Eh-pH (Eh = redox potential which is function of H+ ion) plot

provides information about the existence of species in particular pH region and number of

protons involved during reduction. The Eh-pH plots for UO22+ (10-5 M) in presence of PPA

(5×10-3 M) for both the reduction peaks are given in Fig. 3.9(i) and (ii). The plot for peak I

(Fig. 3.9 (i)) shows two linear regions with discontinuity at pH 4.5, while peak II (Fig. 3.9(ii))

shows single linear region upto pH 4. The speciation plot shows the existence of single

dominant species UO2PhPO3 (1:1) in the pH region from 2 to 7, indicating no change in the

nature of species at pH 4.5. Hence the discontinuity at pH 4.5 could be due to change in

redox mechanism. The slope of linear portion of Eh-pH plot is related to the number of

protons involved during reduction and is given by following expressions.

dEp/dpH = - 0.059 P/αn (For irreversible reduction) (3.8)

dEp/dpH = - 0.059 P/n (For reversible reduction) (3.9)

where, P = no. of protons involved in reduction. The slope of linear portion of region A for

peak I was found to be -0.048 V using equation 2.27, while the number of protons involved

during reduction was calculated as 0.4, which can be neglected due to its insignificant value.

This suggests that no proton is involved during this reduction step. The corresponding values

107
of the slope and number of protons obtained from the linear portion of region B for peaks I

and II were found to be -0.074 V and 1.2 and -0.062 V and 1.0, respectively.

3.3.9. The Ep vs. log ν plot (determination of heterogeneous kinetic parameter in acidic

condition): For an irreversible electrode process Ep is defined by equation 2.30. The Ep

values were found to vary linearly (R2 = 0.99) with log ν for reduction peak I (region A) at

pH 3 as shown in Fig. 3.10(c). Further, the absence of oxidation peak in reverse direction

(Fig. 3.8(i)) confirms irreversibility of reduction peak I upto pH 4. The value of αn can be

easily calculated from the slope of Ep vs. log ν. For the data plotted in Fig. 3.10(c), the slope

is 0.096, which gives αn as 0.61, which is close to 0.5, the value of α for irreversible

reduction and confirms the single electron (n = 1.2) transferred in the reduction process. The

value of k0 can be determined from the intercept of the same plot (-0.372) provided E0 is

known. The value of E0 in equation 2.30 obtained from the intercept of Ep vs. ν curve, was

found to be -0.204 V, which gave the k0 value as 0.732 s-1.

3.3.10. Estimation of number of electron transfer at pH 5: Fig. 3.8(ii) implies oxidation

peak in reverse direction of applied potential at pH 5. The ratio of reduction to oxidation peak

current was calculated to be (1.3), which is close to unity. Furthermore, Fig. 3.10(d) shows

that the reduction potential is not affected significantly on varying the scan rate. These results
[98]
are characteristics of reversible electron transfer process . For a reversible reduction

process the difference between the reduction peak potential and its half value (∆Ep) is related

to number of electrons transferred (n) by following equation [75-76]:

A.AØÙ
KY L KY× = 2
(3.10)


At 50 mV the Ep − Ep/2 was obtained as 0.047 V, which gives n as 1.21, that is, close to 1.

3.3.11. The ip vs. √ν plot (determination of diffusion coefficient): The cyclic

voltammograms for U(VI)-PPA system at two pH values 3 and 5 and at varying scan rates are

shown in Fig. 3.10 (a) and (b). In both the figures the peak current increases with scan rate

108
for peak I, confirming diffusion control reduction process. The diffusion coefficient of

UO2PhPO3 was evaluated at both pH values by using the Randles-Sevcik equation 2.31 (used

at pH 3) and 2.32 (used at pH 5) [121-122]. The value of D0 calculated at pH 5 from the slope

(7.30 × 10-8, R2 = 0.997) of linear plot of ip vs. ν1/2 (Fig. 3.10f) is 6.76 × 10-5 cm2 s-1 while the

same calculated at pH 3 from the slope (4.86 × 10-8, R2 = 0.996) of linear plot of ip vs. ν1/2

(Fig. 3.10e) is 5.03 × 10-5 cm2 s-1. Both the calculated values of D0 are in close agreement.

3.3.12. Determination of heterogeneous electron transfer rate constant for UO2PhPO3:

The heterogeneous electron transfer rate constant “ks” was calculated by using the relation

developed by Klingler and Kochi (equation 3.11), which is based on peak separation between

cathodic and anodic [136].

F€H2GÜ M/ F y 2G
E0 = 2.18 Û Ý "ŽÞ ÛL «KY6 L KY3 ¬Ý (3.11)
λ λ

Taking α as 0.5, the value of heterogeneous electron transfer rate constant “ks” was

calculated at 50 mVs-1 using D0 = 6.76 × 10-5 cm2 s-1 and found to be ks = 0.304 × 10-3 cm s-1.

3.3.13. Reduction mechanism: Based on finding of the results, the reduction mechanism of

UO2PhPO3, below and above pH 4 can be summarized as given below.

pH ≤ 4: Peak I, region A: UVIO2PhPO3 + e- [UVO2PhPO3]-

Peak II: [UVO2PhPO3]- + H+ + e- [UIVO2HPhPO3]-

pH > 4: Peak I, region B: UVIO2PhPO3 + H+ + e- [UVO2HPhPO3]

It is worth mentioning that during the reduction of [UVIO2PhPO3] to [UVO2HPhPO3] and

subsequently to [UIVO2HPhPO3]−, the structure of the complex does not change as it is only

electron transfer process. However, the second reduction step is followed by the chemical

reaction to form UIV-PPA i. e. [U(IV)PhPO3]2+ which has a different structure.

3.3.14. ESI-MS measurements: ESI-MS is used here to corroborate the number and

stoichiometries of the UO22+-PPA complexes in solution and to confirm the results from

cyclic voltammetry. Mass spectra acquired for the UO22+-PPA system are shown in Fig.

109
S3.4a, b and m/z values with corresponding species [134] are given in Table 3.4. As clear from

Table 3.4 and Fig. S3.4a, the intense peaks at m/z values 427, 445 and 463 are corresponding

to mainly UO2PhPO3 (1:1) species with its proton and one and two water adduct. Therefore,

validating the existence of UO2PhPO3 (1:1) as major species over the others in solution. This

confirms that finding of reduction peaks of UO22+ in presence of PPA in CV are because of

(1:1) UO2PhPO3 reduction.

3.3.15. Determination of stability constant of U(VI)-PPA complex: At constant ionic

strength I = 0.1 M and pH 5 the shifts in potential with increasing PPA concentration have

been measured and used to evaluate the F0(PPA) using equation 2.41. Plot of the F0(PPA)

versus PPA concentration is given in Fig. 3.9(iii). The plot being a straight line (R2 = 0.992)

provides the slope = 9.54 × 106. Thus, log β value of UO2PhPO3 was found to be (6.98 ±

0.12), which is in excellent agreement with the literature data [134].

3.4. Conclusions

A complete electrochemical investigation of Uranyl with Citrate and PPA under

varying conditions of pH, Uranyl to ligands ratio and UO22+ concentration has been carried

out. The cathodic shift in reduction potential of UO22+ with the addition of Citrate, at both the

higher (10-3M) and lower (10-5M) metal ion concentration indicated the formation of Uranyl

Citrate complexes. At higher metal ion concentration (≥3x10-4 M) the dimeric species

[(UO2)2Cit2]2− is dominant while at lower metal ion concentration (≤2x10-4 M) the

monomeric species [UO2Cit]− dominates the speciation. Based on results, it has been

observed that the speciation of UO22+ in Citrate is independent of Citrate concentration and

depends only on UO22+ concentration. ESI-MS results show definitive evidence for existence

of monomer [UO2Cit]− and dimer [(UO2)2Cit2]2− species at the experimental conditions

through their m/z values at 459 and 919 for monomer and dimer respectively. The

chronopotentiometry, chronoamperometry and in situ spectroelectrochemical measurements

110
corroborated the existence of chemical reaction as the protonation of the reduced species

produced after first reduction step. Presence of U(V) species in Citrate medium [UVO2Cit]2-

with its characteristic absorption bands in visible and near-infrared regions at 732, 743, 774,

785, 798 and 982.8 nm were observed. Cyclic voltametry studies of U(VI)-PPA system

revealed negative shift in electrode potential with respect to UO22+, which confirms the

formation of UO2PhPO3. PPA can stabilize U(IV) upto pH 4 while above it (pH > 4) peaks

are observed owing to U(VI) to U(V) followed by U(V) to U(IV) reduction due to

involvement of slow disproportionation of U(V) while above pH 4.5 single reversible

reduction peak due to U(VI) to U(V) reduction occurs due to absence of disproportionation of

U(V). The m/z values at 427, 445 and 463 validate presence of UO2PhPO3 species. It may be

concluded that the identification of species UO2PhPO3 and its stability constants obtained

here, offer a broad speciation model for the U(VI)-phenylphosphonate system. This will be

useful for appraisal of the role of aromatic phosphorus functional groups in binding of uranyl

by HS.

111
 Figures and Tables
(i) U-Citrate

(a) (b)

(c) (d)

Figure 3.1. Cyclic voltammetry curves: (a) [UO22+]= 10-5 M, (i) in absence of Citrate
at pH 4 (ii) in presence of [Citrate]= 5x10-3 M at pH 4 (iii) same as (ii) at pH 6.5; (b)
[UO22+]= 10-3 M, (i) in absence of Citrate at pH 4 (ii) in presence of [Citrate]= 5x10-2
M at pH 4 (iii) same as (ii) at pH 6.5 (c) Square wave Voltammetry curves with
varying pH, Condition: [UO22+]= 10-3 M, [Citrate]= 1x10-3 M (d) Variation of cyclic
voltammograms with scan rates

112
 (a) (b)

(c) (d)

Figure 3.2. Eh-pH plots, Condition: (a) [UO22+]= 10-5 M, [Citrate]= 5x10-3 M and I=
0.1 M NaClO4 (b)[ UO22+] = 10-3 M , [Citrate]= 5x10-2 M and I= 0.1 M NaClO4; (c)
for Peak II (d) for Peak III, both (c) & (d) are at [UO22+]= 10-3 M, [Citrate]= 1x10-3 M
and 0.1 M NaClO4.

113
 (a) (b)

(c)

(d)

Figure 3.3. (a) E vs. logν plot for peak I and (b) i vs. √ν plot (c) is the variation of peak
current functions (i/√ν) with scan rates at pH 4 while variation of
chronopotentiometric constant (iτ1/2 ) with i for several values of pH is in (d),
Conditions: (a) to (d) [UO22+]= 10-5 M, [Citrate]= 5x10-3 M and I= 0.1 M NaClO4.

114
Figure 3.4. (a) E(V) vs. log [1-(t/τ)1/2] plots at pH 4 (b) Variation of chronopotentiometric
constant (iτ1/2) with pH at fixed i = 10x10-8 A. (c) Variation of Peak Current function (i/√ν)
with pH at 50 mV/sec scan rate (d) Variation of E(t=0) with log i at pH 5.

115
Figure 3.5. Plot of i(A) vs. t(sec) with varying pH is in (a) and (b) is the plot of i(A) vs. t-1/2.

Condition: (a) and (b) [UO22+]= 1x10-5 M, [Citrate]= 5x10-3 M and I= 0.1 M NaClO4.

Figure 3.6. (a) & (b) are the absorption spectra with varying potential from -0.01 V to
-1 V after every 25 min. (c) and (d) are the absorption spectra measured with varying
both potential (from -0.1 V to -1 V) and time of pentavalent uranium. The appearance
of absorption bands are at 732, 743, 756, 774, 785, 798 and 982.8 nm respectively.
Condition: (a) to (d) [UO22+]= 4x10-3 M, [Citrate]= 4x10-3 M and I= 0.1 M NaClO4.

116
Figure 3.7. The Variation of Ep (a) with [UO22+] concentration at fixed [Citrate]= 1x10-2 M,
I= 0.1 M NaClO4 and pH 4; (b) The variation of F0[UO22+ Conc.] with [UO22+ Conc.] at pH 4.

Table 3.1. The observed slopes and calculated value of number of protons from Eh-pH
plots

Region of Eh-pH plots Monomer [UO2Cit]− Dimer [(UO2)2Cit2]2−

Slope No. of Slope No. of
protons protons
Plot I, linear region A -0.032 0.27 ~ No -0.038 0.32 ~ No
(pH≤5) proton proton
Plot I, linear region B -0.123 4.16 ~ 4 -0.122 4.13 ~ 4
(pH≥6)
Plot II (pH≤5) -0.091 0.78 ~1 -0.096 0.8 ~ 1

117
Table 3.2. The observed slope and calculated value of D0 from i vs. √ν plot

Taken: A= 4x10-3 cm2,

pH Monomer [UO2Cit]− Dimer [(UO2)2Cit2]2−
Conc.( C0*) Slope D0 Conc.( C0*) Slope D0
−3 2 −3
mol cm (cm /sec) mol cm (cm2/sec)
4 7.26x10-9 2.138x10-8 1.21x10-5 3.87x10-7 8.70x10-7 7.07x10-6

6.5 8.76x10-9 8.166x10-8 9.39x10-6 3.887x10-7 2.29x10-6 3.74x10-6

Table 3.3. The value of αn and k0f,h for [UO2Cit]−and [(UO2)2Cit2]2−at lower and higher
current densities.

Applied Monomer [UO2Cit]− Applied Dimer [(UO2)2Cit2]2−

Current Slop αn Inter k0f,h Current Slope αn Intercep k0f,h
(A) e cept (cm/sec) (A) t (cm/sec)
-6
Lower 0.14 0.42 -0.14 6.16x10 Lower 0.11 0.52 -0.11 1.20x10-5
Current Current
-9
(6x10 ) (4x10-7)

Higher 0.13 0.45 -0.15 8.69x10-6 Higher 0.13 0.45 -0.14 1.13x10-5
Current Current
(9x10-9) (7x10-7)

118
 (ii) U-PPA

Figure 3.8. (i) and (ii) are the CV plots (a) UO22+ at 10-5M in absence of PPA and (b) in

presence of 5x10-3M PPA conc. (i) at pH 4 (ii) at pH 5. The 3D plots of (iii) CV at pH 4 and

4.5 (iv) DPV at pH 4 and pH 4.5. The 3D plots of (v) CV and (vi) DPV at pH 4,7 and 9.

119
 (i) (ii)

(iii)

Figure 3.9. The Eh-pH plot

lot (i) for reduction peak I and (ii) reduction peak II. (iii) Plot of F0

(PPA) vs. [PPA Conc.]

120
Figure 3.10. The i(A) vs E(V) plot with increasing scan rate from 50 to 100mV/s (a) at pH 3

; (b) at pH 5. The E vs logν plot for peak I (c) at pH 3 and (d) at pH 5. The i(A) vs √ν plot (e)

at pH 3; (f) at pH 5.

121
Table 3.4. The species with their m/z values

Species m/z value

Bare metal ion, UO2(CH3O) 301

UO2(C6H6O3P) = [UO2(PhPO3) + H ]+ 427.02

UO2(C6H6O3P)(H2O) = [UO2(PhPO3) + H +(H2O)]+ 445.05

UO2(C6H6O3P)(H2O)2 = [UO2(PhPO3) + H +(H2O)2]+ 463.05

122
 Chapter 4

Electrochemical, Spectroscopic and Theoretical Studies on Redox

Speciation of Neptunium with Phenylphosphonic Acid

AIM: Probing the systematic knowledge of neptunium (Np), such as, speciation and

coordination as function of its oxidation states in presence of chelating agents is essential

aspect of its solution chemistry. The present chapter aimed at investigating the redox and

complexation of Np with phenylphosphonic acid (PhPO3H2) (PPA) as mimic for binding of

aromatic phosphorus functionalities in humic substances by using electrochemical and UV-

Visible absorption spectroscopy and density functional calculations.

123
4.1. Introduction:
Neptunium (Np), is one of the artificial elements produced in significant quantities in

nuclear reactors by α decay of 241Am and (n, 2n) reaction of 238U followed by β decay of 237U
[137] [137-139]
. Neptunium is key constituent in spent nuclear fuel, nuclear waste and is
[140]
considered to be most problematic actinide . It remains one of the least understood major

transuranium elements though several decades have passed since the first experimental

isolation of Np (1940) [141]. It is an α-emitter with a long half-life [e.g. t1/2 (237Np) = 2.14x106

years], having high solubility under environmentally relevant conditions. Thus, the long lived
237
Np builds up in spent nuclear fuel and high-level liquid waste (HLW) with time and is one

of the important radionuclide of interest to consider for the transportation and migration in

geosphere. Np can exist in variety of possible oxidation states from III to VII in aqueous

solution and the relative stabilities of the same are strongly affected by pH and the presence
[142]
of complexing ligands . Np in its higher valence states viz. NpO2+ & NpO22+ are highly

soluble among all its oxidation states, which in turn makes these two oxidation states of Np

more mobile in geosphere. The reduction of these oxidation states to lower oxidation states

leads to its precipitation and immobilization, thus the redox speciation of Np has phenomenal
[143]
effect on its release, solubility and migration behaviour . Neptunium speciation in

aqueous media is mainly dominated by the pentavalent cation, NpO2+, under a wide range of

environmental conditions. Np redox chemistry is dominated by the dynamic equilibria as

represented below [144-146]:

NpO22+ ⇔ NpO2+ ⇔Np4+/Np3+ (4.1)

This redox mobility makes Np speciation highly dependent on the aqueous solution

composition and the formation of coordination complexes that disturb the Np redox

equilibrium. Further, for redox-sensitive radionuclides like Np, speciation is very complex

due its propensity to exist in multiple oxidation states, susceptibility to hydrolysis,

dependence on solution conditions and ability to coordinate with a wide range of ligands.
124
Thus, precise identification of speciation is tough, resulting in knowledge gap due to lack of
[144]
comprehensive understanding of its behaviour . The reliable spectroscopic signatures,

complete understanding of Np redox reactions, and accurate determination of electrochemical

potentials in presence of chelating agents, are of primary concern to generate input database

for the accurate prediction of its transportation and migration in geochemical models.

Therefore, there has been a renewed charm on understanding the redox speciation of Np
[26]
species in presence of chelating agents . In this context, it is quite interesting to ascertain

the aqueous solution species of Np-phosphonate. Understanding of this system provides

significant role in actinide solution chemistry to gain knowledge about transuranic ions

regarding metrical information about a metal ion’s speciation.

Phenylphosphonic acid (PPA): Polycarboxylic and aminopolycarboxylic acid complexants

are frequently used in actinide isolation and waste remediation, endure some significant

limitations viz. ineffective complexation with actinides in acidic solutions, limitation of

solubility and resistance for degradation [106]. The complexation tendency of Phosphonic acid

towards the metal ions is stronger than the isostructural carboxylic acid [134]. One of the most

important features of phosphonate ligand is its more probable deprotonation compared to

carboxylic acid therefore metal ion can more effectively compete with H+ for truly anionic

ligand binding sites in acidic solutions [147]. Therefore, recently simple phosphonic acid based

chelating agents emerge as tenable option as sequestering agent for f-element. This ligand

assimilating doubly ionizable phosphonate groups (-PO3H2), possess many qualities which

are unique chemically and assurance for more efficient separation processes related to waste
[103-104]
remediation and environmental restoration . Furthermore, these powerful f-element

complexants can be easily destroyed at the end of their useful life by raising the temperature

or adding mild oxidizing agents, which mitigates the possibility of ligand promoted actinide
[147]
migration . High fraction of phosphorus (P) exists in organic forms as derivatives of

125
 [148-149]
phosphonic acid in soils rich in organic matter . The P content in humic substances

(HS; Humic substances are naturally occurring polydisperse and heterogeneous mixtures of

organic molecules that have a high affinity for metal ions) is 800-1500 mg/kg. Therefore, the

PPA with P=O and P-OH functionalities can be acknowledged as primitive ligand for

aromatic phosphorus functional groups in humic acid. Unique features of Phosphonic acids

boost it as versatile ligands in the recent past with increasing attention due to their potential

applications in nuclear waste remediation and actinide separation processes [149].

The complexation studies on Np have been reported with inorganic ligands (CO32-,

ClO4-, NO32- and SO42-) [145-146, 150]

and some other organic chelating ligands including

carboxylic acids, amides, and hydroxamic acids [151-155]. The crystal studies of Np with mono
[156]
and di phosphonate [157] are also available in literature. However, there is no report in the

literature on aqueous solution chemistry of Np in presence of PPA as chelating agent. In the

present work, the electrochemical and absorption spectroscopy methodology are employed to

gain insight into the speciation and coordination chemistry of Np as a function of oxidation

states and to benchmark the reduction potential and spectral characteristic of corresponding

Np species. Quantum chemical calculations (density functional theory) are carried out to

understand the possible coordination modes of Np with PPA in different oxidation states at

the molecular level.

4.2. Experimental and Instrumentation: Details are provided in Chapter 2.

4.3. Results and discussion

4.3.1. Redox behviour with pH: The cyclic and differential pulse voltammograms of Np

recorded in 0.1 M NaClO4 (pH = 2.5) using a GC electrode in absence and presence of PPA

ligand are given in Fig. 4.1. In cyclic voltammograms the two clear reduction peaks in which

first is reversible and second irreversible are obtained in both cases. The electrochemistry of
[145-146, 150, 158-160]
Np in aqueous solution has been studied earlier and reported that the

126
reversible peak is due to reduction of Np(VI) to Np(V). Therefore, in the both case the first

peaks, which are reversible, observed at 0.248 V [in absence of PPA] and 0.023 V [in

presence of PPA ligand] on the cathodic scan and their corresponding oxidation peaks

obtained at 0.392V [in absence of PPA ligand] and 0.207 V [in presence of PPA ligand] have

been attributed to Np(VI)/Np(V) reduction according to the following equation 4.2:

NpVIO22+ + e- → NpVO2+ (4.2)

Further, to obtain the number of electron transfer during first reduction peak in case of cyclic

voltammograms related to Np-PPA complex the following equation 4.3 [75-76] has been used.

Ep-Ep/2 = 0.0565/n (4.3)

At 50 mV the Ep−Ep/2 was obtained as 0.070 V, which gives n as 0.81, that is, close to 1.

However, there is ambiguity in assigning the second reduction peaks in both cases. Earlier

studies explained that it may be either Np(V) to Np(IV) or Np(V) to Np(III). Atshusi et al. [8]

have reported Np(V) to Np(III) reduction in perchlorate solution during electrochemical

study on Np. In the present study, in both cyclic voltammograms, we obtained the second

reduction peaks at -0.417 V (in absence of PPA) and -0.565 V (in presence of PPA) at more

negative potential with irreversibility. This reveals that it is kinetically hindered, arduous to

reduce and involves slow electrode reaction, indicating that the second reduction peaks are

associated with reduction of NpO2+ which requires the breakage of the actinyl bonds and

release of two axial oxygen atoms of NpO2+. Hence the second reduction peaks are due to
[146]
reduction of Np(V) to Np(IV) or Np(III). Further, as explained in the previous studies

that the electrode potential of redox couple of Np(V)/Np(IV) and Np(IV)/Np(III) (only

separated by~ 0.2 V) are close hence there is possibility of overlap of following redox

reactions which results in directly two electrons transfer during reduction [146]:

NpO2+ + 4H+ + e- → Np4+ + 2H2O (4.4)

And Np4+ + e- → Np3+ (4.5)

127
This two electron transfer reaction can be corroborated by appearance of larger current

amplitude of second cathodic wave in cyclic voltammogram of Fig. 4.1. Therefore, the

second reduction peak obtained in both Np metal ion and its complex with PPA ligand can be

attributed to two electron reduction process namely NpO2+ to Np3+. This has also been

confirmed by evaluating the number of electrons transferred during reduction in Np(V)-PPA

complex using Laviron equation 2.30. The cyclic voltammetry data analysis results related to

reversible reduction peak (Peak first) are given in Table S4.1. The table shows that ipc/ipa is

nearly fixed at 0.8 with no significant change with varying scan rates from 0.02 to 0.09 V/sec.

Further, the difference in cathodic and anodic peak potentials (∆Ep) also does not show any

measurable variation with increase in scan rates. These observations authenticate the nearly

reversibility of first reduction peak. In presence of PPA ligand a significant cathodic shift in

both peak potentials are observed in cyclic voltammogram recorded at same metal ion

concentration, indicating strong complexation of Np by PPA ligand in both oxidation states

of Np viz. Np(VI) and Np(V). The shift in the potential is related to the complexation

tendency of ligand. The cathodic shift (∆Ep) for peak I was obtained to be ∆EpI = 0.225 V

while for peak II it was ∆EpII = 0.148 V, corroborating strong complexation of Np(VI) by

PPA than that of Np(V). The region of existence of Np complexes with both oxidation state

viz. Np(V) & Np(VI) with varying pH are presented in the redox potential (Eh) vs. pH plots

in Fig. 4.2 (a) and (b). The linear behaviour from pH 1.75 to 3.5 as indicated by region A in

Fig. 4.2 (a) implies the region of occurrence of Np(VI)-PPA complex as a function of pH.

Below pH 1.75, there is no complexation of Np(VI) by PPA ligand while above pH 3.5 the

Np(VI)-PPA complex is unstable. The similar linear variation [region B] is also obtained in

case of Np(V)-PPA complex for which region of stability as a function of pH is somewhat

extended upto pH 5.5 above which it does not exist in solution. The variable occurrence of

complex of Np(VI) and Np(V) with pH may be due to instability of oxidation states with pH.

128
Change in reduction potential of the complex with varying pH indicates involvement of

protons during its reduction process. The number of protons involved during reduction is

related to the slope of linear segment of Eh-pH plot by the equation 2.28 for reversible

reduction [used for Peak I] and equation 2.27 for irreversible reduction [used for peak II].

The observed value of slope of linear region A and B and corresponding number of protons

calculated using equations 2.28 and 2.27 for both complex are given in Table 4.1, which

shows that one proton is involved during their reduction process.

4.3.2. Kinetic Study of reduction process of Np-PPA complexes

Studies on the heterogeneous electron transfer kinetic parameters (k0, α, and D0) of

Np-complexes in different oxidation states is also important to understand their migration

behaviour in redox environment and to elucidate the redox based remediation of soil [98]. The

reduction process of Np(V)-PPA complex appear to be irreversible in nature due to absence

of corresponding oxidation peak in cyclic voltammogram as evident from Fig. 4.1. This
[161]
irreversibility is further established by using Laviron equation , where the peak potential

(Ep) for an irreversible electrode process is expressed by equation 2.30. The Ep vs. log ν plot

grants about the irreversibility of reduction process and number of electrons involved during

reduction process and is used to find out the kinetic parameters (k0 and α). As evident from

Fig. 4.3(b), The Ep values are observed to vary linearly (R2 = 0.99) with log ν for reduction of

Np(V)-PPA complex [peak II], which confirms the irreversibility of reduction process for the

complex. The value of αn and k0 are calculated from the slope (-0.054) and intercept (-0.639)

of Ep vs. log ν plot and given in Table S4.2. The value of αn calculated from the observed

slopes is 1.09. Assuming α as 0.5, the value of n was calculated as ~2 for Np(V)-PPA

reduction process, thus corroborating the two-electron transfer reaction during its reduction

[peak II]. The heterogeneous electron transfer rate constant k0 for reduction of Np(VI)-PPA

129
[peak I] is calculated by following equation 4.6 on the basis of cathodic and anodic peak

separation [136]:

F€H 2Gx M/ F y 2G

E A = 2.18 Û Œª
Ý "ŽÞ ÛL Œª
«KY6 L KY3 ¬Ý (4.6)

In this equation, the notations D0, Epa and Epc stands for diffusion coefficient, anodic peak

potential and cathodic peak potential, respectively. Taking α as 0.5, the value of

heterogeneous electron transfer rate constant “k0” of Np(VI)-PPA complex is calculated at 20

mVs−1 using D0 = 5.05x10-5 cm2 s−1 [reported in Table 4.2] and found to be k0 =1.73x10-3 cm

s−1.

In order to evaluate the diffusion coefficient of Np-PPA complexes in both oxidation

states viz. Np(VI) and Np(V), the cyclic voltammetry measurements are carried out at

different scan rates varying from 20 to 90 mV/sec. The data are given in Fig. 4.3 (a). For both

reduction peaks [I & II] the peak current increases with scan rates. The ip vs. ν1/2 plot for the

complex Np(VI)-PPA and Np(V)-PPA are shown in Fig. 4.3 (c) and (d) respectively. The

plots (b) and (c) depict the linear relationship between ip and ν1/2, indicating diffusion control

reduction process of both complexes. The diffusion coefficient (D0) of Np(VI)-PPA and

Np(V)-PPA complexes were evaluated using the Randles-Sevcik equations viz., 2.31 (used

for peak II) and 2.32 (used for peak I) [121-122] and are given in Table 4.2.

4.3.3. Reduction mechanism: The plausible reduction mechanism of Np(VI)-PhPO3 and

Np(V)-PhPO3 complexes can be summarized as follows:

Peak I: [NpVIO2PhPO3] + H+ + e- → [NpO2VHPhPO3] (4.7)

Peak II: [NpVO2PhPO3]- + H+ + 2e- → [NpIIIO2HPhPO3]2-

↓ Rupture of Np-O bond
NpIII-PhPO3 (4.8)

4.3.4. Complexation mechanism: The complexation of Np(H2O)5+ with PhPO3H2 (PPA) can

be schematically represented as shown in Fig. 4.4. The mechanism involves the dissociation

of a proton from the PPA group and association of monoprotonated PPA with Np(H2O)5

130
which on further step forms complex with completely deprotonated PPA. In similar way the

complexation of Np(VI) with phenylphosphonic acid ligand can also be elucidated.

4.3.5. Spectrophometric Studies

The hydrated NpO2+ cation shows absorption band at 980 nm (ε = 395 M-1cm-1) due

to f-f transition which is widely used to determine the concentration of Np(V) in solution as

well as in the studies on Np(V) complexation with various ligands. The intensity as well as

position of absorption band can be used to characterize the Np(V) complexes and the

variation of absorption spectra of NpO2+ on addition of ligand can be used to determine the

stability constants of the various species formed. The spectrophotometric titrations showed a

decrease in absorbance with appearance of a single well defined isobestic point [Fig. 4.5(a-

b)] on addition of ligand. The presence of single isobestic point indicates the formation of

only one species on addition of ligand to metal ion solution. The data analysis of

spectrophotometric titration by Hyperquad 2006 [Fig. 4.5(c)] also corroborated the presence

of only 1:1 complex NpO2(PPA)- viz. [NpO2(PhPO3)]- while the Np(V) complexes with

protonated ligand were found to be absent. The determined stability constant and molar

absorbance for the Np(V)-PPA complex along with some other NpO2+ carboxylate and

dicarboxylate complexes that could resemble in mode of binding to PPA are given in Table

4.3. The f-f transitions are influenced by the ligand field around the neptunium atom which is

dominated by strong axial oxygen atoms and weaker equatorial water molecules. On binding

with the complexing ligand, the increase in ligand field at equatorial position leads to further

splitting of energy levels. The increase in ligand field results in decrease in the energy gap

between excited state 3H4 and the ground state 1G4, thereby showing the Nephelauxetic effect,

that is, red shift in the λmax on complexation is proportional to ligand field around NpO2+.

The λmax of NpO2(PPA)- shifted from 980 nm (for pure NpO2+) to 988.2 nm. The change in

λmax is higher than those of NpO2+ monocarboxylate complexes and simple dicarboxylate

131
complexes (ex: NpO2(mal)- complex) but very close to that for 1:1complex of NpO2+ with

oxydiacetate ligand (oda) wherein NpO2+ can form a 1:1 tridentate complex with oda. As the

interaction of Np(VI) with hard donor ligands are mainly electrostatic in nature, the log β of

the complex should increase with the basicity of the ligand (Linear Free Energy

Relationship). Therefore, for Np(V) complexes with hard donor atom, the ∆λmax should also
[162]
increase with the log β. Yang et al. demonstrated the linear variation of log β with ∆λmax

of Np(V) complexes with carboxylates. Fig. 4.6 shows that the ∆ λmax and log β value

obtained in the present work also follow the similar relationship.

4.3.6. DFT Calculations

The interaction of PPA with NpO2+ and NpO22+ were studied using DFT calculations.

The geometries of all the species involved in the complexation process were optimized and

interaction energy (∆E) for the complexation process was calculated. For instance, the ∆E of

reaction

àÞ (   )Ø + áℎáž# ↔ [àÞ (  )ž (áℎáž )]
#
+ 2  (4.9)

is calculated as,

XK = K[ÅYây (ãy â)ä(å.åâä)]U + 2Kãy â L KÅYây (ãyâ)çæ L Kå.åâäyU (4.10)

Phenylphosphonic acid (PPA) can bind with NpO2+ and NpO22+ through either deprotonation

of either one or both the hydroxyl group. In order to understand the most favourable path, the

geometries of all the possible complexes were optimized, which are given in Fig. 4.7 along

with calculated electronic charges on atoms. The energies (Ex) of all the species and

interaction energies of Np(V) and Np(VI) in aqueous solutions with both deprotonated and

monoprotonated ligand are given in the Table 4.4.

4.3.6.1 Structure of NpO2(H2O)5+ and NpO2(H2O)52+ : The optimized structure of

NpO2(H2O)52+ (Fig. 4.7) shows that the oxygen atoms of five water molecules are located in a

plane and are nearly equidistance from Np atom (average Np-OH2O = 2.447 Å). The

132
calculated bond distances for NpO2(H2O)52+ are in good agreement with the experimentally
[163]
observed bond distances (Table 4.5) . The good agreement between theoretically

calculated with experimentally obtained bond distances validates the computation method

(Table 4.5) used in the present work. The smaller bond distances in NpO2(H2O)52+ compared

to that in NpO2(H2O)5+ [164]

are due to higher electrostatic interaction in the former. The

difference in the Zeff of NpO22+ and NpO2+ is larger than that for hydrated forms,

NpO2(H2O)52+ and NpO2(H2O)5+. This can be attributed to the closer approach of oxygen

atoms of water molecules and axial oxygen to Np which leads its higher charge neutralization

in NpO2(H2O)52+.

4.3.6.2 Complexation of Np(V) with PPA: The negative value of formation of completely

deprotonated species (NpO2PPA- = [NpVO2PhPO3]-) (Herein, PPA= PhPO3H2, PPAH- =

[PhPO3H]- and PPA2- = [PhPO3]2- respectively), ∆E values [Table 4.4], shows its higher

stability over mono protonated complex (NpO2PPAH = [NpVO2PhPO3H]). The higher

negative charge on PPA2- results in higher electrostatic interaction between Np and ligand

donor atoms (Fig. 4.7) which in turn results in shorter average Np-OL bond distance (2.40 Å)

in NpO2PPA- compared to that in NpO2PPAH (2.57 Å). The closer approach of deprotonated

ligand binding atoms to Np atom reduces its interaction with the coordinated water molecules

and thereby increases the average Np-OH2O (2.85 Å) compared to that in monoprotonated

species (2.57) (Table 4.5). The higher stability of NpO2PPA- is in agreement with the

experimental observation using cyclic voltametry and UV-Vis spectrophotometry. The

positive ∆E indicates the weaker interaction of protonated ligand compared to water.

4.3.6.3 Complexation of Np(VI) with PPA: Np(VI) was found to form stronger complexes

with both PPA2- and PPAH- than Np(V) which can be attributed to higher Zeff on Np atom.

This was also evident by cyclic voltammetry results where more cathodic shift was observed

in Np(VI)-PPA complex than Np(V)-PPA. The higher stability of Np(VI) complexes is also

133
reflected in the geometrical parameters of these complexes. The Np-OL and Np-Oax bond

distances in Np(VI) complexes are found to be shorter than that in Np(V) complexes. Among

deprotonated and protonated complexes, Np(VI) found to form more stable complex with

completely deprotonated species. It is interesting to note that in case of completely

deprotonated species of both Np(V) and Np(VI), third water molecule moves away from first

coordination shell of NpO2+ and NpO22+. The strong interaction of PPA2- to Np atom leads to

reduction in its affinity to water molecule, thereby favouring the less coordinated structure.

4.3.7. Determination of stability constant of [NpVO2PhPO3]-

The shifts in potential in cyclic voltammetry measurements in the presence of

increasing amounts of complexing ligands were utilized to determine the stability of

complex. The peak potential was observed to shift with varying PPA concentration at fixed

Np concentration. The stability constants can be obtained by Deford−Hume formalism

[93]
as described in chapter 2 [section 2.6 (i)] . The F0(X) is related to the current and

potential data by following equation.

F0(X)=antilog{[0.434αnF/RT][∆Ep]+[log(Ip)s/(Ip)c]} (4.11)

Where, ∆Ep = (Ep)s-(Ep)c, that is, the shift in potential; n= number of transferred

electrons; Ip indicates the peak current; c and s represent the complexed and free anion

respectively. The shifts in potential with increasing PPA concentration have been measured

and used to evaluate the F0[PPA] using equation 4.11 at constant ionic strength I =0.1 M. The

F0[PPA] vs. PPA concentration plot has shown in Fig. 4.8. This plot being a straight line (R2

=0.992) provides the slope (β) =6.450x103. Thus log β value of [NpVO2PhPO3]- was found to

be 3.81±0.02, which is in excellent agreement with that evaluated by spectroscopy (log β =

3.84).

4.4. Conclusions

134
 A systematic study is carried out to investigate the redox speciation of Np, which is in

its relative infancy, in presence of Phenylphosphonic acid (PPA) under varying

physicochemical conditions by electrochemical, spectroscopy and DFT methodology. The

cathodic shift in both reduction potentials of Np in presence of PPA ligand and the

bathochromic shift in λmax are clear gesture for formation of Np-PPA complexes. The

presences of new solution species of Np in its two different oxidation states (V, VI) with the

[PhPO3]2- viz. Np(V)-PhPO3 and Np(VI)-PhPO3 are identified. This study affirms the

presence of Np(VI)/Np(V) and Np(V)/Np(III) redox couples over the other probabilities

under present experimental conditions. The speciation model presented here, recommends

that organic P existing at low concentration in humic substances is involved significantly in

binding of humic and fulvic acids with Np in soil and therefore is extremely significant for

redox based studies on migration, remediation strategies of soils contaminated with Np and

nuclear waste treatment.

135
 Figures and Tables

(a) (b)
-5
Figure 4.1. (a) Cyclic voltammetry curves: [Np]=10 M and I= 0.1 M NaClO4, Black
voltammogram is in absence of phenylphosphonic acid at pH 2.5 while Red voltammogram is
in presence of [PPA]= 1x10-3 M at same pH. (b) Differential pulse voltammetry curves: at
same solution conditions as described in above.

Region A
(a) (b)
Figure 3. Eh-pH plots, (a) For reduction peak I and (b) For reduction peak II; Condition:
[Np]=10-5 M, [PPA]= 1x10-3 M and I= 0.1 M NaClO4. Region B

(a) (b)

Figure 4.2. Eh-pH plots, (a) For reduction peak I and (b) For reduction peak II; Condition:
[Np]=10-5 M, [PPA]= 1x10-3 M and I= 0.1 M NaClO4.

136
Figure 4.3. (a) Variation of cyclic voltammograms with scan rates from 20 mV/sec to
90mV/sec. (b) E vs. logν plot for Np(V)-Phenylphosphonate (Reduction peak II); Condition:
at [Np]=10-5 M, [PPA]= 1x10-3 M and I= 0.1 M NaClO4 (c) and (d) are i vs. √ν plot for
Np(VI)-Phenylphosphonate (reduction peak I) and Np(V)-Phenylphosphonate (reduction
peak II); Condition: (a)-(c) at [Np]=10-5 M, [PPA]= 1x10-3 M and I= 0.1 M NaClO4.

137
Figure 4.4. Schematic representation for the complex formation of Np(H2O)5 by PhPO3H2.

Figure 4.5. The absorbance spectra (left) and the molar absorbance (right) of the NpO2+ -
PPA complexation. ([NpO2+] = 4.23 X 10-5 M with 0.5 M PPA at pH 2)

138
Figure 4.6. Correlation between the stability constant (log β) and the magnitude of
wavelength shift (∆λmax) where, ∆λmax = λ(NpO2L)-λ(NpO2+).

Figure 4.7. Optimised structure of Np(V) and Np(VI) complexes with PPAH- and PPA2- (A)
Np(V) with PPAH-- NpO2PPAH (B) Np(V) with PPA2- -NpO2PPA- (C) Np(VI) with PPAH--
NpO2PPAH+ (D) Np(VI) with PPA2- - NpO2PPA (Red – Oxygen, Blue – Neptunium, yellow
– Phosphorous, Gray – Carbon, white – Hydrogen).

139
Figure 4.8. The variation of F0[PPA Conc.] with [PPA Conc.].

Table 4.1. The observed slopes and calculated value of number of protons from Eh-pH plots.
Reduction Peaks Slope No. of Protons
Np(VI)-Phenylphosphonate (Peak I) -0.053 1
Np(V)-Phenylphosphonate (Peak II) -0.047 1

Table 4.2. The observed slope and calculated value of D0 from i vs. √ν plot.

Np(VI)-Phenylphosphonate (Peak I) Np(V)-Phenylphosphonate (Peak II)

2
Slope D0 (cm /sec) Slope D0 (cm2/sec)
5.40x10-6 5.05x10-5 5.72x10-6 1.05x10-5

140
Table 4.3: The stability constant, λmax, ∆λmax and molar absorbance of the 1:1 complex of
NpO2+ with PPA along with the available literature data on 1:1 NpO2+ complexes of some
dicarboxylate (acronym full forms: mal- malonic acid, oda- oxydiacetic acid, ida-
iminodiacetic acid, ppa- phenyl phosphonic acid)

Complex log β λ max / ∆ λ max / ε / mol-1 L cm-1 Ref.

nm nm

NpO2(ppa)- 3.84 988.2 8.2 302 ± 8 p.w

NpO2(acetate) 1.93 984.9 4.9 316 [61]

NpO2(benzoate) 0.7 984.9 4.9 330 [60]
NpO2(mal)- 2.63 987.4 7.4 358 ± 10 [62]
NpO2(oda)- 3.79 988.6 8.6 289 ± 10 [63]
NpO2(ida)- 5.87 990.4 10.4 375 ± 2 [63]
NpO2(mida)- 990 10.0 384 [63]
NpO2(dpa)- 989.9 9.9 360 [63]

Table 4.4. Calculated energies of all the species (EX) and interaction energies of Np(V) and
Np(VI) complexes (∆E)

Species ENpw (a.u.) EL (a.u.) Ecomplex(a.u.) EW(a.u.) ∆E(a.u.) ∆E(eV)

NpO2PPAH -1047.00 -799.30 -1693.48 -76.30 0.21 5.81
NpO2PPA- -1047.00 -798.55 -1693.01 -76.30 -0.06 -1.78
NpO2PPAH+ -1046.60 -799.30 -1693.33 -76.30 -0.04 -1.15
NpO2PPA -1046.60 -798.55 -1692.95 -76.30 -0.41 -11.21

141
Table 4.5. Bond distances (Å) in all the Np species involved in complexation process

Bond distance
Species Bond distance (Å) Bond distance (Å) (Å)
Np-OH2 Np-PPA O=Np=Oax
NpO2+ 1.734, 1.734

2.546, 2.605, 2.541, 1.805, 1.805

NpO2(H2O)5+
2.524, 2.614 ( 2.566) (1.805)

1.82, 1.81
NpO2PPAH
2.60, 2.53, 2.59 (2.571) 2.44, 2.69 (2.5665) (1.817)

NpO2PPA- 2.62, 2.52, 3.42 (2.85) 2.40, 2.40(2.40) 1.83, 1.85 (1.84)
2+
NpO2
2.446, 2.445, 2.447, 1.751, 1.751
NpO2(H2O)52+
2.449, 2.449 (1.751)
NpO2(H2O)5(ClO4)2
Experimental 2.42 1.74
NpO2PPA 2.55, 2.41, 3.56 (2.84) 2.24,2.25(2.24) 1.79, 1.78 (1.78)

NpO2PPAH+ 2.47, 2.48 ,2.51 (2.48) 2.535,2.207(2.371) 1.77, 1.77 (1.77)

142
 Chapter 5

Chemical and Redox Speciation of Uranyl ions with three hetero-

bifunctional Phosphonocarboxylate Chelates

AIM: In this chapter, the comprehensive speciation (redox and molecular) of uranium in its

two oxidation states namely, uranyl(VI) and uranyl(V) were investigated with three

environmentally relevant phosphonocarboxylate (PC) chelators differing in (CH2)n spacer

using multi techniques.

143
5.1 Introduction

Phosphonocarboxylates: Phosphonocarboxylate (PC) is a phosphorus oxoanion and

heterobifunctional organophosphonate chelator. Combining two different functional groups,

such as carboxyl and phosphonic, in PC molecule (Scheme 5.1), yields a novel chelator with

high complexing strength for metal ion through its multiple coordination sites and allows to

probe the speciation behaviour of uranyl ions in the presence of both phosphonate and
[104-106]
carboxylate groups . Its phosphonic group comprising two OH and one P=O moieties
[42-44]
has a high affinity towards actinides due to their dibasic nature . It has unique chemical

properties such as high aqueous solubility and ionization at physiological pH, greater steric

flexibility, and compelling complexing propensity even in acidic solutions at pH < 2 [104, 106,
134, 165]
. Therefore, the PC chelator would be an excellent uranophile due to the formation of

aqueous soluble complexes with UO22+ over a wide pH range and could be applicable as a

tenable option for in vivo and in vitro sequestering agent for UO22+. PC chelators are released
[166-167]
into the hydrosphere from a variety of industrial and consumer activities . Both

phosphonate and carboxylate functional groups of PC can be considered as “building blocks”

of glyphosate and natural organic matter, i.e., humic substances, which are environmentally
[134, 168-170]
persistent into the litho- and hydro-sphere . Furthermore, both carboxyl and

phosphonic functional groups are constituents of the cellular wall of microbe, i.e., bacteria

that are capable of surviving in highly harsh habitats like uranium waste piles [171]. Therefore,

the PC would be an appropriate environmentally relevant chelator that can be considered as a

model system for understanding the interaction of uranium (U) with glyphosate, humic
[171]
substances and the multifunctionality of bacterial surfaces . Since PC facilitating

adsorption and precipitation of metal ions [172], thus, this kind of chelator would be a suitable

choice to promote the biomineralization of U-phosphate minerals via microbially-mediated

organophosphate hydrolysis for immobilization of U.

144
Scheme 5.1. Structure of Phosphonocarboxylates.

In literature, previous studies are limited only to the crystal structures for

homo/hetero-bimetallic U-PAA, U-phosphonocarboxylate, and U-diphosphonoterephthalic

[173-176]
acid but no such kind of study with PFA and PPA was found . To the best of our

knowledge, no studies have been reported on aqueous speciation, solution thermodynamics,

redox characteristics, and coordination modes on the interaction of UO22+ with the considered

phosphonocarboxylates, namely, PFA, PAA, and 3-PPA ligands. The aqueous speciation of

uranyl(V) with PCs is not reported in literature. The redox energetics, Eh-pH characteristic,

PCET reduction pathway and heterogeneous electron-transfer kinetic parameters of uranyl

(VI)-PC complexes were obtained from cyclic voltammetry. The stoichiometry and

thermodynamics of interaction of uranyl(VI) (logβ, ∆G, ∆H and ∆S) with PCs have been

evaluated from UV-visible spectrophotometric and calorimetric titrations. The structural

analysis of uranyl (VI)-PC complexes are investigated by EXAFS and DFT calculations. The

redox stability of uranyl(V) with PC in the aqueous solution was also explored with varying

pH and the stability and structure of the uranyl(V)-PC complexes were reported. The

spectroelectrochemical measurements were implemented to validate the existence of

uranyl(V) species in the presence of PCs in aquatic solution.

145
5.2. Experimental, Instrumentations and Equations: Detials are provided in the chapter 2.

5.3. Results and Discussion

The accurate prediction of the speciation and the basic chemistry behind the aquatic

interactions are described in the following sections:

5.3.1. Protonation of PCs: The protonation process is an inseparable mechanism while

studying the complexation phenomenon, especially with the protonated/deprotonated ligands;

and the protonation thermodynamic data are a prerequisite to obtain the complexation

thermodynamics data. The determined protonation constants along with the other

thermodynamic parameters are shown in Table 5.1. From, the table it could be observed that

the protonation constant values for the first protonation is around 1-2, second protonation at

3-5 and third protonation at above 7. The determined enthalpies of protonation along with

free energies calculated from log KP values and entropies of protonation for all the three

Phosphonocarboxylates are given in Table 5.1. From the table, it can be observed that the

contribution from T∆S is predominant than that of ∆H values. This indicates that the

protonation reactions of all the three Phosphonocarboxylates are entropy driven.

5.3.2. Aqueous speciation (molecular and redox) of uranyl(VI) with PCs:

5.3.2.1. Molecular speciation (Stoichiometry and Thermodynamic) and physical

evidence by UV–Visible spectrophotometry, Calorimetry and ESI-MS: The chemical

nature of the participating chelator and the geometry arrived by its coordination on the

equatorial plane of uranyl(VI) (i.e. UO22+), has effects on the intensities and positions of
[177-178]
electronic transitions of uranyl ion . The present studies involve absorption

measurements in the titration mode, where the chelator solutions are added in increments to a

fixed volume of uranyl(VI) solution, in the range of 380-480 nm arising from vibronically

perturbed electronic transitions [177-178]. The absorption spectra profile for the complexation of

UO22+ with 3-PPA and its deconvoluted spectra showing the individual absorption spectra of

146
free uranyl(VI) and the UO22+-3-PPA complex are given in Fig. 5.1(i-ii), respectively. Similar

kind of absorption profiles and deconvolution were also observed in the case of UO22+-PFA

and UO22+-PAA complexation. The deconvolution of absorption spectra titration data was

done by HypSpec software to determine the maximum wavelength of absorption (λmax) and

the corresponding molar absorptivity (ε) at λmax of each species formed in all the three

complexation systems. All these systems showed a red shift in absorption spectra on the

addition of PCs with an increase in the absorption intensities too. The λmax with

corresponding ε values for all the species determined in the present studies are shown in

Table S5.1. HypSpec software was used to determine the stability and the species formed by

uranyl(VI)-PCs complexation. Various chemical models like (i) different combinations of the

formation of 1:1 and 1:2 uranyl(VI)-PC complexes; (ii) different protonated form of

complexes such as MLH, MLH2 and MLH3 kind of species; (iii) hydrolytic species such as

UO2(OH)+, (UO2)2(OH)22+, (UO2)3(OH)5+; (iv) the metal-chelator-hydroxide mixed

complexes of the form MLx(OH)n (x/n=0,1, 2,….); (v) the polymeric species of the form

MxLy(OH)n are tried as different models to fit the spectrophotometric data. The model

including the formation of metal complexes with monoprotonated PC chelators of the form

MLH was found to be in convergence criteria [Fig. 5.1(iii)]. The physical evidence of

speciation obtained by fitting absorbance data was further validated by ESI-MS experiments.

Fig. S5.1(i-iii) shows the ESI-MS spectra of UO22+ with the PCs and corresponding

assignments of species in terms of their respective m/z values are reported in Table 5.2. The

m/z values in the table specify the formation of MLH type of species and hence authenticate

the stoichiometry of complexes obtained by HypSpec software. The determined stability

constants are presented in Table 5.3, which indicates an interesting observation related to the

higher stability of uranyl(VI)-PCs complexes in the aqueous phase and suggests that the

mode of coordination in these complexes to be tridentate or higher. But, the literature reports

147
states that the linear UO22+ geometry restricts the participation of all the three oxygens (two

from the phosphonate group and one from the carboxylate group), which is attributed to the

electrostatic repulsion between the axial oxygen of UO22+ with the second oxygen donor of
[108]
phosphonate group . The exceptionally enhanced stability of the uranyl(VI)-PCs

complexes is due to the formation of stereognostic intramolecular hydrogen bonding (IMHB)

between the -OH of monoprotonated phosphonate group and the axial UO22+ oxygen atom on

the complex formation (as observed in DFT calculations, described later). The log KML

values for all three UO22+-PCs are found to be nearly the same. The ring size in combination

with steric strain results in the observed trend of complex stabilities. Calorimetry titration was

employed to determine the complexation enthalpies for the interaction of uranyl(VI) with the

three PCs. The determined complexation enthalpies (equation 2.26) with all other solution

thermodynamic parameters are embedded in Table 5.3. From the table, it can be observed

that the complexation process is majorly entropy driven with very small values of

complexation enthalpies relative to T∆S values. All the complexation enthalpies are

exothermic and follow the trend of [UO2(PFAH)(H2O)3] < [UO2(PAAH) (H2O)3] < [UO2(3-

PPAH) (H2O)3]. Due to higher stability of the [UO2(PFAH)(H2O)3] complex owing to the

presence of a most stable five-membered ring, compared to [UO2(PAAH) (H2O)3], the ∆H of

[UO2(PFAH)(H2O)3] is more exothermic.

5.3.2.2. Redox Speciation (Redox energetic and kinetic, Pourbaix diagram, and

pathways of electron transfer by electrochemical studies): To gauge the complexation and

speciation, the solution redox behaviour of uranyl(VI) with the varying architecture of PCs

(viz. PFA, PAA & 3-PPA) were probed by cyclic Voltammetry (CV). The CV measurements

were performed to understand the influence that chelator electronic and structural changes

exert over the redox response of UO22+ due to complexation. Representative CV curves [(i)-

(v)], corresponding to UO22+ species and UO22+ in the presence of three PCs chelators,

148
obtained in the potential sweep region from 0 to -1 V, are shown in Fig. 5.2. The CV (i)

obtained for UO22+, specifies the reversible reduction wave at -0.176 V and corresponding
[116-118]
oxidation at -0.112 V, is attributed to U(VI/V) activity . Importantly, alteration in

redox potential and redox wave characteristics of UO22+ with PCs were observed in CV

curves (ii-iv). This is a clear indication of the interaction and complexation of all three PCs

with uranyl(VI) and the significant effect of equatorially attached PCs on the redox behaviour

of uranyl(VI) species. The cathodic shift in reduction wave potential was found in complexes

of UO22+ with PFA, PAA and 3-PPA chelators. The absence of oxidative wave in CV curves

(ii-iv) during anodic potential sweep [from -1 to 0 V] indicates the irreversibility of reduction

wave in complexes due to slow redox kinetics relative to that of UO22+ species in solution.

The measured peak potential (Epcom), formal potential (Efcom), the relative shift in potential

(∆Epcom) and visualized characteristic of reduction wave of UO22+ complexes with three PCs

are summarized in Table 5.4. The number of electrons associated with the reduction wave of

complexes was computed and their corresponding values have been mentioned in Table 5.4.

As obvious from the table, the number of electron is one hence the irreversible reduction

wave in the complexes is assigned to the U(VI)-U(V) process. The significant cathodic shift

in reduction wave potential of complexes than the UO22+ is consistent with the more electron-

rich propensity of UO22+ due to binding of strongly electron-donating PC chelators and

perturbation in the UO22+ electronic state because of complexation [179]

. Moreover, the

cathodic shift in reductive wave potential of UO22+-PC complexes was found to be larger than

that of other known values of UO22+-complexes (U(VI)/U(V) redox couple) with other

ligands/chelators such as citrate [180] and phenylphosphonate [148] [Table 5.4].

Pourbiax diagrams (Eh-pH plot) of uranyl(VI) with three PCs are constructed by

experimental results [Fig. 5.3(i)]. To get an insight into the thermodynamically stable region

and to estimate the numbers of protons associated with electron transfer (ET) step of U

149
species as a function of physicochemical parameter viz. pH, it is significantly imperative to

report the electrochemical phase diagrams (Eh-pH plot). The Eh-pH plots of all three

uranyl(VI) complexes show the discontinuity in linearity in the pH region 1.5 to 8, resulting

in two linear regions A and B with different slopes [Table 5.5]. The number of protons

associated with the ET step in both region A and B was calculated from their respective slope

values (equation 2.27) and are given in Table 5.5. The number of protons in region A in all

three complexes was observed to be ~ 1. This shows the one electron and one proton

involvement in the reduction wave of uranyl(VI)-PC complexes in linear region A. Therefore,

the reduction wave obtained in CV curves (ii-iv) of complexes in pH region A is attributed to

PCET (Proton coupled electron transfer) step. The speciation plots [described later] of

complexes confirm the dominancy of single complex species up to pH ≤ 6.5. At pH ≥ 6.5, the

uranyl(VI) hydroxyl species leads over the uranyl(VI)-PC complexes. However, the

uranyl(VI) hydroxyl species remain soluble in the presence of PCs in the aqueous solution up

to pH 8, as no precipitation was noticed during the experiments. Further, the observed slope

of complexes in region B is lower than that of region A [Table 5.5] and electrochemical

calculation in region B corroborates the U(VI)-U(V) couple as a reduction wave. It suggests

the change in speciation and the invariant nature of the reductive wave concerning ET in two

different regions A and B. The invariant nature of reductive wave of complexes concerning

ET in both pH regions A and B suggests that three PCs deliver sufficient stability to

U(VI)/U(V) couple in aqueous solution in the pH range 1.5 to 8. Previous electrochemical

[115-120, 135]
studies on uranium described the instability of uranyl(V) in the aqueous solution
[119]
due to its disproportionation nature. Suzuki et al. reported the slow disproportionation

nature of uranyl(V) in acidic pH (2-5) in solution, hence elucidating its slight stability in this

pH region while beyond this pH the disproportionation was rapid resulting in its

disappearance. Furthermore, in our previous studies on redox speciation of uranyl(VI), the

150
disproportionation was observed in near neutral (pH>5) and in the acidic region (pH <4.5) in
[180] [148]
the presence of citrate and phenylphosphonate respectively. However, with the

present PCs, an interesting observation was found related to the enhanced stability of

uranyl(V) and the absence of disproportionation in a wider pH range from acidic (pH 2) to

near alkaline (pH 8) in the aqueous solution.

The effect of scan rate variations on reductive wave potential and peak current are

summarized in Fig. 5.3(ii-iv). The reductive wave potential of complexes was found to be

dependent on scan rates [Fig. 5.3(iii)] with the linear relationship between the Ecom and logν

(equation 2.30 and 2.35) and hence corroborates the redox irreversibility of UO22+-PC

complexes. The slopes of Ecom vs. logν plot for UO22+- PC complexes are given in Table 5.5.

The probability of disproportionation reaction of uranyl(V) was neglected due to observance

of the cathodic shift in potential with nearly 30/αn mV per tenfold increase in scan rate [124,
180]
. Herein, the observed slopes [Table 5.5] in complexes are lower than the expected value

for Nernstian one ET reduction process. This reveals the complex kinetic and coupled
[124, 126, 180]
chemical reaction with the ET step . The decrease in peak current function

(icom/√ν) with the scan rates (CV) [Fig. 5.4(i)] and the variation in

chronopotentiometric constant (iτ1/2, where τ is the transition time for reduction wave)

with the applied currents (chronopotentiometry; CP) [Fig. 5.4(ii)] were observed in

UO22+-CP complexes. Ideally, for diffusion-controlled irreversible ET process, the

icom/√ν and iτ1/2 quantities should be independent of scan rate (equation 2.31) and the

magnitude of applied current [according to sand equation [75-76]: iτ1/2 = (√πnFA√DC)/2]

respectively. However, the present observation in icom/√ν and iτ1/2 quantities further

suggests the coupled chemical reaction with the ET step. Fig. 5.4(iii) describes a

typical chronoamperometry (CA) data in terms of normalized icom vs. t-1/2 related to

UO22+-PAA complex which indicates a transition between two linear regions with

151
different slopes and authenticates the association of the chemical reaction with the ET

step in UO22+-PC complexes [128, 180]. With the assumption of coupled chemical reaction,

the slope of the linear portion of Ecom vs. logν plot can be represented by equation 2.29 [124,
126, 180]
. The value of αn of complexes, calculated from their respective slope using equation

2.29 is given in Table 5.5. Fig. 5.3(ii) depict the proportional relation between the reduction

wave current and scan rates in UO22+-PC complexes. The icom vs. √ν plots for complexes [Fig.

5.3(iv)] indicates that the icom varies linearly with √ν. This is consistent with Randles-Sevcik

equation 2.31 and diffusion-limited reductive electron transfer at the electrode in UO22+-CP

complexes. The diffusion coefficient (D0) of complexes, were evaluated from their respective

slope [icom vs. √ν] using equation 2.31, and have been shown in Table 5.5. In CP, for

diffusion-controlled irreversible reduction of UO22+-CP complexes, the values of αn

and kof, h obtained from slope and intercept of the linear portion of the E vs. log [l - (t

/τ) ½] curves (equation 2.33) [Fig. 5.4(iv)] are given in Table 5.5.

5.3.3. Structural studies-binding mode: (EXAFS and DFT)

5.3.3.1. EXAFS study: The EXAFS experiments are conducted to get an insight into the

coordination situation around the U atom in UO22+-CP complexes. The normalized XANES

spectra of UO2CO3, U(VI)-PAA, U(VI)-PFA and U(VI)-3-PPA samples [Fig. 5.5(i)] reveal

that uranium is in the sixth oxidation state. The χ ( R ) versus R plots at U L3-edge generated

using Fourier transform from the µ (E ) versus E spectra (equation 2.17 and 2.18) are shown

in Fig. 5.5(ii) for the U(VI)-PAA, U(VI)-PFA and U(VI)-3-PPA samples. The best fitted

theoretical spectra, 1-3.2 Å in R space, along with the experimental data for the respective

samples have been shown in Fig. 5.5(ii) and the best-fit parameters have been given in Table

5.6. The correctness of the fit has been determined by the value of the R factor
defined by

equation 2.19 and mentioned in Table 5.6. The first peak at 1.3 Å and the second peak at 1.9

Å in the samples correspond to shells of axial oxygen atoms and equatorial oxygen atoms

152
respectively. EXAFS data for U(VI)-PAA was found to fit in one oxygen shell at R=2.34 Å

whereas in the case of U(VI)-3-PPA and U(VI)-PFA the data fitted in two oxygen atom shells

at the equatorial plane. In U(VI)-PAA, three oxygen atoms of coordinated water molecules

and one oxygen atom of phosphonate and carboxylate are found to be at the same distance

(R~ 2.34±0.002 Å). In U(VI)-PFA, three coordinated water molecules are obtained at a larger

distance (~ 2.41 Å) compared to chelator oxygen atoms (~2.29 Å). A similar trend was also

observed for U(VI)-3-PPA. The bond distances between U(VI) and the oxygen atom of water

molecules in U(VI)-PFA and U(VI)-3-PPA are very close to that reported in the literature
[181]
. Furthermore, the U-P and U-C distances were observed to be at 3.60±0.02 Å (N=

1.075±0.01; σ2= 0.0023) and 3.23±0.01 Å (N= 1.075±0.01; σ2= 0.001) in the U(VI)-3-PPA

respectively. These values are in agreement with the monodentate binding of phosphonate

and carboxylate functional group with the UO22+ [182-183]

. Hence, the EXAFS analysis

suggests the coordination mode F (Scheme 5.2) in the present UO22+-PC complexes.

5.3.3.2. Theoretical Study (DFT calculations): We performed DFT calculations to

corroborate the experimental results and to find out the energetically stable molecular

structure of the uranyl(VI)-CP complexes and the reason behind their higher logβ values. The

structure optimization of complexes was tried with all possibilities of coordination modes and

it was found that the structure with chelates formation by binding through one oxygen of

phosphonate and another oxygen of carboxylate along with three water molecules in the inner

sphere of UO2 moiety are energetically more stable [Fig. 5.6(a)]. The binding energetics for

all the geometries are shown in Table 5.7. From the table, it can be observed that the free

energies of formation in aqueous complexes are very close to each other with a variation of

±10-15 kJ/mol. A similar observation was also found in experimentally determined free

energies of formation, which also has small differences with the same order of the

complexation strength.

153
 The bond distances and the partial charges on individual atoms in the stable optimized

geometries and their comparison with the values in bare PCs are also estimated to understand

the complexation process at the molecular level. The bond distances between U and all the

coordinating atoms in the optimized structure of the UO22+-PCs are shown in Table 5.8. The

calculated bond distances (viz., U–Oax, U–Oeq and U–Owater) of the complexes through DFT

are nearly consistent with that by EXAFS measurements. Most surprisingly, DFT

calculations reveal an important interaction between the axial oxygen of UO22+ and the

monoprotonated phosphonate group [Fig. 5.6(a) and Table 5.8]. The intrinsic structural

feature of PCs provides a spatial advantage in simultaneously coordinating equatorially with

UO22+ and forming stereognostic intramolecular hydrogen bond (IMHB) with axial oxygen of

UO22+ [30-31]
. This stereognostic IMHB plays a vital role in stabilizing the complexes as it

could provide an additional driving force for the coordination of UO22+ and therefore enhance

the chelating ability of PCs. The equatorial binding of PCs pushes the axial oxygens of UO22+

away from the metal ion and results in the elongation of axial O-U-O bonds. The elongation

of U-O bonds originated from axial oxygens and water molecules are visible indicators for

strong complexation of uranium by PCs and the same extent of elongation of these two bond

distances are good supporters for the nearly same logβ values of the complexes. Important

key observations can be made from partial charge calculations [Table S5.2]: (i) The charge

on uranium ion is much lower in complex form than in aquated form, (ii) The axial oxygens

have a higher negative charge in complex form than in aquated form, and the axial oxygen

involved in H-bond has relatively more negative charge than the other axial oxygen in

complex than in aquated form, (iii) The negative charge on all the oxygen atoms of both

phosphonate and carboxylate is lowered on complex formation than in free chelator, and (iv)

The positive charge on hydrogen atom involved in H-bond is slightly higher in complex form

than in bare chelator form.

154
 The slight variations in the stability and the entropies of formation observed

experimentally can be better explained by the conformational changes in CP molecules on

complex formation. The distance between the oxygen of phosphonate and oxygen of

carboxylate (O-O) in bare PCs and complexes, the angle subtended at U by these two

coordinating atoms (∟O-U-O of complex) and the angle subtended at U by the two axial

oxygen atoms (∟O-U-O of UO2) are given in Table S5.3. The experimental trends showed

an increase in complexation entropy from UO2-PFAH to UO2–3-PPAH system. The linearity

of UO2 moiety also deviated on complex formation in all the UO22+-PC systems. The extent

of deviation from linearity in UO22+ is nearly the same in all the three complexes is a further

indication for the nearly same stability of all the three complexes. The angle subtended by the

PCs atoms at central metal ion is higher in UO2–3-PPAH complex followed by UO2-PAAH

and UO2-PFAH. Thus, the chelate ring formation has a higher strain in the case of UO2-

PFAH complex and lowest in the case of UO2–3-PPAH complex. The order of the angle

subtended by PCs during UO22+ binding can be related to their spatial binding requirement.

The higher the angle subtended by CP, the higher is the spatial requirement. Therefore, the

order of the angle subtended by CP explains the experimentally obtained ∆S for

complexation [Table 5.3].

Based on EXAFS and DFT analysis the probable structure of uranyl(VI)- PC

complexes in the aqueous phase could be assigned as F (Scheme 5.2). The presence of IMHB

interaction enhances the binding affinity and selectivity for U and prevents its desorption in

the aquatic phase by PCs [30-31].

5.3.4. Pathways of electron transfer (reduction-mechanism): The plausible reduction

mechanism of UO22+-CP complexes can be described by Scheme 5.3 [124, 180]

which shows

the stoichiometry of uranyl(V)-CP complexes as [(UVO2)(HO3P-(CH2)n-CO2; n=0,1

and 2]−.

155
5.3.5. Aqueous speciation (stability and structure) of uranyl(V) with PCs and
[132, 184]
Spectroelectrochemical evidence: To the best of our knowledge, except carbonate
[180]
and citrate chelators, no study has been reported on the aqueous speciation of uranyl(V)

with the organic chelator. As discussed earlier (section 3.1.2), in the presence of PCs the

uranyl(V) does not undergo disproportionation from acidic pH 2 to near alkaline pH 8 in the

aqueous solution and hence it was anticipated that the uranyl(V) has aqueous redox stability

with the PCs in wide pH range. D. Cohen et al. [132] and Ikeda et al. [185] reported the stability

of uranyl(V) in aqueous solution by electrolysis in very harsh experimental conditions such

as the high concentration of carbonate (> 0.8 M) and limited pH range (11.7 to 12) and

suggested that any deviation from these experimental conditions will result into the brownish

precipitation. Faizova et al. [186] reported the stabilization of uranyl(V) in aqueous solution by

aminocarboxylate chelator dpaea2− (dpaeaH2 = bis(pyridyl-6-methyl-2-carboxylate)- in the

pH range 7-10 and the role of iron (Fe2+) binding in this stabilization phenomenon [187]
. The

present studies represent the aquatic redox stability of uranyl(V) by three PC chelators in a

broader pH range (2 to 8) with modest experimental conditions than the previous studies [132,
185]
. Herein, the appropriate reasons behind the aqueous redox stability of uranyl(V) and its

molecular parameters viz., stability (logβ) and structure with PCs were discussed.

The formal redox potential (Ef) of ET step (i) (Scheme 5.3), is described by
[180]
equation 3.3 . By substituting logβVI values of uranyl(VI)-PC complexes in

equation 3.3, the logβV values of uranyl(V)-CP complexes are evaluated and provided

in Table 5.9. The evaluated stability constant values of uranyl(V) complex with three

PCs were considerably higher than that reported by carbonate [logβ= 6.6±0.3][184] and

citrate [logβ=6.10±0.12][180]. The DFT calculations were carried out on uranyl(V)-CP

complexes to understand the higher stability of uranyl(V)-CP complexes in the

aqueous phase. The DFT optimized structure of the uranyl(V)-PAA complex is shown

156
in Fig. 5.6(b) and bond distances and partial charge on atoms (involved in hydrogen

bonding) of uranyl(V)-CP complexes are given in Table 5.9. Fig. 5.6(b) suggests the

presence of IMHB interaction between axial oxygen of uranyl(V) and monoprotonated

phosphonate group in uranyl(V)-CP complexes and heterobidentate coordination mode

of the three CP chelators with uranyl(V) and hence corroborates the proposed structure

F1 of uranyl(V)-CP complexes as shown in scheme 5.3. Table 5.9 indicates the shorter

bond distances and higher partial charges on atoms involved in IMHB interaction in

uranyl(V)-CP complexes as compared to that of uranyl(VI)- PC complexes [Table 5.8

and Table S5.2]. This implies stronger IMHB interaction in uranyl(V)-CP complexes

compared to uranyl(VI)-CP complexes. The IMHB interaction in uranyl(V)-CP

complexes along the O=U=O axis is an important factor that provides steric protection
[188-189]
against the cation-cation interactions (CCIs) between two uranyl(V) moiety and

dimeric intermediate formation. Both the electronic and steric effects, viz., strong

heterobifunctional equatorial chelation and steric protection through IMHB, of PCs

disfavour the disproportionation of uranyl(V) in the aqueous phase even in the absence

of a bulky chelator. Further, the possibility of rearrangement reaction of uranyl(V) due

to increased basicity of oxo group of uranyl(V) formed after reduction of uranyl(VI) is

supposed to be negligible in the presence of PCs due to steric protection [188-189] of oxo

group of uranyl(V) through IMHB interaction.

In-situ UV-vis spectroelectrochemical studies were performed at two different pH 4

[Fig. 5.7(a-b)] and 8 [Fig. S5.2(a-b)] to validate the aqueous redox stability of uranyl(V) with

PCs (as observed in the CV) and the existence of uranyl(V) species in wider pH (2 to 8) and

to acquire the electronic absorption spectra of uranyl(V)-CP complex in aquatic phase. With

the applied cathodic potential from -0.1 V to -2.6 V, the decrease in absorbance at 413 nm,

423 nm and 435 nm were observed at both pH 4 and 8. Since the absorbance at 413 nm, 423

157
nm and 435 nm are associated with the absorbance of uranyl(VI) in an aqueous medium

hence the decreasing trend with the applied cathodic potentials demonstrates a decrease in its

concentration at both pH 4 and 8, and thus the reduction process of uranyl(VI)-PAA complex.

The isosbestic points were seen at 445 nm, 453 nm, 477 nm, 484 nm, and 551 nm in

absorbance spectra obtained with applied cathodic potentials at pH 4 and 8. The presence of
[129, 131]
isosbestic points affirms the existence of a single redox equilibrium . Since the

reduction process of UO22+ to U(IV) involves the two ET steps along with U-O bond-

breaking chemical reaction, suggesting no single redox equilibrium. Therefore, it was

expected that the UO22+ to U(IV) reduction process would occur without isosbestic points.

Hence, the presence of isosbestic points in the present case validates the conversion of

uranyl(VI)-PAA to uranyl(V)-PAA species through the reduction process with the applied

cathodic potentials at both pH 4 and 8. In wavelength region 560 nm to 950 nm, the

appearance of new absorption peaks at 571 nm, 633 nm, 677 nm, 850 nm and 900 nm were

found with applied cathodic potentials at pH 4 and 8 [Fig. 5.7(b) and Fig. S5.2(b)]. These

new absorption peaks, which arise due to f-f transitions in the 5f1 configuration in the visible

and near-infrared region, can be assigned to uranyl(V)-PAA species as the absorbance at

these peaks have an increasing trend with the applied cathodic potentials. The assignment of

peaks positions was further corroborated by previous literature reports [129, 131-132, 180].

5.3.6. Aqueous speciation modelling of uranyl(VI) and uranyl(V) with PCs: The aquatic

speciation calculations on complexation of uranyl(VI) and uranyl(V) with PCs have

performed with Hyperquad simulation and speciation (HySS) software by using their

respective formation constant values (logβ). The speciation modelling of uranyl(VI)-

PC along with uranyl(VI) hydroxyl species is shown in Fig. 5.8(a), which shows the

complexation process is pH-dependent and predicts the dominancy of the MLH type

of complex of uranyl(VI)-PCs in the pH range 2 to 6.5. It also indicates that at higher

158
pH >6.5, the uranyl(VI) hydroxyl species dominates over the complex species. The

speciation models of uranyl(V)-CP species along with that of carbonate and citrate are

shown in Fig. 5.8(b). From Fig. 5.8(b), it is evident that uranyl(V)-CP species is

predominant in wider pH (2-8) than uranyl(V)-carbonate and uranyl(V)-citrate species.

The uranyl(V) has aquatic redox stability in wider pH range [~47 % of pH region, Fig.

5.8(c)] as well as higher logβ values with PCs than the other ligands/chelators used in

the previous studies [180, 184].

5.4. Conclusions

The foregoing results deliver systematic investigation on aquatic speciation

(molecular and redox) and binding modes of uranyl(VI) with three PC organic chelators as a

function of pH and reveal that these kinds of chelators have a very high complexation

tendency for uranyl(VI) and uranyl(V) in the aquatic environment. The comprehensive

experimental determinations in combination with the theoretical estimations successfully

assessed the redox variables, trends in complexing strengths and structural factors of

uranyl(VI)- and uranyl(V)- PC complexes at the molecular level. Molecular speciation

studies highlight the MLH type complexes and describe their thermodynamic stabilities and

energetics in terms of higher stability, exothermic enthalpies and entropy-driven

complexation. EXAFS analysis and DFT calculations deduced the accurate structure as F

(scheme 5.2) of the uranyl(VI) complexes. Redox speciation studies by CV confirms the one-

electron reduction of uranyl(VI) to uranyl(V) species in the presence of PCs, provides the

redox energetics, Eh-pH characteristics and electron transfer kinetics of uranyl(VI)

complexes, and identifies their reduction pathways as PCET. The present studies describe the

stability, structure, and primitive aspects behind the absence of disproportionation of

uranyl(V) with PCs and validates its existence in the aquatic environment by

spectroelectrochemical measurements.

159
 Schemes, Figures and Tables

Scheme 5.2. Coordination modes of PC chelators.

Scheme 5.3. Pathway of electron transfer (reduction-mechanism) of Uranyl(VI)-PC

complexes.

160
 0.06
20
0.05
Optical Density / a.u Increasing [PPA] ML
16
0.04

ε / (mol lit cm )
-1
0.03 12
M

-1
0.02 8

0.01 4

0.00 0
360 390 420 450 480 510 360 390 420 450 480 510
Wavelength / nm Wavelength / nm

(i) (ii)

100

90

etoM
80
0.142
70

tiv
ity

ity
la
60

nre
s

s
n

n
te

te
50

tio
In

In
a
40

rm
0.138

fo
30

%
20

10

0.134 0
Obs-Cal c i ntensi ty (unwei ghted)
5.0E-4
e

e
lu

lu
a

0 a
v

v
-5.0E-4
0 0.10 0.20 0.30 0.40
ti tre vol ume/ml

(iii)

Figure 5.1. The complexation of uranyl(VI) with Phosphonopropionate (3-PPA) (i)

Absorption spectra with increasing the addition of 3-PPA; (ii) The absorption spectra of

individual species: free uranyl(VI) and 1:1 UO22+-3-PPA complex. (iii) Hyperquad fitted

speciation diagram for the complexation of uranyl with phosphonoacetate (PAA) ([UO22+] =

0.003 M, [PAA] = 0.02 M).

161
Figure 5.2. Cyclic Voltammetry Plots of Uranyl(VI) and its complexes with PCs. (i)

[UO22+]= 10-5 M (ii-iv) [UO22+] with [PFA], [PAA] and [3-PPA] at 5x10-4 M

respectively (v) [PAA]= 5x10-4 M; all at I= 0.1 M NaClO4 and pH=4.

162
 (i) (ii)

(iii) (iv)

Figure 5.3. (i) Eh-pH plots of [UO22+]= 10-5 M with [3-PPA]= 5x10-4 M, (ii) i(A) vs.

E(V) plot with varying scan rates 10-100 mV/sec and (iii) E vs. log ν plot of UO22+

with 3-PPA, (iv) i(A) vs. √ν plot of UO22+-3-PPA.

163
(i) (ii)

(iii) (iv)

Figure 5.4. The different electrochemical plots of UO22+-PAA. (i) is the variations of peak

current functions (i/√ν)) with scan rates (CV). (ii) is the variation of

(i 1/2) with i(A) (CP). (iii) is the plots of i(A) vs.

chronopotentiometric constants (iτ v t-1/2

[1-(t/τ)1/2] plots (CP). i(A) and E(V) are considered as icom and
(CA). (iv) is the E(V) vs. log [1

Ecom.

164
(i)

(ii)

Figure 5.5. (i) Normalized XANES spectra of UO2CO3, U(VI)-PAA, U(VI)-PFA and U(VI)-

3-PPA at U L3-edge. (ii) Fourier transformed EXAFS spectra of U(VI)-PFA, U(VI)-PAA and

U(VI)-3-PPA at U L3-edge. The experimental spectra are represented by Scatter points and

the theoretical fit is represented by Solid line.

165
 [UO2 (PFAH) (H2O)3] [UO2 (PAAH) (H2O)3] [UO2 (PPAH) (H2O)3]
(a)

(b)

Figure 5.6. Optimized DFT structures:

structures (a) Structures for the optimized geometries of
Uranyl(VI)- monoprotonated CP complexes. (Colour code of atoms: Blue - Uranium, Red -
Oxygen, Gold - Phosphorous, Grey - Carbon and White - Hydrogen). (b) Structure for the
optimized geometries of uranyl(V)-CP
uranyl(V) complex. (Colour code of atoms: Blue-Uranium,
Uranium, Red-
Red
Oxygen, Gold-Phosphorous,
Phosphorous, Grey-Carbon
Grey and White-Hydrogen).

166
 (a)

(b)

Figure 5.7. Spectroelectrochemical electrolysis

electrolysis data at pH 4. (a) is the absorption spectra
with varying cathodic potentials in the wavelength region 375 nm to 550 nm (b) is the
absorption spectra with varying cathodic potentials in the wavelength region 560 nm to 1000
nm.

167
 Spec iation plot of U rany l-3-PPA
100 MLH

M MH-3

etoM
80
M3 H-5
lativ M3 H-7
60
rma nre
tio

40
%fo

20 M4 H-7

MH-1
0
1 3 5 7 9
pH

(a)

(b) (c)

Figure 5.8. Speciation plots of uranyl(VI) and uranyl(V). (a) Uranyl(VI) with 3-PPA (H- is

the -OH group, M is uranyl(VI) and L is 3-PPA) (b) uranyl(V) with CP (PAA), citrate and

carbonate chelators (c) percentage of pH region of uranyl(v) stability with organic chelators.

168
Table 5.1: Protonation constants for three Phosphonocarboxylates. (Experimental conditions:

T = 298 K, P = 0.1 M Pa and I =1.0 M NaClO4).

log KP ∆ G (kJ/mol) ∆ H (kJ/mol) T ∆S (kJ/mol) ∆ S (J/K/mol)

Phosphono Formic Acid (PFA)

LH
7.37 ±0.08 -42.09 ±0.48 -2.54 ± 0.04 39.55 ± 0.52 132.6 ±1.7
LH2
3.16 ± 0.02 -18.05 ± 0.10 0.72 ±0.02 18.77 ±0.12 63.0 ± 0.4
LH3
1.99 ± 0.01 -11.34 ± 0.04 2.31 ±0.03 13.66 ±0.07 45.8 ± 0.2

Phosphono Acetic Acid (PAA)

LH
7.39 ±0.07 -42.18 ±0.40 -1.41 ±0.03 40.77 ±0.43 136.7 ±1.4
LH2
4.67 ±0.04 -26.69 ±0.23 -4.13 ±0.04 22.56 ±0.27 75.7 ±0.9
LH3
1.86 ±0.01 -10.63 ±0.05 5.70 ±0.07 16.33 ±0.12 54.8 ±0.4

Phosphono Propanoic Acid (3-PPA)

LH
7.31 ±0.08 -41.76 ±0.47 0.79 ±0.01 42.55 ±0.48 142.7 ±1.6
LH2
4.56 ± 0.06 -26.03 ±0.36 0.70 ±0.01 26.73 ±0.37 89.6 ±1.2
LH3
2.07 ± 0.02 -11.84 ±0.11 8.63 ±0.08 20.48 ±0.19 68.7 ±0.6

169
Table 5.2. Assignment of Species from m/z values obtained in ESI-MS spectra.

Sl. No. m/z Assignment

[UO2]+
270.05
[UO2(HO3PCO2H)(H2O)2]+
431.02
1. Species of PFA & [UO2(HO3PCO2)(CH3OH) + Na]+
449.03
Uranyl [UO2(HO3PCO2)(CH3OH)(H2O) + Na]+
467.05
192.9 [(O3PCO2H)+3Na]+
148.9 [(H2O3PCO2H)+Na]+
[(C2H4O5P)(UO2)]+
409.02
2. Species of PAA 427.03 [(C2H4O5P)(UO2)(H2O)]+
& Uranyl 445.04 [(C2H4O5P)(UO2)(H2O)2]+
470.99 [(C2H3O5P)(UO2)(HO) + 2Na]+
485.01 [(C2H3O5P)(UO2)(H2O)3 + Na]+
[UO2(HO)(CH3OH)(H2O)]+
337.05
3. Species of 3-PPA 505.08 [(C3H6O5P) UO2(CH3OH)2(H2O)]+
& Uranyl 513.04 [(C3H5O5P)UO2(CH3OH)(H2O) + Na]+
527.06 [(C3H6O5P)UO2(CH3OH)2(H2O) + Na]+
543.03 [(C3H5O5P)UO2(CH3OH)2(H2O) + K]+

170
Table 5.3. Thermodynamic parameters for the complexation of Uranyl with three PCs.
(Experimental conditions: T = 298 K, P = 0.1 M Pa and I =1.0 M NaClO4, [UO22+] = 0.003
M, [L] = 0.02 M; L = PFA/PAA/3-PPA).

Complex log β ∆ G (kJ/mol) ∆H T ∆S ∆S

(kJ/mol) (kJ/mol) (J/K/mol)
UO22+-PFAH 12.21 ± 0.05 -69.70 ± 0.28 -6.44 ±0.06 63.26 ± 0.28 217.1 ± 0.9

UO22+-PAAH 12.92 ± 0.09 -73.24 ± 0.51 -4.97 ± 0.06 68.27± 0.51 224.0 ± 1.7

UO22+-3-PPAH 13.06 ± 0.07 -74.56 ± 0.40 -3.62 ± 0.03 70.94± 0.40 237.9 ± 1.3

Table 5.4. Summary of Cyclic Voltammetry data of UO22+-PCs and comparison of potential
of U(VI)/U(V) redox couple with various complexing chelators.

System Characteristics Electrochemical CV: E vs. Refere

Thermodynamic Parameters ν plot nce

Peak Shift in Redox No. of Efcom

Potential Peak behaviour electro (Formal
(Epcom)(V) Potential ns in redox
(∆Epcom) ET Potential)
(V) step
UO22+ -0.176 ---- Reversible 1 -0.142 V [62]
UO22+-PFAH
-0.405 -0.229 Irreversible 1 -0.395 V p.w.

UO22+-PAAH -0.429 -0.253 Irreversible 1 -0.408 V p.w.

UO22+-3-PPAH -0.412 -0.236 Irreversible 1 -0.373 V p.w.

UO22+-Citrate -0.234 -0.058 Irreversible 1 -0.218 V [59]

UO22+- -0.292 -0.116 Irreversible 1 -0.204 V [60]

Phenylphosphonate

171
 Table 5.5: Summary of electrochemical parameters obtained from fitting of Plots.

System CV: E vs. log ν CV: i vs. SQRT ν CV: Eh-pH plots CP: E(t) vs. log[1-(t/τ)1/2] plot
plot plot
Slope αn Slope D0 Region A/B Slope (S) αn Interce k0f, h
(10-8) (cm2/sec) Slope No. of pt (cm/s
(10-5) protons ec)
(10-8)
UO22+- 0.062 0.475 7.30 7.85 -0.091 ~ 1 (A) @ i= 6E-09 0.470 -0.272 1.76
PFAH -0.024 ~ 0 (B) S= 0.125

UO22+- 0.056 0.526 8.07 8.66 -0.093 ~ 1 (A) @ i= 4.5E- 0.500 -0.276 4.75
PAAH -0.015 ~ 0 (B) 08
S= 0.117

UO22+-3- 0.065 0.454 6.41 6.32 -0.093 ~ 1 (A) @ i= 3E-08 0.453 -0.296 5.04
PPAH -0.014 ~ 0 (B) S= 0.130

172
Table 5.6. Bond length, coordination number and disorder factor obtain by EXAFS fitting for
U(VI)-PCs at U L3-edge.

Pat Paramete PAA Paramete PFA Paramete 3-PPA

h r r r

U - edge U - edge U - edge

U- R (Å) 1.73±0.001 R (Å) 1.79±0.001 R (Å) 1.78±0.001
O1
N 2.54 ±0.024 N 2.0 ±0.016 N 2.10 ±0.11

σ2 0.0033±0.000 σ2 0.0015 σ2 0.0011±0.001

2 0
U- R (Å) 2.34±0.002 R (Å) 2.29±0.002 R (Å) 2.25±0.01
O2
N 5.08±0.048 N 2.0 ±0.016 N 2.10 ±0.11

σ2 0.0101±0.000 σ2 0.0155±0.000 σ2 0.0127±0.003

3 8 5
U- R (Å) 2.41±0.002 R (Å) 2.43±0.002
O3
N 3.0 ±0.024 N 3.05±0.15

σ2 0.001 σ2 0.0075±0.001
9
R-factor 0.0011 R-factor 0.016 R-factor 0.007

173
Table 5.7. The binding energy (B.E) and free energy of formation for all the three

uranyl(VI)-CP complexes in gaseous as well as aqueous phase.

Gaseous Phase Aqueous Phase

Complex B. E (kJ/mol) ∆G (kJ/mol) B. E (kJ/mol) ∆G (kJ/mol)

[UO2(PFAH)(H2O)3] -1581.540 -1617.263 -120.653 -156.407

[UO2(PAAH)(H2O)3] -1581.980 -1610.323 -149.353 -177.726

[UO2(3-PPAH)(H2O)3] -1539.842 -1555.298 -141.362 -156.849

Table 5.8. The calculate bond distances (in A0) between the uranium and the coordinating

atoms in stable optimized geometries of uranyl(VI)-CP complexes.

Complex U-O U-O (P) H- U-O U-O (H2O)

(UO2) bond (COO)

[UO2 (H2O)5] 1.748, 2.471, 2.470, 2.482,

1.748 2.486, 2.490 (2.480)

[UO2(PFAH)(H2O)3] 1.780, 2.222 2.528 2.266 2.538, 2.581, 2.583

1.790 (2.567)

[UO2(PAAH)(H2O)3] 1.780, 2.223 2.138 2.219 2.543, 2.585, 2.596

1.794 (2.575)

[UO2(3-PPAH)(H2O)3] 1.779, 2.243 2.039 2.213 2.542, 2.558, 2.602

1.795 (2.567)

174
Table 5.9: Stability constant, bond distances and partial charges of Uranyl(V)-CP complexes.

Systems Stability Bond distances Partial Charges

constant U-Oaxial Chelation U-O H-Oaxial on IMHB atoms
(logβ) (IMHB)
Uranyl(V)- 10.17±0.06 1.856 2.375(phospho) 1.902 Oaxial = -0.858
PFAH.3H2O 1.836 2.400(carboxy) H(-OH-Phos)= 0.521

Uranyl(V)- 10.55±0.11 1.859 2.383 (carboxy) 1.892 Oaxial = -0.862

PAAH.3H2O 1.830 2.362(phospho) H(-OH-Phos)= 0.523

Uranyl(V)-3- 11.28±0.09 1.850 2.390(phospho) 1.881 Oaxial = -0.861

PPAH.3H2O 1.830 2.298(carboxy) H(-OH-Phos)= 0.523

175
 Chapter 6

Speciation of Actinides in Deep eutectic solvents

Aim: Reserach related to advancem

advancement of economical novel green technology is paramount

necessity for the advancement of the nuclear fuel cycle. Within the freamework of “Green

chemistry” deep eutectic solvent (DES), represents an emerging class of environmental

benign and sustainable non-aqueous

aqueous media alternative to the conventional organic solvents

and ionic liquids in the 21st century. Owing to its unique physicochemical properties, DES

metal ion hijacker” for processing diverse kind of uranium (U)

can works as a potential “metal

(also americium)
um) matrices and “designer
“ solvent” for greening analysis of U in nuclear

material samples. In addition, it can be used as “promising

“ electrolyte” for oxidative redox

process of americium. The present chapter is divided in three subparts (a) direct sequest
sequesting,

speciation and analysis of U-matrices

matrices using Maline scaffolds (b) dissolution and probing

speciation of uranium oxides in new imidazolium based DESs, and (c) speciation of

americium in malonic acid based DES.

176
6.1. Introduction:

Nuclear energy, a mature technology and an attractive large-scale cleanest energy

source, is a viable option for global future energy needs because of its relatively low carbon
[1-2]
footprint . However, the prime concern of expanded use of nuclear energy are the

reprocessing and management of spent nuclear fuel (SNF) and high level waste (HLW) due
[33, 190]
to their long-term radiotoxicity and associated economic and environmental issues .

The irradiation of nuclear fuels in reactor, during electricity production, generates SNF which

contains large amounts of unused nuclear fuels, minor actinides and fission products.

Uranium (U) is primarily utilized as a fuel source for nuclear power generation and its

increasing demand as fuel material in nuclear technology activity evokes processing of metal

oxides present in naturally occurring ores as well as in spent nuclear fuel (SNF) for complete

utilization of its energy potential [33, 190-192]. Americium (241Am), a minor actinide and a major

contributor to the long-term radiotoxicity of HLW, significantly limits the storage capacity of
[193-194]
geologic repositories owing to heat production . In case of closed nuclear fuel cycle

scheme, the Am must be separated from lanthanides or curium before transmutation (i)

because its high-neutron cross sections would otherwise interrupt the fission efficiency of the

recycled fuel, and (ii) to facilitate radiologically safe fuel fabrication process [193-194].

In NFC, the current approaches of reprocessing fall into two major categories as
[34]
PUREX and pyrochemical processes . The complexities of both processes and resulting

technical challenges have opposed critically for their operation in reprocessing and demand
[35]
the development of alternative method . The first step in reprocessing involves the

dissolution of oxide fuels (mainly uranium). However, the dissolution of U matrices such as

oxides/salts/alloy is very difficult due to their poor solubility and high strength of the metal-
[39, 195-196]
oxide bond and it usually takes place in very concentrated nitric acid (~13M

HNO3). For quality assurance and nuclear forensics, the routine analysis of uranium containg

177
nuclear material samples, the sample dissolution procedure employs the time consuming
[37]
repetitive evaporation steps with hazardous concentrated acids (HNO3 and HF) . The

handling of these highly concentrated acids creates operational hurdles due to generation of

the large volume of harmful NO and NO2 gases and corrosive environment etc. Instead, if a

green dissolution is possible, it will be worthwhile to replace nitric acid in reprocessing of the

present and advanced nuclear fuels. In analysis of U, the conventional method routinely

employed for quantification of U in nuclear materials is redox titrimetry using

biamperometric endpoint detection which have several drawbacks viz. generation of

hazardous acid waste and the involvement of various metallic impurities (Cr, Fe, Ti, Ag, etc.)
[52]
. Another option for analysis of U is the electrode modification which is very complex,

expensive, tedious and time-consuming. It should be restricted in routine sample analysis.

Therefore, development of an alternate greening analysis methodology for U is higly

required. The Am separation from HLW is highly challenging due to its similar chemical and

physical properties compared to the lanthanides (Ln). Selective extraction of Am vs. Ln

through judicious ligand design is the mainstream approach for Am separation but this

approach requires multiple steps and can cause more down-stream complication due to ligand

degradation. Selective oxidation of Am(III) to its higher oxidation state is another approach
[193-194]
which could facilitate its separation from lanthanides/cm in nuclear waste streams .

Therefore, the development of electrochemical methodology for selective oxidation of Am to

its higher oxidation has become a recent research interest.

A holistic approach for the advancement of nuclear technology related to NFC

[68, 96]
activities is the usage of the concept of ‘‘green-chemistry’’ . Within the framework of

green chemistry the deep eutectic solvents (DESs) have emerged as a neoteric designer green

non-aqueous media alternative to the conventional organic solvents and ionic liquids in the

21st century [62-64]

with unique solvating potential and tuneable physicochemical properties.

178
 [197-199]
DESs have been applied to diverse field of research such as electrochemistry ,

metal/metal oxides processing [196, 200], catalysis [201]

, extraction/separation [202]
, and clean-up
[203]
of heavy metal . It will be innovative if this new chemical media i.e., DES can be

explored for the dissolution, analysis, extraction and recovery of actinides from their primary,

secondary sources, spent fuels or high-level nuclear wastes (HLW). Abbott et al. showed that
[200, 39]
malonic acid as HBD based DES viz., Maline is strongly acidic and its solvation
[200]
potential for metal oxides correlates well with that in aqueous HCl . Our interest lies in

NFC, it becomes appropriate to select the imidazolium cation as HBA since it is usually air
[204-205]
and moisture stable , fairly stable to radiolytic degradation and also its physical

properties such as density, surface tension, refractive index, etc. are not significantly affected

upon irradiation. Therefore, malonic acid as HBD and imidazolium cation as HBA are ideal

candidate for the preparation of DES and most suitable for the applications in NFC.

Literature survey implies the lack of direct sequestration of U from its solid matrices and the

greening analysis methodology for U. The present work aims to exploit Maline most

appropriately in different facets of NFC by acquiring the primitive chemical aspects on

dissolution, redox and molecular speciation by IR, TGA and UV-Vis absorption,

electrochemical and EXAFS methods respectively. Voltammetry methodology was

developed to obtain the analytical figures of merit for routine U analysis using Maline as

electrocatalytic media. Interaction of Uranyl with Maline was probed by luminescence, UV-

Vis absorption and calorimetry titration. The thermodynamic interaction parameters were

evaluated to understand the driving force and mechanistic of dissolution of uranium matrices

in Maline [206]. Molecular dynamics and DFT simulations were carried out to authenticate the

experimental observations and to provide the optimized structure, free energy and molecular

orbital (MO) diagram of U species with Maline. The use of DES as co-solvent for Am

separation is reported [71] however, no studies have been reported on the speciation of Am in

179
DES. The aim of the present study is to describe the speciation of Am in two DES containing

mainly oxygen atoms as functional moiety viz., Choline dihydrogen Citrate-Malonic acid

(CDHC-MA). Probing speciation of Am in DES is indispensable for the advancement of

[61, 207]
SESAME (SElective Separation of AMericium by Electrochemical means) and

SANEX (Selective ActiNide Extraction) processes [208] and for the growth of analytical tools

including coulometry and redox titration for Am analysis.

6.2. Experimental: the details discussed in chapter 2.

6.3. Results and Discussion. Described in following subparts (a) to (c)

(a) U in Maline

6.3.1. Direct Sequestration and Characterization: Maline has unusual solvation potential

which can been explained based on the hole or liquid crystal theory, binding theory and
[39, 45, 209]
presence of proton as oxide-binder . According to the hole theory, the preorganized

supramolecular structure of Maline forms a polymer-like matrix, and the metal solute can

dissolve into the space (or holes) of this molecular network. Following the binding theory, the

target metal solute incorporated in the Maline matrix through intermolecular

interaction/chelation of high-density carbonyl chelating group of malonic acid. The presence

of protons in Maline, acting as oxygen acceptor, supports dissolution through water forming

reaction with oxygen atoms of metal oxides. Therefore, in the present case, the choice of

Maline as solvating media for direct and quantitative sequestration of U matrices without any

additives. Eight U matrices: UO3, Uranyl nitrate (UN) UO2(NO3)2, UO2, U3O8, Rb2U(SO4)3,

U-metal, (U, Pu)O2 and U3Si2 and one PuO2 were dissolved using the Maline as solvating

media. The probable mechanism of the dissolution process of UO3 and related charge
[39-40, 46]
balances are given in Scheme S6.1 . The IR spectra (UO3 and UN), TGA data (UO3,

UN and UO2) and UV-visible spectra (UO3) were recorded and have delineated in Fig. 6.1 (a-

180
c). IR spectra [Fig. 6.1(a)] showed a peak near 920 cm-1 which is attributed to the stretching

frequency of [O=U=O]2+ moiety. TGA data curve [Fig. 6.1(b)] described two weight loss

region (R1A, R3) in the case of Maline while three weight loss region (R1B, R2, R3) in U

matrices dissolved Maline. This additional loss at R2 supports the dissolution process of U

matrices in Maline. The experimental and theoretical percentage loss in weight as a function

of temperature corresponding to blank Maline and U matrices dissolved Maline are shown in

Table S6.1 along with probable liberation of the various moiety. Region R1 and R3 were

assigned as decomposition of malonic acid (MA) and choline chloride (CC) moiety of Maline
[210]
with temperature respectively . The three losses R1, R2 and R3 in case of U matrices

dissolved in Maline can be assigned to loss due to choline, only H2O and H2O+HCl, and

malonate respectively. As malonic acid moiety is directly attached to UO22+ (scheme S6.1), it

is expected to get liberated at a higher temperature than choline moiety which is attached to

other end of malonic acid with very weak hydrogen bond interaction between chloride and

hydrogen atom. The region R2, observed in U matrices, may be due to the decomposition of

the equatorially attached moiety of U. In the case of UO3 dissolved Maline, the loss in region

R2 is low compared to UO2 and UN dissolved Maline, which can be due to loss of four H2O

(two from the equatorial position and other two from the solvent environment around UO22+).

In the case of UN and UO2 dissolved Maline, the loss in region R2 is due to the loss of

equatorially bonded two H2O and two HCl from the solvent. The UV-Visible absorption

peaks of species formed after the dissolution UO3 in Maline, blank Maline, and UO22+-

malonic acid complex in aqueous solution are given in Fig. 6.1(c), which reveals the

absorption peaks in the wavelength region 400-500 nm in UO3 dissolved Maline solution.

Comparison of absorption spectra of UO3 species in Maline with that of the uranium-malonic

acid complex at the same concentration of U in the aqueous medium indicates that the

absorption peaks in region 400-500 nm in UO3 dissolved Maline solution are due to the

181
complex species of uranyl [O=UVI=O]2+ with the malonic acid moiety of Maline. Regarding

U species in Maline, shift in absorption maxima wavelength (∆λmax), increase in absorbance

(∆Amax) with respect to that of the uranium-malonic acid complex in aqueous medium and

εmax (at λmax 424 nm) were evaluated to be 10 nm, 0.23 and 18.9 M-1cm-1 respectively.

6.3.2. Speciation studies: (i) Redox speciation by electrochemistry and In situ UV-vis

spectroelectrochemistry: The electrochemical potential window of MALINE was obtained

to be ~3.41 V. Representative cyclic voltammetry (CV) plots of redox-sensitive U matrices

viz. UO3, UN, UO2, Rb2U(SO4)3 (U std.), U-metal, U3Si2 and (U, Pu)O2 in Maline media in

potential sweep region from 1.5 V to -2.4 V were provided in Fig. 6.2(a-c). The CV of

Maline media specifies the absence of redox reaction to interfere with the U redox process in

Maline. CV of U matrices viz. UO3, UN, U std., U-metal and U3Si2 demonstrate two

successive reductive waves (peak 1 & 2) in Maline. The presence of two successive reductive

waves in CV was further corroborated by inspection of two reductive waves in their

corresponding more sensitive DPV plots [Fig. S6.1(a-c)]. Redox characteristics related to

reductive waves of U matrices in Maline were proclaimed in Table 6.1. In the case of UO2

dissolved Maline solution, the prominent reductive wave was observed at nearly -1.424 V in

the CV. However, its corresponding DPV specifies two reductive waves in which the first

reductive wave is small in peak current intensity than that of UO3 and lies in the same

potential region where the first reductive wave of UO3 exit. This implies that the nature of the

first reductive wave in DPV of UO2 might be the same as that of UO3 but the concentration of

oxidative species for the first reductive wave in the case of UO2 dissolved Maline solution is

small enough compared to that of UO3. To get the clarity in nature of reductive waves of UO2

in Maline, the CV and DPV on U3O8 dissolved Maline solution were performed [Fig. 6.2(a)

and Fig. S6.1(a)]. Being mix-valent oxide, the DPV of U3O8 designates three one-electron

transfer reductive waves which could be assigned as U(VI)-U(V), U(V)-U(IV) and U(IV)-

182
U(III). The first reductive wave in U3O8 attained with nearly the same peak potential and

current intensity to that of UO3 while the third reductive wave in U3O8 [DPV: Fig. S6.1(a)]

attained at potential (-1.423 V) where the dissolved UO2 species in Maline have its prominent

reductive wave (at -1.430 V). These findings reveal that the nature of oxidative species under

reduction in the first reductive wave in UO3, U3O8 and UO2 are nearly the same and further

suggests that the nature of oxidative species under reduction at -1.430 V in UO2 Maline

would be analogous to oxidative species under the third reductive wave of U3O8 at -1.423 V.

The UVIO22+ kind of species formed through oxidative dissolution of UO3 (Scheme S6.1) [40]

in Maline (described later), therefore, it is the main oxidative species to be reduced in the first

reductive event. However, due to the slow kinetics of oxidative dissolution of UO2 in Maline,

the concentration of UVIO22+ oxidative species is small which in turn reflects in small peak

current in the first reductive event in DPV and almost negligible in the CV of UO2 in Maline

[Fig. S6.1(a) DPV; Fig. 6.2(a) CV]. Though the kinetic of oxidative dissolution process in the

case of UO2 in Maline is slow, however, it has sufficient solubility through carbonyl

chelation of preorganized supramolecular scaffold of Maline. Hence the reductive peak in

UO2 species attained at -1.424 V is associated with the conversion of dissolved U(IV) species

in Maline to U(III) species. Fig. 6.2(c) and Fig. S6.1(c) exhibits the CV and DPV of PuO2

and (U, Pu)O2 in Maline respectively. As evident, the first reductive wave (peak 1) is

common in both PuO2 and (U, Pu)O2 [inset Fig. 6.2(c)] and is attributed due to the reduction

of dissolved Pu species in Maline. The second reductive wave (peak 2) obtained at -1.565 V

only in (U, Pu)O2 in CV, is further corroborated by the presence of reductive wave in

dissolved (U, Pu)O2 relative to PuO2 in Maline in DPV [Fig. S6.1(c)], is belonging to the

reduction of dissolved UO2 species of (U, Pu)O2. The dissolution of UO2 species of (U,

Pu)O2 was assumed to follow the same pattern as that was in the case of UO2 in Maline

(described above). The reductive waves (1 and 2) potential of UN, U Std., U-metal and U3Si2

183
in Maline [Fig. 6.2(b)] in their respective CV were found nearly in the same potential regions

where the UO3 keeps its peculiar reductive waves (1 and 2) respectively. This recommends

that the nature of species formed through the dissolution of UN, U Std., U-metal and U3Si2

matrices in Maline is analogous to that of UO3 in Maline. The effect of scan rates on their

peculiar reductive waves potential (Ep) and current (ip) were studied by CV and is

summarized in Fig. 6.2(d). As evident, in each U matrix, the cathodic shift in Ep and

enhancement in ip of their peculiar reductive waves with scan rates increment were observed.

The linear relationship was achieved in their corresponding ln|ip| vs. Ep-Ef and ip vs. √ν plots,

which are consistent with equation 2.34 and Randles-Sevcik equation 2.31 respectively,

approving the irreversibility and diffusion-controlled process of reductive waves in each U

matrix. For each U matrix, the values of αn and ko corresponding to their peculiar reductive

wave in Maline were evaluated from their respective slope and intercept of ln|ip| vs. Ep-Ef

plots respectively and are described in Table 6.1 along with the value of diffusion coefficient

(D0) calculated from their respective slope of ip vs √ν plots obtained by using the equation

2.31. Based on the values of αn, the two reductive waves in UO3, UN, U std., U-metal and

U3Si2 in terms of electron transfer process are described as U(VI)-U(V) conversion (Peak 1)

and U(V)-U(IV) conversion (Peak 2) and hence corroborating that these U matrices are

exhibiting two consecutive single electron transfer (SET) reduction mechanism (Scheme 6.1).

In the case of UO2 and (U, Pu)O2 the reductive wave is U(IV)-U(III) conversion. To validate

the electrochemical measurements by CV (i.e. SET reduction mechanism) and to acquire the

absorption spectral features of reduced species of UO3 in Maline, the insitu UV-vis

spectroelectrochemical experiment were performed [Fig. 6.3(i-iii)] with decreasing

potentials. Fig. 6.3(i) implies the continuous decrease in absorbance at 412, 424 and 438 nm,

which are concomitant with the absorbance bands of U(VI) species (formed through

dissolution of UO3) in Maline, with decreasing potentials from no applied potential (NO V)

184
to -2.25 V due to diminution in its concentration through reduction process in its lower

oxidation states. On the other side, the growth of new absorbance peaks was observed at 512,

541, 572 and 843 nm through reduction steps [Fig. 6.3(ii-iii)]. Importantly, the incessant

increasing intensity of absorbance peaks was found at 512, 541, 572 nm but the absorbance

peak intensity at 843 nm increased initially and then decreased with decreasing potentials

[Fig. 6.3(iii)]. This kind of absorbance intensity variation at 843 nm with decreasing

potentials is reminiscent of U(V) species formation in Maline by fast kinetic of first reductive

wave upto potential -0.678 V afterwards the kinetic of second reductive wave became faster

compare to first, resulting in lowering in the concentration of U(V) species and thus

absorbance intensity at 843 nm. The incessant increase in absorbance peaks at 512, 541, and

572 nm are assigned for U(IV) species formation in Maline from both reduction steps (1 and

2) with decreasing potentials. The observed position of absorbance peaks related to U(V) and

U(IV) species in Maline are in agreement with the literature reports [129, 131, 180]. Interestingly,
[116-118]
U(V) species is quite stable and its disproportionation reaction was not observed in

Maline.

The electrochemistry of U in aqueous solvents has been widely studied earlier [98, 116-
118.148, 179-180, 211-212]
and it has been reported that the redox potential of U(VI)/U(V) couple
[98, 179, 211]
was obtained approximately at -0.250 V on GC and Pt electrode while nearly at -
[98, 179, 211]
0.2 V on Hg as working electrode . Moreover, the reported value of the diffusion

coefficient was in the order of ~ 10-6 cm2/sec [98, 179, 211]. Compare to the aqueous solvent, the

redox potential and diffusion coefficient of U in Maline deviates significantly [Table 6.1] [197-
198, 213]
. This deviation could be described in term of solvation mechanism viz. solvent

reorganization, associated free energy changes and speciation effect. The diffusing U species

in Maline media are in concentrated ionic solution thus ion-ion interactions in this media is

quite momentous and hence cannot fit into the model of non-interacting solvents. According

185
 [214]
to “hole theory”, used by Abbott et al. to elucidate the diffusion of ions in DES, ionic

transport occurs only when the size of diffusing ions matches the holes within the solvent

structure. For U species, the solvation mechanism in Maline is different from that observed in

the aqueous solvent. In aqueous solvent, Marcus theory on electron transfer processes

proposed the reorganization of solvents dipoles [213]. In Maline, its constituents comprising of

hydrogen-bonded anionic complex and a bulky choline cation. The solvent reorganization in

Maline arises by the ionic translation which is quite different from the solvent dipole

reorientation in the aqueous solvent. Therefore, in Maline, the self-diffusion of

ions/molecules play an important role in the reorganization process and the same has been

evaluated by molecular dynamics simulation [described later] in the present studies. The

deviation in the redox potential of U in Maline compare to aqueous solvent is expected due to

the difference in the solvent reorganization mechanism in Maline and the aqueous solvent.
[213]
The solvation structure model in two different solvents has portrayed in Scheme S6.2 .

The redox reaction is accompanied by solvent reorganizations producing entropy/enthalpy

changes and hence the change in free energy [∆G°; ∆G° = -nF(∆E°)] associated with a redox

reaction. Therefore the change in ∆G° associated with a redox reaction is affected by the

solvation structure of U species in the solvent. The shift in redox potential depends on the

extent of the solvent reorganization. The extent of solvent reorganization depends on the

ability of the oxidized/reduced species to make/break the solvation structure. A redox

reaction in the aqueous medium often disrupts the highly ordered solvation structure of water

molecules (Scheme S6.2), therefore, leading to drastic changes in entropy through solvation

of U species in the aqueous medium. In contrast to aqueous solvent, Maline has a much less

ordered structure (Scheme S6.2) therefore no preferential solvation of the oxidized/reduced

redox species leading to no significant changes in entropy on oxidation/reduction. Hence the

value of free energy changes (∆G°) related to redox reaction of U species occurring in Maline

186
is significantly lower. Furthermore, the speciation effect is also an important contributing

factor for change in electrochemical properties of U species in Maline compared to aqueous

solvent due to the presence of highly coordinating functionalities as chloride and malonic

acid within the supramolecular scaffold of Maline.

(ii) Molecular speciation by EXAFS: In aqueous solvent the chemistry of H+ and OH-

dominate the species formed in solution conversely in the case of Maline, there is

coordination competitions between chloride anion (Cl-), HBD malonic acid (MA) and H2O

for binding with U(VI) (UO22+) during the dissolution process. The coordination competitions

and structural analysis of formed species through the dissolution of UO3 in Maline have been

revealed by EXAFS spectroscopy. The normalised XANES spectrum of UO3 dissolved

Maline solution (U sample) at U L3 edge is shown in Fig. 6.4(i) along with that of UO2CO3

standards. XANES spectra indicate (VI) oxidation state of U in the sample and corroborate

the absorption spectra obtained in UV-Visible spectroscopy is due to the formation of U(VI)

(oxo) species (UO22+) in Maline through dissolution. Three spectral features characteristic of

the U bond are denoted as A, B and C in the XANES spectrum. The relative position of all

three features is related to the U-Oeq and U-Oax bond lengths and their coordination number.

The axial oxygens are responsible for peak B and equatorial oxygens are responsible for peak

C. The exact peak position of all three locations is obtained by the peak fitting method, where

an arctan function is used for absorption jump and three Gaussian functions are used for peak

A, B and C. The separation between peak A and B is 9.45 eV for the U sample slightly lower

compared to UO2CO3 (9.96 eV), which indicates longer U-Oax bond for our sample. Also, the

distance between peak A and C is 38.99 eV for the U sample and 36.18 eV for UO2CO3,

which indicates slightly longer U-Oeq bonds. The χ ( R ) versus R plots, generated using

Fourier transform of µ (E ) versus E spectra following the methodology described in equation

2.16 to 2.18, are shown in Fig. 6.4(ii) at the U L3 edge. A k range of 3-11 Å-1 has been used

187
for Fourier transform. Based on the XANES input, the theoretical spectra are generated for

the U structure. The best fit results are shown in Table 6.2. The first peak at 1.4 Å is the

contribution of two oxygen atoms from the axial position at 1.80 Å, confirming uranyl kind

of species [O=U=O]2+ formation via dissolution. The second coordination peak at 2.11 Å is

fitted using the two oxygen coordination shells at 2.52 Å and 2.55 Å with four and two

oxygen atoms respectively. With the HBD malonic acid component of Maline as the

chelating ligand, the existence of two dissimilar types of oxygens viz. four and two in the

primary coordination shell of U species are associated with coordination of two malonic acid

moiety of Maline through carbonyl oxygens and two H2O molecules respectively. Despite

high Cl- concentration, no U(VI)-Cl bond at distance ~ 2.74 Å [215] was observed in the U(VI)

primary coordination shell. This specifies that U(VI) exhibits exceptional coordination with

malonic acid (HBD of Maline) and H2O after the dissolution of UO3 in Maline and the

stoichiometry of species would be [UVIO2(MA)2(H2O)2]2+. The coordination of H2O instead

of Cl- in the primary coordination shell of U(VI) was further verified by TGA data of UO3,

which implies the wt% loss [Table S6.1] due to the equatorial attached molecule is 8% which

is corresponding to the loss of two H2O molecules from the equatorial position of U and two

from the solvent environment and hence authenticating the equatorial attachment of two H2O

in the primary coordination shell of U(VI) in Maline.

6.3.3. Molecular dynamics (MD) and Density functional theory (DFT) simulations:

Initially, the bulk phase of DES (molar mixture of choline chloride and malonic acid in ratio

1:2 i.e. 500:1000) (equation 2.37) was equilibrated in NPT ensemble followed by 50 ns

production run at 298.153 K temperature and 1 bar pressure in dry condition and with 20%

water. The calculated density was found to be 1.196 gm/cc and 1.188 gm/cc for dry and

water-saturated (20%) pure DES respectively, which are in excellent agreement with the
[216]
experimental results of 1.231 gm/cc and 1.211 gm/cc respectively . The equilibrated

188
structure of the Maline DES system containing uranyl ion in the presence of water molecules

is displayed in Fig. 6.5(a). The U-Cl bond distance and U-O(water) calculated from the peak

position of the radial distribution function (RDF) [Fig. S6.2(a-b)] are 2.85 Å and 2.55 Å

respectively. The U-O(water) distance matches well with that assessed experimentally by

EXAFS. The diffusion coefficient (D0) of U in Maline was also calculated from mean square

displacement (equation 2.38). The calculated value of diffusion coefficient, 2.8x10-8 cm2/sec,

was found to be in good agreement with that obtained experimentally by CV [Table S6.1].

Using DFT simulation the structure of U in Maline has been optimized at the M06-2X/TZVP

level of theory and is displayed in Fig. 6.5(b). After obtaining a reasonable structure, next, we

deal with the thermodynamic function to evaluate the stability of the metal ion-ligand

complex. The Gibbs free energy of the complex in the gas phase was evaluated at the M06-

2X level of theory and found to be -270.3 kcal/mol. Moreover, the binding character of the

complex of UO22+ ion with MA was studied by evaluating the energy levels of MOs at the

B3LYP/TZ2P/ZORA level of theory [217-218]. The MO diagram of LUMO, LUMO+1, HOMO

and HOMO-1 of the metal-ligand bonding for [UO2-(MA)2-(H2O)2]2+ complex (isosurface

value of 0.017 a.u. was used) is given in Fig. 6.5(c). The calculation of HB numbers against

time for pure Maline DES and in the presence of water shows that the average number of

hydrogen bonds per malonic acid molecule was found to be 0.20 and 0.18, 0.16 and 0.15 in

pure DES and in the presence of with water, respectively. It has been seen that the number of

H-bonds is decreased due to the addition of water however with more dilution (as from 10%

to 20%) there is no significant decrease in the number of hydrogen bonds. This is attributed

due to the unique hydrogen bonds during a short trajectory in Maline and hence it has a large

number of hydrogen bonding interaction and also the hydrogen bonds are present for longer

times [219]. This governs the interaction of U with Maline in the aqueous phase.

189
6.3.4. Interaction of Uranyl with Maline in aqueous phase by Luminescence and

Solution Thermodynamic Studies: Luminescence spectra of UO22+ in diluted Maline were

measured by successive addition of Maline in the pure aqueous solution of UO22+ and have

been shown in Fig. 6.6(a). As evident from the figure, the UO22+ peaks intensity showing the

quenching effect with the increasing Maline concentration. The comparison study of

quenching strength of Maline and malonic acid on the luminescence intensity of UO22+ was

also carried out at the same concentration and presented in Fig. 6.6(b). The results indicate

that Maline is a better luminescence quencher than malonic acid in the aqueous phase.

Therefore, this study affirms that the diluted Maline does not resemble as one of its

constituent malonic acid and could be recognized as an aqueous chelator (different from

Malonic acid) for Uranyl.

The thermodynamic stability and energetics of interaction provide crucial inputs to

understand the basic chemistry behind the dissolution and then the affinity of Uranyl (UO22+)

with the Maline. In the present case, the interaction of Uranyl with Maline was probed with

absorption spectrophotometry and isothermal titration calorimetry. The absorption spectra

show a redshift with increased intensity [Fig. 6.6(c)] on the addition of Maline in Uranyl

solution. The absorption data were fitted by using HypSpec programming to determine the

interaction strength (as log K) and to deconvolute the spectra profile to find out the

absorption profile for Uranyl and UO22+-Maline DES system [Fig. 6.6(d)] separately. The

free Uranyl ion maxima (λmax) is at 414 nm, while on interaction with DES, it was shifted to

421 nm; while the molar absorbance (ε) is changed from 7.54 mol*lit*cm-1 in free Uranyl ion

to 20.54 mol*lit*cm-1 in UO22+-Maline DES system. The thermodynamic stability (log K) for

the interaction was found to be 1.20 ± 0.01 and is relatively higher than the complexation

constants of Uranyl ion with most of the inorganic anions such as chloride, perchlorate and

nitrate. This could be attributed to the thermodynamically favourable dissolution of the

190
Uranyl salts in the Maline medium and also the significant interaction of Uranyl with Maline.

The incremental addition of Maline to aqueous Uranyl nitrate solution results in thermogram

as shown in Fig. 6.6(e), which on integration would provide the heat of interaction at each

step of addition. The cumulative heat released [Fig. 6.6(f)] in the process was analysed to

calculate the enthalpy of the interaction process. The interaction of UO22+ with Maline was

found to be endothermic (∆H = 18.3 ± 0.6 kJ/mol) and is purely an entropy (∆S = 84 ± 2

J/K/mol) driven.

6.3.5. Uranium Analysis methodology: In the present case, the analysis methodology was

developed based on U sample digestion in Maline followed by Voltammetry detection of U

for quality control of nuclear fuels, nuclear material accounting and nuclear forensic

prospects. The differential pulse voltammograms were recorded with increasing

concentration of UO3 in Maline as shown in Fig. 6.7(a). The figure shows the proportional

relationship between the response peak current (ip) and added conc. of UO3. The calibration

plot [Fig. 6.7(b)] specifies the linear relationship between response peak current (ip) and

added conc. of UO3. The sensitivity, detection limit, limit of detection (LOD) and

quantification (LOQ) of calibration plot were evaluated to be 0.834 (slope of log ip vs. log

conc. U plot), (1.103±0.022)×10-2 mg/ml, 0.079×10-2 mg/ml and 0.264×10-2 mg/ml

respectively. For the present methodology, the precision, accuracy and method validation

were assessed by analysing three U samples by using the calibration plot and results were

described in Table 6.3, which were further verified by other techniques viz. EDXRF and D.C.

Arc AES. The precision and accuracy of the present methodology estimated to be 0.140%

(RSD) and 0.218% respectively [Table 6.3]. Moreover, the determined concentration of U

from the present methodology is close to that of other techniques. Repeatability and

reproducibility of present methodology were checked by intraday and interday successive

determination of U sample and corresponding RSD of precise peak currents were found to be

191
1% and 0.92%. Fig. 6.7(c), infers no interference of U reductive wave peak with other

potentially interfering metal ions (Fe, Cr, Eu, Zn, Mg, Cd, Co, Ce and Ni). Furthermore,

higher selectivity for U over other metal ions by Maline was evident from Fig. 6.7(d). The

precision (0.140%) of the present U analysis methodology is better than that of (0.2%) the

Biamperometry method [52].

Related to the green aspects of our developed methodology, we have evaluated the
[96]
green chemistry metrics (using equation 2.49 to 2.51) of the present developed

methodology and previous method which is based on hazardous acidic/additives dissolution

of uranium matrices and their analysis by biamperometry [scheme S6.3(a-b)]. Their

respective green chemistry metrics have been given in Table 6.4. We have discussed the E-

factor, atom economy, reaction mass efficiency, mass intensity, quantifiable energy and

chemical consumption, and steps involved in the present developed methodology and
[220]
previous method in table 6.4. As evident from table, within the framework of green and
[221]
sustainable chemistry the developed methodology, in the present studies, indicates a

holistic approach which: (1) is cost wise economical as well as step and reagent economical

(2) uses green and sustainable Maline natural deep eutectic solvent for sequestering and

analysis of uranium matrices (3) does not generate any hazardous waste (4) has no adverse

effect on working human and environment (5) has no energy and efficiency sacrifice.

Therefore, the present methodology shows a significant advancement in terms of sustainable

chemistry and provides a new “greener and sustainable approach” which replaces the usage

of hazardous acids as well as additives during the dissolution of uranium matrices and further

eliminates the use of hazardous reagents [acids, oxidant and reductant (use of stoichiometric

amounts of oxidants or reductants inevitably leads to some hazardous waste, posing

environmental concerns] and tedious and time-consuming electrode modification steps

throughout analysis of uranium by biamperometry and electrode modification process

192
 [220]
respectively. The present methodology follows the principles of green chemistry and
[222]
green analytical chemistry and denotes a suitable replacement for the hazardous acidic

processing of U samples followed by biamperometry or modified electrode analysis.

(b) U in Imidazolium cation based DESs

6.3.6. Characterizations

6.3.6.1 Physical properties of imidazolium-based DES: For application of the present new

DES for dissolution, redox chemistry and electrochemical processing of uranium oxides led

us to generate reliable data on their physicochemical properties.

Density: The density of both DES was measured in a temperature range from 10 to 85 °C and

at atmospheric pressure [Fig. 6.8 (a)]. It was observed that the densities of DES 1 and 2

decrease linearly over the studied temperature interval (equation 6.1). The density of DES 1

was observed to be slightly lower than that of DES 2. It is expected that the substitution of

the CH2 (malonic acid) atom by a heavier atom, i.e., an O atom (in diglycolic acid), results in

a slight increase in density in the case of DES 2.

Õ
è <3Óä ? = g + ~ × \(é) (6.1)

Where ρ is the density in g/cm3, T is the temperature in K, and a and b are adjustable

parameters.

Viscosity: The viscosities of the selected DES were measured in a temperature range from 35

to 60 °C and at atmospheric pressure [Fig. 6.8 (b)]. The fitting parameters A (mPa·s), B (K),

and x0 (K) are shown in Fig. 6.8(b). From this figure, it can be observed that, like most ILs

and DES, the viscosity-temperature profile can be satisfactorily fitted to the Vogel-Fulcher-

Tamman (VFT) equation 6.2. The viscosity of DES 1 (604 mPa.Sec at 298 K) is lower than

193
 [216,
that reported for Choline Chloride: Malonic acid (1:1) DES (1389 mPa.Sec at 298.15 K)
223]
. This indicates that DES 1 may have some ease of handling-advantage over Choline

Chloride: Malonic acid (1:1) DES.

ë
ê = : × exp ( # H
) (6.2)

Where A (mPa·s), B (K), and x0 (K) are the fitting parameters.

Melting point: The thermograms [Fig. 6.8(c)] show the melting point of C10minBr, Malonic

acid and DGA as 21oC, 133.4oC and 140.3oC as against the reported values of 16oC, 135-

137oC and 140-144oC, respectively [224]. The melting point of DES 1 and DES 2 were found

to be -27.7°C and -8.7°C respectively. The peak found near 150°C is due to loss of H2O and

HBr, which is in agreement with the TGA data given in Table 6.5.

6.3.6.2 Karl Fischer Titrations: The water content of the neat DES was evaluated to be

15.35% and 14.8% in DES 1 and 2 respectively.

6.3.6.3 IR spectra: Fig. 6.9(a) represented IR spectra for UO3 (red line) and UO2 (blue line)

dissolved DES along with pure DES (black line). The intensive IR bands appearing at 920

cm-1 in both UO3 dissolved DES (red line) was assigned to the antisymmetric stretching

modes of UO22+ [inset Fig. 6.9(a)]. However, interestingly, the IR bands above were found to

be absent in the case of UO2 dissolved DES (1 and 2). This showed that through the

dissolution process, probably, only UO3 got converted into a species that gave UO22+ in
[40]
solution through the oxidative dissolution process , but UO2 did not show this kind of

conversion and probably remained as U(IV) in both DES. This might be due to the absence or

the slow kinetics of oxidative dissolution of UO2 in DES 1 and 2.

6.3.6.4 TGA-DSC data: The weight percentage loss versus temperature and their

corresponding derivative plots of both pure DES and uranium oxides [UO3 and UO2]

dissolved DES are shown in Fig. 6.9 (c-d). The wt % loss vs. temperature plots indicated a

loss in two ranges of temperatures, designated as R1 and R2. The observed and calculated wt

194
% loss in both regions R1 and R2, for both pure DES and uranium oxides dissolved DES, are

given in Table 6.5. The molecules liberated during the loss are also indicated in Table 6.5.

The calculated and the observed loss in weight were found to be agreeing with each other.

The water content of DES 1 and DES 2 was found to be 15.35% and 14.8%, respectively.

This implies the association of 8.5 molecules of water for 2 building entities (2 C10mimBr+ 2

Malonic acid) of DES 1 and 8 molecules of water for 1.5 building entities (1.5 C10mimBr+

1.5 Malonic acid) of DES 2. It is also known from the IR spectra that UO3 dissolved in DES

has a UO22+ group, whereas it exists as U4+ in UO2 dissolved DES. This highly charged

uranium is associated with 4 Br- to neutralise the charge. The percentage loss in the R1

region for UO3 dissolved DES 1 is less as fewer number of HBr is liberated as compared to

UO2 dissolved DES 1. In the case of UO2 dissolved DES 1, four molecules of HBr were lost

in addition to the loss of accompanying 8.5 H2O. In the case of DES 2, the number of

associated molecules of water per molecular unit of DES was calculated to be 11. The

number of water molecules liberated from neat DES 2, UO3 dissolved DES 2 and UO2

dissolved DES 2 was found to be 5, 4 and 11, respectively in region R1. There is no loss of

HBr in the case of DES 2 in region R1, which could be due to the much stronger binding of

Br in DES 2. In contrast, HBr was lost along with other moieties in the region R2 at high

temperature in DES 2 as well as uranium oxide dissolved DES 2. The % loss of water in DES

2 is low compared to DES 1 in region R1. This indicated the higher stabilization of both

uranium oxides dissolved in DES 2 as compared to that in DES 1. The 60mg of uranium

oxides were dissolved in 1ml of DES 1 and DES 2 separately and was used in the TG-DSC

experiment. The weight loss percentage for uranium [UO3 and UO2] dissolved in DES 2 was

calculated to be 14 and 81 % in regions R1 and R2, respectively, assuming UO2 as the final

residue left behind. These values were not agreeing with the experimental values, which

indicated the solubilization of uranium oxide in DES.

195
6.3.6.5 UV-Visible spectral data: UV-Visible absorption spectra were recorded for the

solution of dissolved UO3 in DES [Fig. 6.9(b) (and inset Figures)] to understand the

mechanism of the dissolution process. For comparison, Fig. 6.9(b) included the spectra of

aqueous uranyl ion (in 1 M perchloric acid) in the presence of a higher concentration of

malonic acid (2.72 M) and diglycolic acids. It is clear from the figure that the spectral

features of UO3 [which converted to uranyl (UO22+) after dissolution in DES 1 and 2] in both

the solvents were different from that of uranyl in malonic acid and diglycolic acid in aqueous

solution [1 M HClO4] showing that the species in two cases were not the same. Importantly,

the values of molar absorption coefficient of uranyl in DES 1 (εmax=45) and DES 2 (εmax=44)

were found to be higher than those of the uranyl-malonic (εmax=6) or digcolyic acid (εmax=7)

complexes in aqueous.

6.3.7. Dissolution Mechanism: Based on the above characterizations, the plausible

dissolution steps in the case of UO3 in DES 1 are described in Scheme 6.2, leading to an

interesting finding related to the formation of uranium oxo (O=U=O)2+ species through
[40]
oxidative dissolution procedure . It may be true to propose that the dissolution steps of

UO3 in DES 2 will similarly follow the scheme. In contrast, in the case of UO2, the oxidative

dissolution process seems to be absent or slow in either of DES 1 and 2 since the probability

of formation of uranium oxo species according to scheme 6.2 is less.

6.3.8. Redox Speciation of uranium oxides dissolved in DES

6.3.8.1. Potential window and redox behaviour of the DES 1 and 2

The electrochemical potential window of the DES was of interest and was given in

Fig. 6.9(e) along with that of the aqueous phase. It can be seen from the figure that DES 1 has

a potential window of 2.79 V while DES 2 has 2.66 V. The observed potential windows for

DES 1 and 2 were larger than those of aqueous solvent (~ 2 V). Also, both DES have an

extended cathodic potential range as compared to that of the aqueous phase and hence these

196
DES (1 and 2) are amenable and appropriate for reductive electrochemical prospects. It can

also be seen that the neat DES 1 has two reductive peaks, of its own, at 0.481 V and -1.052 V

respectively, while the DES 2 has one reductive peak at 0.373 V. These peaks did not

disappear even on long time flushing with N2 gas implying that both DES are redox-active. It

was expected that the reductive peaks observed in both neat DES might be due to the
[225-226]
reduction of imidazolium cation moiety of C10mimBr. In previous studies , the

identification of reduction products of imidazolium cation (i.e., C10mim+) has been reported

and accordingly its reduction products are N-heterocyclic carbene and subsequent dimmers.

To simulate the reduction products of DES 1 and 2 in the present case, the cyclic

voltammetry studies were performed on their reduction with varying scan rates, which infers

two SET (single electron transfer) steps in the case of DES 1 while one SET in DES 2

(scheme S6.4). In the case of DES 2, where only one reduction peak is observed is attributed

to the formation of a single product, i.e., N-heterocyclic carbine [225-226]. The DGA in DES 2,

may stabilise this due to the presence of ‘O’ in the DGA. In the case of DES 1, two SET

(single electron transfer) processes may take place. Unlike in the DES 2 case, malonic acid in

DES 1 does not have any coordinating atom in between. This makes it proceed to the second

reduction step, resulting in two reduction peaks in DES 1.

6.3.8.2. Voltammograms

The voltammetric studies, mainly on two uranium oxides UO3 and UO2 in DES

1 and 2 were carried out. In addition, the voltammetric studies on mix-valent (VI and
[227]
IV at the ratio of 2:1) oxide of uranium viz. U3O8 was performed to corroborate

the electrochemical outcomes of UO3 and UO2 and to get an insight into the

mechanistic aspects of the dissolution procedure of UO3 and UO2 in both DES 1 and 2.

Fig. 6.10(a-b) shows the cyclic (CV) and differential Pulse (DPV) voltammetry plots

of solutions containing uranium oxides (UVIO3 and UIVO2) dissolved in DES 1 and that

197
of pure DES (without any uranium dissolved) in the potential region from 1.2 to -2.3

V. It can be seen from Fig. 6.10(a), two reductive peaks in case of UO3 at -0.305 V

(Peak I) and -1.106 V (peaks II), one reductive peak at -0.968 V in case of UO2 are

present. It also includes the data for U3O8, which has two reductive peaks (-0.295 V

and -1.150 V respectively) in DES 1. The DPV (more sensitive than CV) of UO3 and

UO2 in DES 1 was also recorded and is given in Fig. 6.10(b) which shows the trend of

the same two and one reductive peaks, respectively as acquired in their respective CV

and thus corroborate the CV results. Similarly, the CV plots of UO3 and UO2 in DES 2

are shown in Fig. 6.10(c) which describe two reductive peaks (I at -0.355 V and II at -

1.156 V) and one reductive peak (III at -1.327 V) for UO3 and UO2, respectively. The

corresponding DPV plots of uranium oxides in DES 2 are shown in Fig. 6.10(d) which

authenticates the same reductive trends as were seen in their CV plots. The peak (Ep)

and formal potentials (Ef) of reductive peaks of UO3 and UO2 in both DES 1 and 2

were provided in Table 6.6.

Another notable feature in Fig. 6.10(a) and 10(c) is the absence of oxidative peaks

in the reverse potential scan in the CV plots, suggesting the irreversibility of dissolved

species of UO3 and UO2 in both DES 1 and 2. This irreversibility in the reductive

peaks of UO3 in both DES was expected due to sluggish electron transfer kinetics

because of the required U-O bond-breaking chemical reaction after the electron

transfer steps. This reveals the formation of uranium oxo species, i.e., UO22+ through

the oxidative dissolution procedure of UO3 in both DES 1 and 2 (Scheme 6.2). On the

other hand, in CV and DPV of UO2 in DES 1, no reductive peak was observed in the

first peak potential region of UO3. This suggests that the similar oxidative dissolution

process found in UO3 was absent in UO2 in DES 1. This result is also supported by the

IR spectra of dissolved UO2 species in DES 1 [Fig. 6.9(a)] indicating the absence of

198
IR peak at 920 cm-1 of UO22+. Meanwhile, Nockemann et al. [228-229]
reported the

dissolution of uranium compounds in ionic liquid has taken place by coordination of

the functional moiety of ionic liquid with uranium ion. Following a similar concept, it

can be proposed in our case too, that the dissolution of UO2 could be through the

chelation of functional groups viz. malonic acid and bromide ion of DES 1. Now in

the case of U3O8 [Fig. 6.10(a-b)], two reductive peaks in CV and DPV plots were

observed in the same potential regions as of UO3 which reinforces our idea that U3O8

in DES 1 too follows the oxidative dissolution process similar to UO3 and the

formation of similar kinds of species i.e., UO22+. In the case of DES 2, the DPV of

UO2 [Fig. 6.10(d)] reveals the reductive peak I (at -0.162 V) with low current intensity

in the same potential region where the UO3 has its first reductive peak (-0.169 V).

However, it is to be noted that, unlike the DPV, the CV of UO2 did not show any

reductive peak in that potential region [Fig. 6.10(c)]. The above small peak at -0.162 V

in DPV is related to the redox activity of dissolved species of UO2 in DES 2 and is

probably because of more sensitivity of DPV than CV. Further, the appearance of

small current intensity [Fig. 6.10(d)] suggests the slow kinetics of oxidative

dissolution of UO2 as compared to that of UO3 in DES 2. However, based on the CV

plot [Fig. 6.10(c)], the dissolution through DGA chelation was assumed as a major

conversion process in the case of UO2 in DES 2, which was corroborated by the DPV

plot of U3O8 in DES 2. The DPV of U3O8 in DES 2 [Fig. 6.10(d)], indicates three

reductive peaks at -0.171 V (I), -0.898 V (II) and -1.232 V (III). Since U3O8 is a
[227]
stoichiometric mixture of two UO3 and one UO2 , it can be noted as follows: Out

of the three reductive peaks, the two reductive peaks of U3O8 occurred at nearly the

same respective potentials of reduction of UO3 (I and II) and the third reductive peak

of U3O8 occurred at the same potential as that of one single reductive peak of UO2

199
(III). Hence, the dissolution process of U3O8 in DES 2 could be the result of both

dissolution mechanisms as envisaged in UO3 and UO2, i.e., in addition to the oxidative

dissolution, there is a possibility of simultaneous dissolution through coordination of

functional groups (viz. DGA and Br-) of DES 2. Therefore, the finding of reductive

peaks I, II and III in the case of U3O8 validates two different mechanisms of

dissolution processes of UO3 and UO2 in DES 2.

Here, a special mention has to be made of a challenge in the identification of

reductive peak of blank DES 1 and that of UO3 (peak II) as they occur at almost

overlapping potentials (blank DES: at -0.948 V in DPV and at -1.016 V in CV vs. -

0.902 V in DPV and at -1.106 CV) [Fig. 6.10(a-b)] which created ambiguity during

the identification of these reductive peaks. This was resolved by recording the DPV

plots with increasing concentration of UO3 in DES 1. It also gave a value addition to

this exercise which established a method for the analytical determination of uranium

concentration in DES, by respective calibration plots. These DPV plots clearly

indicated the enhancement in response peak current (ip) of reductive peaks I and II of

UO3 with increasing UO3 concentration in DES 1 [Fig. 6.11(a-b)]. The linear

relationship (Adj. R-Square =0.997 and 0.991 and slope= 2.131x10-6 and 3.962x10-6

A/mg.ml-1 for reductive peak I and II respectively) between the response peak currents

(ip) and concentration of UO3 was observed for both reductive peaks [Fig. 6.11(c-d)].

The change in potential (Ep) of reductive peaks I and II with varying concentration of

UO3 is also examined and two linear region with different slopes was observed [Fig.

6.11(e)]. At point A, the reductive species is blank DES 1 itself, whereas the region

BC is related to the reductive peak I and II of UO3 species in DES 1. Therefore, the

findings of Fig. 6.11(a-e) clearly tell us that the reductive peaks I and II corresponding

to UO3 in DES 1 in CV and DPV [Fig. 6.10(a-b)] are indeed due to the reduction of

200
uranium species in DES 1. Instead of analyzing separately UO3 and UO2 in DES 2, it

was simplified with a similar exercise for U3O8 in DES 2 (because U3O8 gives three

peaks pertaining to both UO3 and UO2) and the results are given in Fig. 6.12(a-b).

Similar to the above case of UO3 a linear relationship was obtained [Fig. 6.12(b)]

between response peak current (ip) and concentration of U3O8 corresponding to the

reductive peaks I to III. The slopes of ip vs. concentration of U3O8 plots were found to

be 1.44x10-6, 7.32x10-7 and 9.03x10-7 A/mg.ml-1 for reductive peaks I, II, and III,

respectively.

6.3.8.3. Validation of Calibration plots by redox-titrimetric biamperometry

The calibration plots [Fig. 6.11(c) and Fig. 6.12(b) (i)] related to uranium

species in both DES were validated by analyzing the unknown concentration of

uranium oxide sample with the present voltammetry method and with another

electroanalytical method viz. biamperometry end point detection based on redox-

[52]
titrimetry . The concentration of unknown uranium oxide samples in DES 1 and 2

was evaluated from their respective calibration plots [Fig. 6.11(c) and Fig. 6.12(b) (i)]

and are given in Table 6.7. Also, the concentration of uranium oxide samples analyzed

by the biamperometry method is reported in Table 6.7 and found to agree with those

determined by the present calibration method.

6.3.8.4. Scan rate variation and determination of transport and kinetic parameters

The scan rate variation was studied for solutions of UO3 and UO2 dissolved in both

DES to find out the diffusion coefficient (D0) and kinetic parameters (k0, αn). The CV

plots of reductive peaks of uranium oxides (UO3 and UO2) in both DES at various

scan rates are recorded and are shown in Fig. 6.13(i-ii) for DES 1. The electrochemical

equation 6.3 was applied to calculate αn at each scan rate. The value of αn is < 0.5 for

UO3 and UO2 in both DES. Fig. 6.13(i-ii) demonstrates the shift in peak potential (Ep)

201
and reductive peak current (ip) enhancement on going from lower to higher scan rates.
[121-122]
Randles-Sevcik equation (equation 2.31) was applied to estimate the diffusion

coefficient (D0) values of UO3 and UO2 in both DES.

º.¶¿µ °±
|­® L ­®/ | = (6.3)
´²³

Where Ep is the peak potential, Ep/2 is half peak potential, F is the Faraday constant, α is the

charge transfer coefficient, n is the number of electrons transferred. The plots between ip

versus √ν were found to be linear (equation 2.31) corresponding to reductive peaks of

uranium oxides in both DES [Fig. 6.13(i-ii)]. Therefore, it can be concluded that in

both DES, the UO3 and UO2 undergo reduction through a diffusion-controlled process.

From their respective slopes of linear plots above, the diffusion coefficient values (D0)

of uranium oxides (UO3 and UO2) in both DES were calculated and reported in Table

6.6. It can be seen from the table, the order of D0 for UO3 is DES 1> DES 2 and

similar is the case with UO2. This shows that in DES 2, the formation of bulkier

uranium species is more likely. However, when we compared the oxides of uranium in

a particular DES, D0 of UO2 > D0 of UO3 in DES 1 but in DES 2 the order is reversed.

As discussed earlier, the irreversibility of the reductive peaks of UO3 and UO2

in both the DES [Fig. 6.10(a) and 10(c)] can further be validated with the linear
[75-76]
relationship between Ep and log ν according to the equation 2.35 . The Ep vs. log

ν plots for the reductive peak of UO3 and UO2 are presented in Fig. 6.13(i-ii). All these

plots show the linear relationship between Ep vs. log ν, corroborating the said

irreversibility of uranium oxides in DES 1 and 2. The value of the formal potential (Ef)

required to calculate αn and k0 was deduced from the intercept of Ep versus ν plot (not

given here) on the ordinate by extrapolating the line up to ν= 0. The values k0 can be

calculated from the above equation 2.35. However, in order to verify the values of k0,

other equations reported in the literature were also used as discussed below.

202
 According to the literature, for irreversible redox process, an expression of ip in
[75-76]
terms of Ep can also be described by the equation 2.34 . A plot of lnip versus (Ep-Ef)

would give a straight line with a slope of (αnF/RT) and intercept of ln (0.227 nFAC0*k0). The

corresponding lnip vs. (Ep-Ef) plots of uranium oxides are provided in Fig. 6.13(i-ii), which

illustrate the linearity between lnip versus (Ep-Ef). The values of αn were calculated from the

slopes of the above linear plots (equation 2.34) for UO3 and UO2 in both DES and are

reported in Table 6.6. As can be seen from the table, the values of αn are < 0.5, corroborating

the sluggishness of the electron transfer process. Substituting the known values for the

respective terms in intercepts from the above plots, one can obtain the values of k0. However,

its determination using the above two equations (2.34 and 2.35) depends on the knowledge of

the value of Ef which is not so easy to obtain for irreversible redox conditions. In those cases

where the calculation of Ef is not so simple, it is derived from the literature (Velasco et al.)
[92]
that equation 2.36 can also be used, eliminating the Ef, for the calculation of k0. Knowing

the values of Ep-Ep/2 at a particular scan rate and with the knowledge of D0 (as

determined above), equation 2.36 can be used to calculate k0. The values of k0 were

evaluated using equations 2.34, 2.35 and 2.36 for UO3 and UO2 in both DES and are

mentioned in Table 6.6. From table, it is clear that the values of k0 calculated from are

found to be nearly the same except that of UO3 in DES 2. The lower values of transfer

coefficient of uranium oxides in both DES, in the present case, indicate the asymmetry

of the configuration during the electron transfer between the initial and final

configurations and also the difference in the mechanism of electron transfer in DES

from that of aqueous solutions [230-231].

6.3.8.5. DES vs. Aqueous

The deviations were observed in redox parameters (viz. peak potential (Ep),

transfer coefficient (α) and diffusion coefficient (D0)) of dissolved uranium species in

203
both DES from that of the aqueous solvent. For example, the redox potential values of

the U(VI/V) redox couple lies in the range -0.2 V to -0.250 V at Hg, glassy carbon

(GC) and Pt working electrode respectively [98, 116-118, 148, 179-180, 211-212]. However, in the

present studies, the same redox couple's peak potential values were observed at -0.305

V and -0.355 V in DES 1 and 2 respectively at the GC electrode. Also, the values of

the diffusion coefficient of uranium species [10-8 cm2/sec] in DES were seen to be

lower than that in aqueous solvent [10-5-10-6 cm2/sec]. This deviation could be

described in terms of differences in (i) solvent reorganization mechanism, and (ii)

[213]
speciation of uranium in present DES and in the aqueous solvent . The solvation

structure of the uranium ion is highly ordered in the aqueous solution while the same
[213]
is expected to be less ordered in the case of present DES . Therefore, the free

energy change (∆G°= -nF∆E°) during a redox reaction of uranium species in the

aqueous solvent through solvent reorganization is more as compared to that in DES.

Accordingly, the difference in redox potential values of uranium species was observed

in two different solvents (viz. aqueous and DES). Also, the speciation of uranium in

both solvents is expected to be different.

6.3.8.6. Reduction-Mechanism: Based on the calculated values of αn [Table 6.6], the

number of transferred electrons was found to be ~ 1 in their respective reductive peaks

of UO3 and UO2 in DES 1 and 2. Further, it was aforementioned that UO3 converted to

UO22+ [U(VI)] through dissolution in both DES. Therefore, the plausible redox

mechanism for UO3 in DES 1 and 2 can be described by scheme 6.3. Two consecutive

SET (Single electron transfer) reduction mechanism was anticipated in case of UO3

dissolved in DES 1 and 2 as discussed in scheme 6.3. In the case of UO2 in both DES,

the reduction mechanism is proposed as one SET through U(IV) to U(III) redox

conversion [231].

204
6.3.9. In situ spectroelectrochemical Studies

In-situ UV-Visible spectroelectrochemical measurements were performed only on

UO3 dissolved DES 1 and 2 solutions for preliminary understanding of the redox stability of

the uranium oxidation states and acquiring the electronic absorption spectra of intermediate

redox species of uranium during electrolysis. Fig. 6.14(a-c) depicts the resultant absorption

spectra recorded at different applied potentials of UO3 in DES 1. As clear from Fig. 6.14(a-c),

in applied potential range from 0.45 to -1 V, the observed spectra no longer passed through

the isosbestic point, indicating the absence of the single redox equilibrium. This observation

validates our earlier CV result [Fig. 6.10(a)], where two redox processes were observed. The

decrease in absorbance values of UO22+ [U(VI)] at 422, 428, 455, 463 and 480 nm was found

with the application of cathodic potential from 0.45 V to -1 V [Fig. 6.14(a) and its inset

figure]. This indicates the conversion of U(VI) to its lower oxidation states. The decrease in

the concentration of U(VI) with cathodic potential was reflected in terms of its absorbance in

the spectra. Fig. 6.14(b) shows the enhancement in absorption intensity and change in the

nature of spectra (regions AB and BC) in the range of the applied cathodic potentials from

0.45 V to -0.042 V as compared to that at no potential. However, at higher cathodic potentials

than -0.042 V, a decreasing trend in absorbance intensity was found. The increasing and

decreasing absorption intensity trends are associated with the increasing and decreasing

concentration of species at the respective applied cathodic potentials, suggesting the

formation of intermediate redox species. Since the one absorption peak at 780 nm was

observed in Fig. 6.14(b), it was assigned to intermediate species, i.e., U(V) in DES 1. The

assigned peak position of absorption spectra corresponding to the intermediate U(V) species

(transient) obtained during electrolysis is in agreement with the previous literature reports [129-
131, 231]
. The U(V) formed this way gets further reduced to U(IV). Therefore, the concentration

of U(V) increases initially because of the fast kinetics of the conversion [U(VI)-U(V)] due to

205
the first reductive peak up to -0.042 V. Beyond this, the kinetics of the conversion of the

second reductive peak [U(V)-U(IV)] becomes faster than the first, resulting in the decrease in

U(V) concentration. Also, it is clear that with applied cathodic potentials, the concentration of

U(IV) species continuously increases. Hence the absorption peaks at wavelengths 569 nm,

609 nm, 630 nm and 646 nm in Fig. 6.14(c), which shows the enhancement in absorption

intensity with applied cathodic potentials from -0.042 V to -1 V, are due to the U(IV) species

in DES 1 [180, 231].

The spectroelectrochemical data of UO3 in DES 2 are shown in Fig. 6.15(a-b). As

obvious from Fig. 6.15(a), with applied cathodic potentials from 0.0419 V to -2.79 V, the

spectral changes were observed with an isosbestic point at 482 nm, indicating the existence of
[129-131]
one redox equilibrium during the region of applied cathodic potentials . Absorbance

intensities at 421, 428, 445, 457 and 466 nm were continuously decreasing with the applied

cathodic potentials from 0.0419 V to -2.79 V. Obviously, these absorption peaks are

associated with the UO22+ [U(VI)] species in DES 2. Hence the decreasing order is due to the

lowering in the concentration of U(VI) species with applied cathodic potentials. In the NIR

region (>725 nm), the absorbance intensities in regions AB and BC at 774, 795, 841, 850,

865, 904 and 921 nm [Fig. 6.15(b)] were found to be dependent on applied cathodic

potentials and show the increasing trend. Literature reports [129-131, 180, 231] suggest the presence

of U(V) species in the NIR region at the above wavelengths. Therefore, in Fig. 6.15(b), the

absorption peaks observed in the above wavelength regions (i.e., AB and BC) are assigned to

U(V) species in DES 2. The species of U(V) is relatively stable (as lower than -1.4 V, no

peaks corresponding to U(IV) is present) in DES 2 and increasing in concentration with the

varying applied cathodic potentials. Therefore, the absorption peaks of U(V) species are

highly intense even when the cathodic potential was varied up to -2.79 V. In Fig. 6.14(b), in

DES 1, only one absorption peak of U(V) was obtained at 780 nm due to the formation of

206
intermediate species (transient) of U(V), while several absorption peaks (at 774, 795, 841,

850, 865, 904 and 921 nm) were observed in DES 2 [Fig. 6.15(b)] due to the formation of

U(V) as an end product (relatively stable).

6.3.10. Simulation studies:

Molecular dynamics (MD) and DFT: The MD simulation was performed to corroborate the

electrochemical results by simulating the diffusion coefficient of uranium dissolved species

in DES and obtaining the probable equatorial coordination of dissolved uranium species

through radial distribution function. Taking the simulation of UO22+ ion, as an example,

which formed after dissolution in DES 1 [discussed above], first the geometries of C8mimBr

(C8 instead of C10 is taken here, as the basis set was already available for C8 and assumed to

apply for C10 also) and malonic acid (MA) were first optimized using M06-2X functional [84]
[85] [86]
and TZVP basis set as implemented in Turbomole suite of package . The atoms of

C8mimBr and malonic acid are represented in Fig. 6.16(a). Initially, the bulk phase of DES

(molar mixture of C8mimBr and malonic acid in ratio 1:2 i.e. 500:1000) was equilibrated in

NPT ensemble followed by 50 ns production run at 298.153 K temperature and 1 bar pressure

in dry condition and with 20% water. The calculated density of C8mimBr was found to be
[232]
1.14 gm/cc which is in excellent agreement with the experimental results of 1.16 gm/cc .

The system containing UO22+ ion was equilibrated in NPT ensemble followed by 50 ns

production run at 298.153 K temperature and 1 bar pressure. In order to study the

coordination environment of the UO22+ ion in DES solution, the enlarged structure of the

complex of UO22+ ion is presented in Fig. 6.16(b). The U-Br bond distance is calculated from

the peak position of the radial distribution function (RDF) of U and Br as displayed in Fig.

S6.3(a) and the values are presented in Table 6.8. The U-Br bond distance was 2.85 Å. The

U-O (O of malonic) bond distance was calculated from the peak position of the radial

distribution function (RDF) of U and O of malonic acid as displayed in Fig. S6.3(b) and the

207
values were presented in Table 6.8. The malonic acid was shown to be monodentate, and only

carbonyl O participated in the first coordination sphere towards the UO22+ ion. The calculated

U-O bond length was found to be 2.55Å. The average number of malonic acid molecules in

the first coordination shell was found to be ~2 [Fig. 6.16(b)]. The diffusion coefficient of

UO22+ ion was calculated from mean square displacement and was found to be 1×10-8

cm2/sec. The simulated value of diffusion coefficient (1×10-8 cm2/sec) is in excellent

agreement with the experimentally evaluated value (1.016×10-8 cm2/sec) (UO3, peak I; Table

6.6). Further, in order to understand the interaction of malonic acid with uranyl ion in the

presence of Br- ion, the structure of uranyl ion with malonic acid has been optimized at the

M06-2X/TZVP level of theory and is displayed in Fig. 6.16(c). The Gibbs free energy of the

complex in the gas phase was evaluated at the M06-2X level of theory and the same is listed

in Table 6.8. Moreover, the binding character of the complex of UO22+ ion with MA was

studied by evaluating the energy levels of MOs at the B3LYP/TZ2P/ZORA level of theory
[217-218]
. The Molecular orbital (MO) diagram of LUMO, LUMO+1, HOMO and HOMO-1 of

the metal-ligand bonding for [UO2-(MA)2-(Br)2] complex (isosurface value of 0.017 a.u. was

used) is given in Fig. 6.16(d).

(c) Speciation of Americium in Malonic acid based Deep eutectic solvents

6.3.11. Redox speciation of Am in CDHC-MA DES: The oxidation process of Am(III) is

not thermodynamically simple and is hampered by high potential (2.6 V vs. SCE) for Am

(III)/Am(IV) couple according to Latimer diagram, which is shown in Fig. 6.17(i)(a). In the

present study, the speciation of americium oxide in CDHC-MA DES is performed using

electrochemical method to understand the feasibility of converting Am(III) to its higher

oxidation state, especially in its actinyl (AmO22+ or AmO2+) ion. Following a direct approach,

the 5 mg of Am-oxide was successfully dissolved in CDHC-MA DES without any additives

208
using dissolution set-up in glove box (discussed in chapter 2). The change in colour of

solvent (yellow colour in Fig. 6.17(i)(b)) and γ-counting through NaI(Tl) and HPGe detector

authenticates the solubility of Am-oxide and its presence in CDHC-MA DES through

dissolution process. The UV-Visible absorption spectra of dissolved Am-oxide sample was

recorded, which shows the dominant absorption peak at 502 nm. This indicates the formation

of Am(III)-DES complex kind of species through the dissolution.

In depth analysis on the electrochemical oxidation of Am(III) in both DES were

carried out by cyclic (CV) and differential pulse voltammetry (DPV). The representative CV

plots in potential region form -0.2 V to 1.5 V at Pt working electrode are shown in Fig.

6.17(ii)(a). The initial results indicate that (i) no interference from blank DES on the

oxidation process of Am(III), (ii) two oxidation peaks with one electron transfer as Am(III) to

Am(IV) and Am(IV) to Am(V) was observed and hence Am(III) can be easily oxidized to its

higher stable oxidation state, (iii) Am(IV) is a stable oxidation state in CDHC-MA and

Am(III)-Am(IV) conversion has much lower oxidation potential (~ 0.68 V) in DES compared

to that in aqueous medium (i.e., 2.6 V vs. SCE). The DPV plot [Fig. 6.17(ii) (b)] with

increasing concentration of Am(III) implies that the oxidation peak II i.e., peak belonging to

AmO2+ formation is relatively unstable. This may be due to the combined effect of three

factors (i) disproportionation of AmO2+ according to equation as 3AmO2+ + 4H+ = Am(III) +

2AmO22+ + 2H2O (rate = k [AmO2+]2[H+]4), (ii) auto-reduction of Am(V) to Am(III), which

depends on AmO2+ concentration and (iii) requirement of Am-O bond formation during

Am(III) to AmO2+ oxidation steps, which is kinetically sluggish. In CV, the scan rates (ν)

variations [Fig. 6.17(ii)(c)] indicates enhancement in peak current of both oxidation peaks

with increasing ν and the linearity between peak current (ip) and square root of scan rate (√ν).

This implies the diffusion-controlled oxidation process of Am(III) in CDHC-MA. From the

slope of ip vs. √ν plot and using Randles-Sevcik equation (equation 2.31), the diffusion

209
coefficient of Am in CDHC-MA was calculated and reported in Table 6.9. The

heterogenous electron transfer rate constant (k0) for oxidation of Am in CDHC-MA

was evaluated using equation 2.34 and reported in Table 6.9. Theoretical calculations

were performed to corroborate the electrochemical results and to obtain the optimized

structure and energetic of Am in both DES. In order to understand the interaction of CDHC-

MA with Am, structure of their complexes have been optimized at the B3lYP/SVP level of

theory and is displayed in Fig. 6.17(i)(d). Further, free energy of complexation in solution

phase was determined using the total energy of the chemical species at the B3LYP/TZVP

level of theory using standard thermodynamic corrections and COSMO solvation model [233].

The calculations reveal that 1:2 type of Am-DES complex formation and their corresponding

free energy were reported in Table 6.9.

6.4. Conclusions:

This study affirms that Maline is a versatile all in one platform working as dissolver

medium, designer solvent for analysis of U in nuclear materials and promising U chelator.

Present studies reveal that Maline and Imidazolium based DESs have unique solvation

potential for diverse kinds of U matrices like oxides, salts, metal powder and alloy without

any additives and hence these DESs could be acknowledged as low temperature direct

sequestering media for processing of U matrices to incorporate U ion in solution. The density,

viscosity and melting point of newly prepared imidazolium-based DES 1 and 2 are reported.

The neat DESs and dissolved uranium matrices have been characterized by IR, UV-Vis,

TGA, Karl-Fischer titrations etc. The present studies indicate that DES 1 and 2 are redox-

active in nature. The redox speciation of U matrices in Maline and imidazolium based DES 1

and DES 2 were successfully probed by electroanalytical techniques viz. CV and DPV. The

redox thermodynamic characteristics (peak potentials (Ep) and formal potential Ef), diffusion

210
coefficient (D0) and kinetic parameters (k0 and αn) of uranium species in above DESs were

determined and compared with the literature. The EXAFS analysis specifies the UO22+ kind

of species formation with malonic acid and H2O at equatorial coordination through

dissolution of UO3 in Maline. Spectroelectrochemical outcomes corroborate the results of CV

and provide the electronic absorption spectra of U(V) and U(IV) species in Maline and

imidazolium based DESs. MD and DFT simulations showed very good agreement with the

experimental interpretations and deliver the optimized geometry, binding energy and MO

diagram of U species in above DESs. The interaction of the UO22+ solution with Maline was

observed to be endothermic and entropy-driven and logK value was found to be 1.20 ± 0.01.

The redox thermodynamic and kinetic parameters of Am redox process and structure of Am

in CDHC-MA were determined. Present studies show significant fundamental advancement

in the research field of the actinide-DES system.

211
 Schemes, Figures and Tables
Part (a) U-matrices in Maline

Scheme 6.1. The plausible reduction mechanism of UO3 in Maline.

SET: Single electron transfer

212
 (a)

(b) (c)

Figure 6.1. Characterization: (a) IR spectra of UO3 and UN dissolved Maline solution. TGA
plots (b) Wt% loss versus Temperature (c) The UV
UV-Visible
Visible absorption spectra of UO3
dissolved in Maline solution, blank Maline and UO22+ and malonic acid complex in aqueous
solution.

213
Figure 6.2. Redox speciation of Uranium matrices in Maline. Cyclic voltammetry plots of (a)

UO3, UN, UO2, U3O8 and blank Maline (b) U std., U metal and U3Si2 (c) PuO2 and (U, Pu)O2

(d) Scan rates variation studies by Cyclic voltammetry (CV) on UO3 dissolved in Maline.

214
 (i)

(ii)

(iii)

Figure 6.3. Insitu UV-visible Spectroelectrochemical Data. (i) Absorbance spectra of U(VI)

in Maline with applied cathodic potentials. (ii) and (iii) are the appearance of new absorption

peaks with applied cathodic potentials related to U(IV) and U(V) species in Maline

respectively.

215
 (i)

(ii)

Figure 6.4. (i) Normalised XANES spectra at U L3-edge along with standard samples. (ii)

Fourier transformed EXAFS spectra of U sample at U L3-edge in (a) R space and (b) K space

along with the best fit. The experimental spectra are represented by Scatter points and the

theoretical fit is represented by Solid line.

216
(a) (b)

-10.0 120A
119A
118A
-10.5

-11.0
Energy level (eV)

-12.0

-13.0

-14.0

-15.0 117A
-15.5 116A

-16.0 115A

[UO2-(MA)2-(H2O)2]2+ complex

(c)

Figure 6.5. (a) Equilibrated structure of the Maline system containing Uranyl ion in the

presence of water molecule. System representation with 5% water. color code: Steel: UO2

species; Red & White: H2O; Cyan: Cl; rest are malonic acid and choline (b) Optimized

structures of [UO2-(MA)2-(H2O)2]2+ (c) The calculated energy levels (eV) of the MOs of the

[UO2-(MA)2-(H2O)2]2+ complex using B3LYP/TZ2P/ZORA level of theory.

217
Figure 6.6. (a) The luminescence intensity of Uranyl with increasing concentration of Maline
(b) Comparison of luminescence intensity of Uranyl with Malonic acid and Maline at two
different concentrations (c) The absorption spectra for Uranyl titration with Maline (d)
Deconvoluted spectra representing the absorption profile for the pure components (e) Raw
calorimetric data for the interaction of Uranyl with Maline (f) Integrated Data showing the
cumulative heat released on successive additions of DES solution to fixed volume of Uranyl
solution; [UO22+] = 0.01 M, [DES] = 0.48 M.

218
Figure 6.7. (a) Differential pulse voltammetry plots with increasing concentration of UO3 (b)
Calibration Plot of UO3 dissolved in Maline solution obtained with increasing concentration
(c) Electrochemical interference study on UO3 dissolved Maline with other metal ions
dissolved Maline (d) Selectivity of Maline for different dissolved metal ions.

219
Table 6.1: Electrochemical thermodynamic and kinetic parameters of U matrices in Maline.

(Irrev. = Irreversible redox behaviour)

Systems Redox thermodynamics and Kinetics parameters

Peak (Ep) & Formal (Ef) αn k0 (cm/sec) D0 (cm2/sec)

Potentials (V)

1. UO3 Peak 1: Ep= -0.524 V (Irrev) Peak 1: 0.263 2.60x10-4 2.71x10-8

Ef= -0.386 V
Peak 2: Ep= -1.511 V (Irrev) Peak 2: 0.206
f
E = -1.198 V
2. UO (NO ) .6H O Peak 1: Ep= -0.495 V (Irrev) Peak 1: 0.304 7.15x10-5 0.71x10-8
2 3 2 2
Ef= -0.387 V
Peak 2: 0.235
Peak 2: Ep= -1.533 (Irrev)
Ef= -1.245 V
3. UO2 Ep= -1.424 V (Irrev) 0.118 9.66x10-4 1.53x10-7
Ef= -1.314 V
4. Rb2U(SO4)3 Peak 1: Ep= -0.591 V (Irrev) Peak 1: 0.277 6.70x10-5 0.23x10-8
Ef= -0.507 V
Peak 2: Ep= -1.480 V (Irrev) Peak 2: 0.229
Ef= -1.391 V

5. U-metal Peak 1: Ep= -0.559 V (Irrev) Peak 1: 0.261 4.99x10-5 0.3x10-8

Ef= -0.509 V
Peak 2: Ep= -1.502 V (Irrev) Peak 2: 0.26
Ef= -1.439 V
6. U3Si2 Peak 1: Ep= -0.459 V (Irrev) Peak 1: 0.539 1.32x10-5 0.5x10-10
Ef= -0.426 V
Peak 2: Ep= -1.555 V (Irrev) Peak 2: 0.222
Ef= -1.430 V
7. (U, Pu)O2 Ep= -1.565 V (Irrev) 0.116 2.79x10-3 3.6x10-7
Ef= -1.532 V

220
Table 6.2: Bond length (R (Å), phase-corrected), coordination number (N) and disorder

factor (σ2) obtain by EXAFS fitting.

Path Parameters U sample

U-O1 R (Å) 1.80±0.01
N 1.94±0.06
σ2 0.0013±0.0009
U-O2 R (Å) 2.52±0.01
N 3.88±0.16
σ2 0.0019±0.0011
U-O3 R (Å) 2.55±0.01
N 1.95±0.05
σ2 0.0019±0.0011

Table 6.3: Analytical figures of merit and validation of developed analytical methodology for

Uranium matrices sample determination in Maline.

Samples DPV EDXRF D.C. Arc AES

(Present study) (mg/ml) (mg/ml)

(mg/ml)

1. UO3-Maline Obtained value= 4.989

(Lower conc. Side) RSD= 0.140%

(Known conc.= 5 Precision= 4.989 ± 0.140%

mg/ml)
Accuracy= 0.218%

2. UO3-Maline Obtained value= 17.990±0.166% 17.9±0.2 18±0.4

(Higher conc. side)

(Unknown conc.)

3. U-metal Obtained value= 2.150±0.205% 2.4±0.3 2.1 ± 0.4

(Unknown conc.)

221
Table 6.4: Comparison of Green metrics of present methodology (direct sequestering and
analysis of uranium matrices with Maline supramolecular scaffold) and previous method (i.e.
hazardous acidic/additives dissolution and biamperometery analysis).

Green metrics Present methodology Previous method

(i)
E-Factor 0 18.82 (i)
21.38 (ii) (This 1592.38 (ii)
amount obtain due to excess
Maline solvent so it may be
considered as non-hazardous
waste)

Atom economy 100 % 1a, 95.24% 1b 53.45%

2
97.67%
Reaction mass 4.1% 0.099%
Efficiency (RME)

Mass Intensity (MI) 24.39 1594.97

Energy Used 3420 KJ 16200 KJ

Chemical Used 1.5 mL to 2 mL of Maline Hazardous acids: (i) 5-10 mL

(a green and sustainable of concentrated HNO3 (15.66
solvent) M); (ii) 5 mL of 6M H2SO4
(iii) Lots of reagents

Steps involved Direct (sequestration as well 2 steps (dissolution) +5 steps

as analysis) (analysis)
Step economy

(i) and (ii) are the conditions without solvents and with solvents respectively. More details calculations are
given in supporting information.
1a and 1b is the atom economy in the case of UO2
2 is the atom economy in the case of UO3

222
 Part (b) U-oxides
U in Imidazolium based DESs

Scheme 6.2: Dissolution procedure

Scheme 6.3: Mechanistic electron transfer process

223
Figure 6.8. (a) measured density of DES 1 with varying temperature and fitting (b) measured

viscosity of DES 1 and fitting (c) Thermograms obtained in DSC for pure components.

224
Figure 6.9. (a) IR spectra of the UO3 and UO2 dissolved in DES 1 (b) UV-Vis spectra of UO3

dissolved DES 1 (c) TGA data of the UO3 and UO2 dissolved in DES in terms of the wt %

loss with temperature (d) derivative plot (e) electrochemical potential window and redox

peaks of DESs.

225
(a) (b)

(c) (d)

Figure 6.10. (a) and (b) are the CV and DPV plots for the oxides of uranium dissolved in

DES 1. (c) and (d) are the CV and DPV plots for the oxides of uranium dissolved in DES 2.

The concentration of uranium oxides ~ 4.5 to 5 mg/ml.

226
Figure 6.11. (a) and (b) are the DPV plots with increasing concentration of UO3 (peak I and

II) in DES 1. (c) and (d) are the ip(A) versus conc. UO3 plots in DES 1 (e) Ep vs.

concentration of UO3 in DES 1.

227
 (a)

(b)

Figure 6.12. (a) is the recorded DPV plots for U3O8 by varying its concentration (DES 2). (b)

(i) to (iii) are the ip(A) vs conc. U3O8 plots for reductive peaks I to III.

228
 (i)

(ii)

Figure 6.13. (i) and (ii) are the scan rates variation studies on uranium oxides dissolved in

DES 1 in cyclic voltammetry (CV). (a) is the CV plots recorded with varying scan rates. (b)

is the E vs. logν plots. (c) is the ln|ip| vs. Ep-Ef plots (d) is the i(A) vs. √νν plots of their

respective uranium oxides.

229
 (a) (b)

(c)

Figure 6.14. In situ UV-visible Spectroelectrochemical Data. (a) Absorbance spectra of

U(VI) in DES 1 with applied cathodic potentials. (b) and (c) are appearances of new

absorption peaks with applied cathodic potentials related to U(V) and U(IV) species in DES 1

respectively.

230
 (a)

(b)

Figure 6.15. In situ UV-visible

visible Spectroelectrochemical
lectrochemical Data. (a) Absorbance spectra of

U(VI) in DES 2 with applied cathodic potentials with the isosbestic point. (b) (i) to (iii)

showing the appearance of new absorption peaks with applied cathodic potentials related to

U(V) species in DES 2 respectively.

ectively.

231
Figure 6.16. MD simulation results: (a) Geometries of (i) C8mimBr and (ii) malonic acid
molecules. (b) Enlarged picture of DES-uranyl system. (i) UO2-Br2, UO2-Br3 and UO2-Br4
and (ii) UO2-2malonic acid. Here, U: pink; O: Red; Br: light blue; malonic acid: Blue. DFT
simulation results: (c) Optimized structures of [UO2-(MA)2-(Br)2] (d) The calculated energy
levels (eV) of the MOs of the [UO2-(MA)2-(Br)2] complex using B3LYP/TZ2P/ZORA level
of theory.

232
 (i)

(ii)

Figure 6.17. (i) (a) Latimer diagram for Am in 1 M perchloric acid (b) dissolved sample of

Am-oxide in DES (c) UV-Visible absorption spectra of Am in DES (ii) (a) CV plots of Am-

oxide in CDHC-MA and blank CDHC-MA (b) DPV plots with increasing concentration of

Am in CDHC-MA (c) CV plots with varying scan rates from 10 mV/sec to 150 mV/sec (d)

the ip vs. √ν plot.

233
Table 6.5: The observed and calculated weight loss along with the liberated molecules at various temperatures in TG-DSC.

Name of % Weight loss Temperature Predicted % Weight loss Temperature Predicted

liquid Range of loss Molecules/atom Range of loss Molecules/atoms loss
for R1/ 0C s loss from the for R2/0C from the loss in weight
Regions of loss loss in weight Regions of loss
R1 R1 R2 R2
(observed) (Calculated) (observed) (Calculated)
Blank
DES 1 39.9 32.5 25-195 2HBr+8.5H2O 59.3 67.5 195-346 2C10mim+2Malonate

Solution
of UO3 in
DES 1 29.5 25.4 23-179 2HBr+8.5H2O 68.2 52.75 179-414 2C10mim+2Malonate

Solution All the remaining

of UO2 in elements after loss of
DES 1 42.7 35.0 23-183 4HBr+8.5H2O 56.9 45.32 183-380
4HBr+8H2O leaving
UO2 as final product
Blank
DES 2 2C10mimBr+2Diglycolic
8.5 9.0 25-170 5.0 H2O 85.9 91.0 170-359
acid+6H2O
Solution
of UO3 in 2C10mim+2Diglycolic
DES 2 3.5 4.4 25-171 4.0 H2O 88.4 78.9 171-359
acid+4HBr+7H2O

Solution
of UO2 in All the remaining
DES 2 elements after liberation
18.2 11.0 25-188 11.0 H2O 79.6 73.6 188-358
of 11 H2O leaving UO2
as final product

234
 Table 6.6. Redox thermodynamic, Diffusion coefficient and kinetic parameters of UO3 and
UO2 in DES (# eqn-5; *eqn-6; @
eqn-7. PI is the reductive peak I. PII is the reductive peak II).

Electrochemical UO3 UO2

parameters
DES-1 DES-2 DES-1 DES-2

Peak Potential -0.305 (CV) (PI) -0.355 (CV) -0.968 (CV) -1.327 (CV)

(Ep) (V) -0.128 (DPV) (PI) -0.167 (DPV) -0.866 (DPV) -1.230 (DPV)

-1.106 (CV) (PII) -1.156 (CV) (PII)

-0.902 (DPV) (PII) -0.954 (DPV) (PII)

Ef (V) -0.191 (PI) -0.225 (PI) -0.928 -1.270

-0.984 (PII) -1.075 (PII)

αn 0.262 0.368 0.403 0.365

k0 (cm/sec) 1.20×10-4 # 1.56×10-4 # 7.0×10-4 #

0.16×10-4 #
2.29×10-4 * 0.18×10-4 * 6.40×10-4 *
0.11×10-4 *
1×10-4 @ 0.23×10-4 @ 4.9×10-4 @
0.1×10-4 @
D0 (cm2/sec) 1.016×10-8 7.872×10-10 9.792×10-8 1.262×10-10

Table 6.7: Validation of calibration plots of DES 1 and 2 by concentration

determination of uranium oxides.

Compounds U content U content

(Unknown conc.) (Present study: Voltammetry) (Biamperometry)

(mg/ml) (mg/ml)

1. (DES 1): UO3 1.80±0.21% 1.78±0.18%

2. (DES 2): U3O8 3.21±0.22% 3.12±0.18%

235
Table 6.8. The calculated values of structural parameters in simulated systems and the
calculated values of Gibbs free energy (kcal/mol) of complexation in the gas phase.

Description coordination System Gibbs free

length energy
(Å) (kcal/mol)

U-Br 2.85 [UO2-(MA)2-(Br)2] -545.2

U-O(malo) 2.55

Part (c) Speciation of Am in CDHC-MA DES

Table 6.9. Experimentally and theoretically obtained parameters of Am in DES.

Parameters CDHC-MA CC-MA

λmax Am (III) 485 nm 502 nm
E (V) [Am(III)- 0.68 0.606
Am(IV)]
Diffusion 1.05x10-8 1.50x10-8
coefficient (D0) cm2/sec cm2/sec

Free energy -52.12 -50.12

(Complex) kcal/mole kcal/mole

236
 Chapter 7

Summary and Future outlooks

Aim: This chapter summarizes the thesis, discusses its findings and contributions, points out

limitations of the current work, and outlines directions for future research.

In the present thesis systematic investigations on comprehensive speciation of actinyl

ions especially U, Np and Am were carried out with aqueous soluble organic chelating

ligands and deep eutectic solvents media using electrochemistry, UV-Visible absorption

spectroscopy, EXAFS, Calorimetry, ESI-MS, in-situ spectroelectrochemistry and theoretical

calculations (DFT and MD).

The summary of works presented in the thesis is divided into two parts:

(a) Speciation of actinyl ions in aqueous soluble chelating ligands: The studies

specifically focusing on fundamental complexation, stability, structural, and redox

transformations and kinetics information about the actinyl species (U, Np and Am) in the

aqueous. The speciation of uranyl and neptunyl was discussed with chelating ligands viz.,

carboxylate and phosphonate-based ligands, like those used in extraction and

237
decontamination process or potentially present in waste repository scenarios. The studies in

the present thesis infer that citrate, PPA and PCs chelators form very stable aqueous soluble

complexes of U and Np, which are quite persistent over a wide range of Eh-pH. The stability

constant (logβ), redox potential and shift in redox potential of uranyl with these chelators

were found to be as citrate<PPA<PCs (Fig. 7.1 and 7.2). The hetero-bidentate chelation in

combination with the intra-molecular hydrogen bonding is responsible for enhanced

complexation tendency of PCs towards UO22+. Redox speciation of actinyl ions is probed to

deduce redox energetic and kinetics of electron transfer process for their redox couples in

aqueous solution across the pH range. In aqueous solution, the peak potentials of actinyl ions

(U and Np) were measured and the potentials were compared in absence and presence of

chelators. To obtain their similarities and differences in terms of the shape of the cyclic

voltammograms, peak potentials, reversibility trends, current responses etc. the

experimentally obtained voltammograms were compared. It could be concluded that citrate,

PPA and PC ligands have major impact on the U and Np redox system in terms of reaction

mechanisms, thermodynamics, and kinetics of their redox reactions. The association of

couple chemical reaction was discovered with electron transfer (ET) steps for UO22+

complexes, which suggesting reduction mechanism as ICI and PCET in citrate and PCs,

respectively. Interestingly, the rare oxidation state of uranium i.e., pentavalent uranyl (UO2+)

species was observed to be redox stable in a wider pH in presence of citrate and PCs in

aqueous solution and its validation for existence, electronic absorption spectra, stability

constant (logβ), and structure were reported by spectroelectrochemistry, cyclic voltammetry

and DFT. This information might be important in detailed understanding of actinide (V)

chemistry.

238
Figure 7.1. Variation of stability constant (logβ) of actinyl ions with various complexing
ligands

Figure 7.2. Variation of shift in peak potential (|∆E|) (logβ) of uranyl ions with various
complexing ligands.

(b) Dissolution and speciation of uranium matrices and americium oxide in actinide

specific deep eutectic solvents: Deep eutectic solvents namely Maline and imidazolium

cation based DESs shows better solvation potential for diverse kinds of actinide matrices. For

the first time, two-imidazolium based DESs were prepared by combining the ionic liquid and

239
carboxylic acid and being reported on the dissolution of uranium oxides. Above DESs

solvents favour the dissolution process of solid uranium samples through their oxygen-

binding sites. Malonic acid based DESs viz., Maline and CDHC-MA works as designer

solvents for (1) quantitative green analysis of NMs such as U, and (2) oxidation of Am to its

higher oxidation state. The CV and DPV studies revealed redox speciation of U matrices and

Am-oxide dissolved in DESs with insights into their redox thermodynamics, the trend

towards reversibility, kinetic parameters, and electron transfer mechanism.

Spectroelectrochemistry validated the results of CV and provided the electronic absorption

spectra of U(V) and U(IV) species in DESs. The differences in the redox parameters of

uranium species in DESs versus aqueous systems were elucidated in terms of the differences

in solvent reorganization mechanisms and speciation effects. Molecular speciation on UO3

dissolved in Maline was probed by UV-visible absorption spectroscopy, calorimetry, and

EXAFS, which provided its coordination modes, stability (log K) and energetic of

interaction. The simulation studies (MD and DFT) corroborated the experimental results of

CV and DFT of dissolved uranium species in DESs and gave an insight into the optimized

geometry, binding energy, and MO diagram of U species in DESs. The present study enables

the analytical determination of U using DES by calibration plot. The simplicity of proposed

analysis methodology, short analysis time, high speed of sample preparation, lack of usage of

hazardous concentrated acids and oxidizing agents, and the use of safe and inexpensive

components recommends the high potential of Maline for routine analysis of U related to

nuclear material/forensic samples. It is expected that using a lower stoichiometric deep

eutectic solvent such as Malonic acid:ChCl (1:1) than the other DES with the stoichiometric

ratio of 1:2 or 2:1 (of HBD and HBA) for dissolution of metal oxides would be more

economical in terms of use of chemical/reagent for its practical application on large scale.

The findings of the present studies related to dissolution, speciation and analysis of U and

240
Am are of great significance in nuclear chemistry from both fundamental and application

point of view and show substantial fundamental advancement in the research area of actinide-

DES system. The knowledge gained by studies on speciation of U and Am solid samples in

the present DESs are significant for advancement of room temperature solvent media as an

appropriate option for processing actinides compared to pyrochemical processing and

highlights potential applicability of present DESs as an alternative solvent to replace

hazardous acids and alkali metal chloride melts in high-temperature pyrochemical process.

In actinide chemistry research area, major contributions of the works in present

dissertation are (i) generation of redox energetic, transport property and electron transfer

kinetic parameters of uranyl and neptunyl ions in presence of carboxylate and phosphonate

based chelating ligands such as citrate, phenylphosphonic acid and phosphonocarboxylate in

aqueous solution, (ii) assessing the impact of carboxylate and phosphonate based chelators on

the redox chemistry and oxidation state stabilization of uranium and neptunium, (iii)

providing stability constant (logβ) values of uranyl and neptunyl ions with above chelating

ligands, (iv) exploring in-situ spectroelectrochemistry as an important tool for redox

speciation of actinides in aqueous and deep eutectic solvent media, (v) discovering non-

aqueous Maline and imidazolium cation-malonic acid/diglycolic acid deep eutectic solvents

as a potential metal ion hijacker for processing diverse kind of solid uranium matrices

including oxides, salts, alloy and metal powder, and (vi) developing new greener and

sustainable methodology for direct sequestering and analysis of uranium in nuclear material

samples.

In this thesis, the problem of usage of hazardous concentrated inorganic acid during

processing of actinide matrices was addressed and it was suggested that environmental

benign DES with unique solvating potential can be a promising media to dissolve solid

matrices of actinides. The key interesting findings of present thesis can be described as (i)

241
existence of new pentavalent uranium species with citrate and phosphonocarboxylate

chelators in aqueous solution, (ii) the logβ value of pentavalent uranium with PC chelators is

obtained to be higher than that of carbonate, (iii) heterobidenticity of three

phosphonocarboxylates with the additional capability of forming unusual stereognostic

intramolecular hydrogen bond (IMHB) with axial oxygen of uranyl, (iv) coupling of chemical

reaction with electron transfer step during reduction of uranyl in presence of citrate and

phosphonocarboxylates, and (v) choline dihydrogen citrate-malonic acid (1:1) DES works as

a promising electrolyte for dissolution of Am-oxide and selective oxidation of Am(III) to its

higher oxidation state in presence of lanthanides.

The works discussed in the present dissertation will potentially help in the design and

manipulation of redox-based remediation strategies of actinyl ions using the provided redox

potentials and electron-transfer kinetics of U and Np in the complexing medium. The

evaluated results in the present studies would help in assessing strategies for (i) microbial

bioremediation of actinyl ions, and (ii) nuclear waste treatment and risk assessment for waste

disposal containing these ions. The findings of present research works have implications for

understanding the mechanism of biotic and abiotic reduction of actinyl species and their

biogeochemical cycles in a natural environment, and elucidating the pathways for the uptake

of actinyl ions by a microbe in geo/hydro-sphere. The studies assume its significance to

predict migration pathways of actinyl ions in geosphere upon their release from DGR. This

work makes a significant contribution to the fundamental understanding and prediction of the

redox chemistry of actinides.

Limitations of the present thesis can be described as below: The speciation studies in the

present thesis were performed at room temperature. The information about the redox and

molecular speciation of uranyl and neptunyl with varying temperature in aqueous and DES

media is beyond the scope the thesis. Herein, the non-aqueous solution was chosen as DES

242
and the studies about the speciation of U, Np and Am in other non-aqueous media such as

ionic liquids and organic solvents are not covered. The present studies involve the speciation

studies of actinides U and Np in aqueous solution while U and Am in DES media whereas the

speciation studies of actinides other than above in aqueous and DES media are outside the

scope of thesis. As bifunctional chelator, the PCs are selected for speciation studies of uranyl.

Thus, speciation studies of uranyl with other bifunctional chelator such as diphosphonates or

dicarboxylates are outside the context of present works. In the present studies, the DESs were

chosen only carboxylate-based moiety as HBD such as malonic acid and diglycolic acid. The

aim of present studies is speciation of actinyl ions therefore the only aqueous speciation

parameters such stoichiometry, stability, and structure of pentavalent species with citrate and

phosphonocarboxylates were reported and the isolation of pentavalent species is beyond the

scope of the thesis.

Future outlook: Following are some suggested future research works based on the presented

works in this thesis: (i) Development of speciation sensor, (ii) Isolation of pentavalent species

using phosphonocarboxylate based chelators, (iii) Understanding the role of temperature on

redox speciation of actinides in aqueous and DES, (iv) Redox speciation of actinides at

modified electrode using ligand functionalized electrodic materials, (v) Aqueous speciation

of actinides with aqueous soluble preorganized macrocyclic and homo-bifunctional ligands,

(vi) Future design and synthesis of U selective novel adsorbents and molecular recognition of

actinides through activation of oxo group of actinyl using PCs based chelator (v)

Development of redox and non-redox based selective sequestration strategies of actinyl ions

(vi) Actinides’ electrodeposition and electrocatalytic recovery, extraction and separation

using DESs and exploring hydrophobic DESs for their potential application in actinide

chemistry.

243
Appendix

Chapter 1 and Chapter 2

Parameters used for speciation modelling

Species formation with their respective logK value in U and Np as below:

Table S1.1. The reactions and parameters used in the aquatic speciation modelling

1. UO22+ + H2O = H+ + [UO2(OH)]+ log K= -5.89

2. 3UO22+ + 5H2O = 5H+ + [(UO2)3(OH)5]+ log K= -15.58

3. 2UO22+ + 2H2O = 2H+ + [(UO2)2(OH)2]2+ log K= -5.57

4. UO22+ + 4H2O = 4H+ + [UO2(OH)4]2- log K= -33.00

5. 3UO22+ + 7H2O = 7H+ + [(UO2)3(OH)7]- log K= -31.00

6. 4UO22+ + 7H2O = 7H+ + [(UO2)4(OH)7]+ log K= -21.90

7. UO22+ + 2H2O = 2H+ + [UO2(OH)2(aq)] log K= -12.0

8. UO22+ + 3H2O = 3H+ + [UO2(OH)3]- log K= -20.00

8. NpO2+ +OH- = [NpO2(OH)(aq)] log K= 2.7

8. NpO2+ + 2OH- = [NpO2(OH)2]- log K= 4.35

244
Chapter 2

Table S2.1. The amount of sample taken and their respective concentration in Maline.

System Amount of Amount of Concentration(mg/ml)

solute (mg) Maline (ml)
UO3 6.3 1.26 5
UO2 7.5 1.5 5
U 3 O8 7.8 1.5 5.2
UO2(NO3)2.6H2O 7.9 1.5 5.26

U Std. 13 1.5 8.66

U metal 2.7 1.2 2.25

U3Si2 17 2 8.5

(U, Pu)O2 5.2 2 2.6

Table S2.2. The amount of sample taken and their respective concentration of uranium

oxides in DES 1 and 2.

System Amount of Amount of DES (ml) Concentration(mg/ml)

solute (mg)
DES 1

UO3 6.6 1.5 4.4

UO2 6.7 1.5 4.46
U 3 O8 4.7

DES 2

UO3 8.9 1.78 5

UO2 5.8 1.2 4.83

U 3 O8 4.8

245
Appendix: Chapter 3

Figure S3.1. Speciation plots: (a) At [UO22+]= 10-5 M in presence of [Citrate]= 5x10-3 M; (b)
At [UO22+]= 10-3 M in presence of [Citrate]= 5x10-2 M; (c) At [UO22+]= 10-3 M in presence of
[Citrate]= 1x10-3 M.

246
 -MS, 0.2-0.2min #(10-13)
x104
459.0829

406.0836
2

339.2299 919.1733
555.1064 619.0872
0
200 400 600 800 1000 1200 m/z

(a)

459.0640
1.0

0.8

0.6
351.5025 704.0155
439.0505
0.4 598.0182 725.9991
0.2 406.0622 675.0595
549.0519
829.5730 879.1030 919.1347
0.0
300 400 500 600 700 800 900 m/z

(b)

247
 919.1

50

40

1018.9
30

20 568.5
1110.0
1020.2
566.6
1109.6
1119.6
10 807.5
1025.9
951.3 1157.9
784.0 1031.9

250 500 750 1000

m/z

(c)

248
 919.1
30

25

20

1018.9

15
568.5

1109.0
1027.7
660.1
1094.0
10

1110.3

190.9 980.8
674.6 1150.2
1026.1
5 945.3
558.3 1091.5
428.4 879.7 1187.5

250 500 750 1000

m/z

(d)

249
 919.1

60

50

459
40

30

981.8
20 1091.1
709.4
919.9
818.5 982.4
745.6
190.9 805.8 928.6
10 455.6 679.4 1035.8

250 500 750 1000

m/z
(e)

Figure S3.2. ESI-MS data conditions: (a) [UO22+]= 10-5 M in presence of [Citrate]= 5x10-3 M
at pH 4, (b) Same as (a) at pH 6.5, (c) [UO22+]= 10-3 M in presence of [Citrate]= 5x10-2 M at
pH 4, (d) Same as (c) at pH 6.4, (e) [UO22+]= 10-3 M in presence of [Citrate]= 1x10-3 M at
pH 3.25, (f) & (g) Theoretically calculated m/z value of isotopic peak for [(UO2)2Cit2]2− and
[UO2Cit]− respectively, (h) Experimentally observed isotopic peak pattern.

250
Figure S3.3. Speciation plot of UO22+(10-5 M) in presence of 5x10-3 M PPA.

(a)

251
 (b)

Figure S3.4. (a) & (b) are ESI--MS results at UO22+ (10-5M) and PPA (10-4M)

Appendix: Chapter-4

Table S4.1. Variation of ∆Ep and ipc/ipa with Scan rates for Np(VI)-PPA reduction (Peak I).

Scan Rates (V/sec) ∆ p = (Epc-Epa)

∆E ipc/ipa
0.02 0.176 0.801
0.03 0.180 0.818
0.04 0.184 0.805
0.05 0.183 0.819
0.06 0.187 0.817
0.07 0.191 0.798
0.08 0.184 0.824
0.09 0.188 0.850

Table S4.2. Parameters obtained from Ep vs. logν plot for Np(V)-Phenylphosphonate
Phenylphosphonate (Peak
II)
Slope -0.054
αn 1.091
n (Taken α=0.5) 2.1
k0 (S-1) 0.258

252
Appendix: Chapter 5

Intens.
x104
437.2154

0.8

431.0269
0.6

403.8867 409.1905
447.9002
0.4

376.3275 467.0536
387.0395

0.2 381.0299
423.0541
393.3156

459.0801 482.8567
463.8603

0.0
380 400 420 440 460 480

-6 -5
(i) ESI-MS spectrum of uranyl(VI) (4x10 M) with PFA (4x10 M) in positive ion mode.
Intens.
x104
409.0232
1.25

485.0104
1.00
359.0306 499.0257
427.0387

445.0502
0.75
352.9783

470.9914
364.9347
506.9952 563.0500
0.50 433.1063 492.9774
513.0429 549.0276
455.0452
374.9626
571.0148
478.9608
0.25 536.9576
419.0897

400.0473

0.00
350 400 450 500 550

-6 -5
(ii) ESI-MS spectrum of uranyl(VI) (4x10 M) with PAA (4x10 M) in positive ion mode.
Intens.
x105
337.0539

359.0331

527.0683
2
375.0002 505.0845

392.9742

513.0481
491.0658
0
325 350 375 400 425 450 475 500 525

(iii) ESI-MS spectrum of uranyl(VI) (4x10-6M) with 3-PPA (4x10-5M) in positive ion mode.

Figure S5.1: (i-iii) ESI-MS spectra of Uranyl(VI) with PFA, PAA and 3-PPA respectively.

253
 (a)

(b)

Figure S5.2: Spectroelectrochemical electrolysis data at pH 8. (a) is the absorption spectra

with varying cathodic potentials in the wavelength region 375 nm to 550 nm (b) is the
absorption spectra with varying cathodic potentials in the wavelength region 560 nm to 1000
nm.

254
Table S5.1: The λmax with corresponding ε values for free UO22+ and its complexes with CPs

[UO2(PFAH)], [UO2(PAAH)] and [UO2(3-PPAH)].

Species λmax (nm) ε (mol-1 lit cm-1)

UO22+ 415 9.4 ± 0.1

[UO2(PFAH)] 421 36.7 ± 0.6

[UO2(PAAH)] 422 23.7 ± 0.3

[UO2(3-PPAH)] 421 20.1 ± 0.3

Table S5.2: The partial charges on the key atoms in the bare ligand and its corresponding
uranyl complex for all the three Uranyl(VI)-CP complexes.

Complex U O UO2 Ob Onb Onb (P- P Ob Onb C (CO2) H (H-

(UO2) (PO3) PO3) OH) (CO2) (CO2) bond)

[UO2 2.126 -0.559, 1.00

(H2O)5] -0.559 7
PFA -1.208 -1.189 -1.029 2.048 -0.778 -0.780 0.451 0.484
[UO2 1.943 -0.606, 0.71 -1.019 -1.085 -0.975 2.165 -0.708 -0.595 0.474 0.517
(PFAH) -0.619 8
(H2O)3]
PAA -1.203 -1.185 -1.037 2.251 -0.807 -0.801 0.737 0.486
[UO2 1.919 -0.603, 0.68 -1.034 -1.111 -0.993 2.327 -0.703 -0.621 0.792 0.517
(PAAH) -0.629 7
(H2O)3]
PPA -1.207 -1.191 -1.032 2.256 -0.808 -0.812 0.735 0.488
[UO2 1.923 -0.606, 0.67 -1.044 -1.124 -1.003 2.318 -0.667 -0.665 0.794 0.517
(PPAH) -0.639 8
(H2O)3]
*superscripts b and nb stands for bonding and non bonding atoms from the ligand respectively.

255
Table S5.3: The O-O distances in bare and complexes forms and the subtended angles at
uranium by axial oxygens of Uranyl(VI) and the coordinating atoms of the ligand in the
complex for the Uranyl(VI)-CPs.

∟O-U-O of
Bare ligand Complex ∟O-U-O of Complex
System UO2 (in
(in A0) (in A0) (in degrees)
degrees)

[UO2 (H2O)5] 180.00 --------

[UO2(PFAH)(H2O)3] 3.164 2.644 171.25 72.17

[UO2(PAAH)(H2O)3] 4.123 2.762 171.48 76.89

[UO2(3-PPAH)(H2O)3] 5.148 2.787 171.10 77.41

256
 Appendix: Chapter 6:

Scheme S6.1. Preparation step of Maline and dissolution process of UO3 in Ma

Maline (with
charge balance).

Maline

257
Scheme S6.2. Proposed schematic solvation structure model of UO22+ species in (a) Aqueous

and (b) Maline solvents. (model not in scale).

258
Scheme S6.3. (a) Steps and chemicals/Reagents
chemicals/Reagents used in the previous method of hazardous

acidic/additives dissolution of uranium matrices and their biamperometry analysis.

259
Scheme S6.3. (b) Reaction scheme and analysis process in the present developed

methodology of direct sequestering

sequestering and analysis of uranium matrices with Maline

supramolecular scaffold.

(Maline-H+ means: Removal of one H+ from Maline.)

(Maline-2H+ means: Removal of two H+ from Maline.)

260
 (a) (b)

(c)

Figure S6.1. DPV plots (a) For the of UO3, UN, UO2, U3O8 and blank Maline and (b) For the
U std., U metal, U3Si2 and blank Maline (c) PuO2 and (U, Pu)O2.

261
 80 12
g(r)U-Cl

60 9

water
g(r)U-O
g(r)U-Cl

40 6

20 3

0
0 2 4 6 8 10
0
0 2 4 6 8 10
o
r(A ) o
r(A )
a
(a) (b)

Figure S6.2. (a) and (b) are the calculated radial distribution function (RDF) for U-Cl- and
U-Owater.

90 12

75

60 8
mal
g(r)U-Br

g(r)U-O

45

30 4

15

0 0
0 2 4 6 8 10 0 2 4 6 8 10
o 0
r(A ) r(A )

(a) (b)

Figure S6.3. Calculated radial distribution function (RDF) for (a) U-Br- (b) U-Omalonic.

262
Table S6.1. The observed and calculated weight loss along with the predicted molecules being liberated at various temperatures in TG-
DSC. (In blank Maline and Uranium matrices dissolved Maline).

Name
of % Weight loss % Weight loss % Weight loss
Temperat Predicted Temperat Predicted Temperat Predicted
liquid
ure Molecules/at ure Molecules/at ure Molecules/
Regions of loss Regions of loss Regions of loss
Range of oms loss Range of oms loss Range of atoms loss
R1 R2 R3
R1 loss for from the loss R2 loss for from the loss R3 loss for from the loss
( ( (
(obser R1/ 0C in weight (observ R2/0C in weight (observ R3/0C in weight
Calculat Calculat Calculat
ved) ed) ed)
ed) ed) ed)
Maline
Choline
DES 43.3 43 100-266 Malonic acid - - 54.5 57.2 266-332
Chloride
Solutio
n of 2Choline 2malonate+8
44.5 42 100-242 8.33 9.0 242-276 2H2O+2H2O 44.1 276-320
UO3 in moity+7H2O 44.8 H2O
DES
Solutio
n of 2Choline 2malonate+7
40.5 42 100-240 15.2 13.7 242-286 2HCl+2H2O 41.8 41.8 286-326
UO2 in moity+7H2O H2O
DES
Solutio
n of 2Choline 2malonate+6
45.5 42 100-240 14.6 13.7 240-287 2HCl+2H2O 38.14 39.6 287-326
UN in moity+7H2O H2O
DES

263
 Appendix: Chapter 6 part (b)

Scheme S6.4: Reduction mechanism of imidazolium-based DES 1 and 2.

264
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 Publications

Publications in Refereed Journal:

a. Published: 07
1. Redox speciation of uranium with phenylphosphonic acid (PPA) in aqueous medium,
Ashutosh Srivastava et al. “Radiochim. Acta” 105 4 (2017) 311–320.

2. Redox speciation of uranyl in citrate medium: kinetics and reduction mechanism with in
situ spectroelectrochemical investigation. Ashutosh Srivastava et al. “New Journal of
Chemistry” 41, no. 24 (2017): 15094-15104.

3. Electrochemical, spectroscopic, and theoretical studies on redox speciation of neptunium

with phenylphosphonic acid. Ashutosh Srivastava et al. “Inorganica Chimica Acta” 482
(2018): 307-316.

4. New Greener and Sustainable Methodology for Direct Sequestering and Analysis of
Uranium Using a Maline Supramolecular Scaffold and Mechanistic Understanding through
Speciation and Interaction Studies. Ashutosh Srivastava et al. “ACS Sustainable Chem.
Eng.” 2021, 9, 23, 7846–7862.

5. New deep eutectic solvents based on imidazolium cation: Probing redox speciation of
uranium oxides by electrochemical and theoretical simulations. Ashutosh Srivastava et al.
“Journal of Electroanalytical Chemistry” 901 (2021): 115752.

6. Chemical and Redox Speciation of Uranyl with Three Environmentally Relevant

Bifunctional Chelates: Multi-Technique Approach Combined with Theoretical Estimations.
Ashutosh Srivastava et al. “Inorganic Chemistry” 61, no. 39 (2022): 15452-15462. (DOI:
https://doi.org/10.1021/acs.inorgchem.2c01991).

7. Dumpala, Rama Mohana Rao, Ashutosh Srivastava, Protonation of

Phosphonocarboxylates in Aqueous Medium: An Experimental and Theoretical Investigation.
“Journal of Chemical & Engineering Data” 67, no. 9 (2022): 2174-2181.

Some others papers as a second author

1. Dumpala, Rama Mohana Rao, Ashutosh Srivastava, and Neetika Rawat. "Experimental
and theoretical approach to probe the aquatic speciation of transuranic (neptunyl) ion in
presence of two omnipresent organic moieties." Chemosphere 273 (2021): 129745.

2. Rao, Ankita, and Ashutosh Srivastava. "Supercritical carbon dioxide and eutectic solvent
in conjunction: Novel method for in-situ solvent preparation-dissolution and uranium
extraction from solid matrices." Separation and Purification Technology 257 (2021): 117950.

Conference/Symposium: 01 (Speciation of Americium in Malonic acid based Deep eutectic

solvents. Ashutosh Srivastava et al. 15th Biennial DAE BRNS Symposium Nuclear and
Radiochemistry (NUCAR-2021), Feb 22-26, 2022, BARC, Mumbai)

279
 pubs.acs.org/IC Article

Chemical and Redox Speciation of Uranyl with Three

Environmentally Relevant Bifunctional Chelates: Multi-Technique
Approach Combined with Theoretical Estimations
Ashutosh Srivastava, Rama Mohana Rao Dumpala,* Pranaw Kumar, Ravi Kumar, and Neetika Rawat
Cite This: https://doi.org/10.1021/acs.inorgchem.2c01991 Read Online

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ABSTRACT: Carbon and phosphorous are two primary elements common to the
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bio-geosphere and are omnipresent in both biotic and abiotic arenas. Phosphonate





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and carboxylate are considered as building blocks of glyphosate and humic





substances and constituents of the cellular wall of bacteria and are the driving
functionalities for most of the chemical interactions involving these two elements.


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Phosphonocarboxylates, a combination of both the functionalities in one moiety,

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are ideal models to dig deep into for understanding the chemical interactions of the


 




two functional groups with metal ions. Phosphorous and carbon majorly exist as


inorganic/organic phosphate and carboxylate, respectively, in the bio-geosphere.










Aquatic contamination is a major concern for uranium, and the presence of




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complexing agents would alter the uranium concentrations in aquifers.



Determination of solution thermodynamic parameters, speciation plots, redox

patterns, Eh−pH diagrams, coordination structures, and molecular-level under-

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standing by density functional theory calculations was carried out to interpret the uranyl (UO22+) interaction with three


environmentally relevant phosphonocarboxylates, namely, phosphono-formic acid (PFA), phosphono-acetic acid (PAA), and
phosphono-propanoic acid (PPA). UO22+ forms 1:1 complexes with the three phosphonocarboxylates in the monoprotonated form,
-




having nearly the same stability, and the complexes [UO2(PFAH)], [UO2(PAAH)], and [UO2(PPAH)] involve chelate formation of



 

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five, six, and seven membered rings, respectively, through the participation of an oxygen each from the carboxylate and phosphonate,
strengthened by an intra-molecular hydrogen bonding through the proton of the phosphonate moiety with uranyl oxygen. The



complex formations are favored both enthalpically and entropically, with the latter being more contributive to the overall free energy
of formation. The redox speciation showed an aqueous soluble complex formation over a wide pH range of 1−8. Electrospray
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ionization mass spectrometry and extended X-ray absorption fine structure established the coordination modes, which are further
corroborated by density functional calculations. The knowledge gained from the present studies provide potential inputs in framing
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the cleanup, sequestering, microbial, and bio-remediation strategies for uranyl from aquatic environments.


 

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1. INTRODUCTION aqueous soluble complexes and altering the redox energetic

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and kinetics of UO22+ species.12−15



Safe handling of radioactive waste is a prime concern for the

The ubiquitously present carbon and phosphorous in bio-
progress and public acceptance of nuclear energy. Uranium, a geospheres have proven applications in the bio-arena as
key fuel element, needs to be contained and concealed to metabolites, informers, and structure builders.16−18 The
minimize the environmental as well as biological hazards posed actively reacting species of these elements in the flora and
by its radio and chemical toxicity.1−4 Mining and milling, fauna are in the form of carboxylate and phosphonates,19,20 and
releases from tail ponds, weapon testing, and accidental the two functional species are founding pillars of humic
releases from storage facilities could potentially contaminate substances and glyphosates.21−23 The molecules consisting of
the geosphere.5,6 Aquatic contamination is a major concern as two functional groups (phosphate and carboxylate) in a single
it can cause the migration and transportation of the entity serve as an ideal model to elucidate the physiochemical
radionuclides from the source.7−9 Precipitation, sorption,
colloid formation, and complexation are the key chemical Received: June 9, 2022
phenomena that can alter the local uranium concentra-
tions.10−12 Further, the physiochemical conditions of the
environment (Eh and pH) will lead to redox speciation as well.
Chelating moieties significantly influence the migration of U in
the aquifer through strong chemical interaction via forming

© XXXX American Chemical Society https://doi.org/10.1021/acs.inorgchem.2c01991

A Inorg. Chem. XXXX, XXX, XXX−XXX
 NJC
View Article Online
PAPER View Journal | View Issue

Redox speciation of uranyl in citrate medium:



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kinetics and reduction mechanism with in situ
Cite this: New J. Chem., 2017,



41, 15094 spectroelectrochemical investigation†


Ashutosh Srivastava,‡a Ashis K. Satpati, ‡b Ritu Singh,a Pranaw Kumar, c






Sumit Kumara and Bhupendra S. Tomar ‡*a




Electrochemical methodology, viz. cyclic and square wave voltammetry, was used to investigate the


dominant species of UO22+–citrate at particular physiochemical conditions on the basis of their redox


behavior. The UO22+ in citrate media exists as UO22+, monomer [UO2Cit]ÿ, dimer [(UO2)2Cit2]2ÿ and polymeric





species. [UO2Cit]ÿ and [(UO2)2Cit2]2ÿ were found to be reduced in two irreversible one-electron steps,



with a chemical reaction coupled between them (ICI reduction mechanism), to a stable [UIVCit]+ species



at pH r 5 and via a single reduction step with two-electron transfers at pH 4 5. Chronopotentiometry



and chronoamperometry techniques were applied to corroborate the finding of an ICI reduction
 
mechanism, and to explore the kinetics of reduction by evaluating heterogeneous electron-transfer
kinetic (k0f,h and a) parameters. Using the Deford–Hume formula, the stability constant (log b) of mono-






meric species was calculated to be 6.8  0.11, which is in agreement with the literature. Spectroelectro-
Received 16th May 2017, chemical measurements were carried out to validate the chemical reaction interposed between the


Accepted 30th October 2017 two-electron transfer steps. Additionally, evidence of a new U(V) species, i.e., [UVO2Cit]2ÿ, in an aqueous



 

DOI: 10.1039/c7nj01701d system was obtained by in situ spectroelectrochemical measurements during electrolysis, and its stability




constant was obtained by cyclic voltammetry. ESI-MS studies on solutions of varying UO22+ : citrate

rsc.li/njc ratios and pH were used to confirm complex stoichiometries.


 

1. Introduction hence, there has been renewed interest in the redox chemistry





of uranium and its complexes in the recent past.

Speciation studies on uranium to predict its distribution and Uranium is a redox-sensitive element and its redox chem-
fate in the environment have been of considerable interest istry is exceptionally rich and diverse11 due to readily accessible
for quite some time.1–4 This becomes important because oxidation states ranging from III to VI and the sensitivity of the
anthropogenic activities such as milling and mining may lead redox potential to the coordination environment around the
to higher concentrations of uranium in the geosphere2,5 than metal ion.11,12 Investigation of the redox properties of uranium
that naturally abundant in soil and water (2–4 ppm and 3 ppb, in the presence of chelating agents13 is important from the point
respectively). Its radiological and toxicological effects have of view of its effect on uranium speciation involving solubility,
been the subject of interest to environmentalists.5–8 Hence, complexation, sorption, precipitation, bioavailability, and toxicity,14
knowledge of the speciation of uranium and its complexes is which are remarkably dependent on the oxidation states and
interesting with regard to understanding its migration behavior physiochemical conditions, viz. the redox potential (Eh) and pH.2
in an aquifer.9,10 Uranium mobility and transportation in the Citric acid (C3H5O(COOH)3) is a naturally occurring a-hydroxy
environment is strongly dependent on its oxidation states and, polycarboxylic acid that forms strong water-soluble complexes
with both U(VI) and U(IV) over a wide range of pH.15 It is a
a
Radioanalytical Chemistry Division, Bhabha Atomic Research Centre,
versatile chelating agent, and is a common constituent of
Mumbai-400085, India. E-mail: [email protected] domestic, industrial as well as nuclear wastes. With appropriate
b
Analytical Chemistry Division, Bhabha Atomic Research Centre, Mumbai-400085, steric arrangement it forms small chelate rings in the equatorial
India plane of the uranyl ion to give highly stable uranyl chelates.2
c
Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai-400085, India
It exhibits relatively consistent removal efficiency, which has
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c7nj01701d
been used extensively for decontaminating contaminated sites
‡ Homi Bhabha National Institute, Bhabha Atomic Research Centre, Mumbai- in nuclear facilities. Uranyl ion complexation with citrate in
400085, India. environmental systems provides higher solubility, increased

15094 | New J. Chem., 2017, 41, 15094--15104 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
 ,QRUJDQLFD&KLPLFD$FWD  ²

Contents lists available at ScienceDirect

Inorganica Chimica Acta

journal homepage: www.elsevier.com/locate/ica

Research paper

Electrochemical, spectroscopic and theoretical studies on redox speciation of

neptunium with phenylphosphonic acid
Ashutosh Srivastavaa,b, Rama Mohan Rao Dumpalaa, Neetika Rawata,b, , B.S. Tomara
⁎

a
Radioanalytical chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
b
Homi Bhabha National Institute, Anushaktinagar, Mumbai 400094, India

A R T I C LE I N FO A B S T R A C T

Keywords: Neptunium (Np) is a key element of concern for the safety aspects regarding the reprocessing and handling of
Neptunium spent nuclear fuel owing to its long half life (t1/2 = 2.14 × 106 years). Np can exist in several oxidation states in
Redox speciation aquatic environments depending on the surrounding conditions in which it exists. The +5 oxidation state of Np
Phenylphosphonic acid as NpO2+ is the most stable and least binding moiety that can migrate in aquatic arena to far away positions
Spectrophotometry
from its source of origin. Humic acids, which are omnipresent in aquifers, are the major source of binding for the
Density Functional Theory
actinides including Np to facilitate their migration and transportation phenomenon. Probing the systematic
knowledge of neptunium (Np), such as, speciation and coordination as function of its oxidation states in presence
of chelating agents is essential aspect of its solution chemistry. The present study aimed at investigating the
redox and complexation of Np with phenylphosphonic acid (PhPO3H2) (PPA) as mimic for binding of aromatic
phosphorus functionalities in humic substances by using electrochemical and UV–Visible absorption spectro-
scopy and density functional calculations. The cyclic voltammetric measurement indicates the complexation of
both oxidation states (V & VI) of Np with [PhPO3]2−. The presence and stability region (via Eh-pH plot) of new
species of Np-PhPO3 in two different oxidation states (V & VI) in aqueous solution at varying physicochemical
conditions are identified. The kinetics for reduction of Np complexes in different oxidation states are explored by
evaluation of heterogeneous electron-transfer kinetic (D0, ko and α) parameters by cyclic voltammetric results.
The spectral parameters, namely λmax and its molal extinction coefficient (ε) are obtained from UV–Visible
spectrophotometric measurements and are found to be 988.2 nm and 302 ± 8 mol−1 L cm−1 respectively. The
electrochemical as well as UV–Visible spectrophotometric measurements showed the formation of 1:1 complex
only and the stability constant (logβ) obtained for the same from both the methods found to be in agreement
with each other. Density Functional Theory (DFT) calculations are carried out to optimize the geometries of Np-
PhPO3 complex for the Np in +5 and +6 oxidation states with [PhPO3]2− in mono and bidentate mode to
identify the most probable coordination mode for complex formation.

1. Introduction considered to be most problematic actinide [12]. It remains one of the

least understood major transuranium elements though several decades
The aqueous chemistry of actinides (An) is of prime concern in have passed since the first experimental isolation of Np (1940) [13]. It
nuclear engineering, especially for nuclear fuel reprocessing and risk is an α-emitter with a long half-life [e.g. t1/2
assessments of radionuclide migration in the geosphere [1–3]. Metrical (237Np) = 2.14 × 106 years], having high solubility under en-
knowledge about actinides speciation in aqueous solution is essential in vironmentally relevant conditions. Thus, the long lived 237Np builds up
understanding the actinides solubility, stability, complexation, redox in spent nuclear fuel and high level liquid waste (HLW) with time and is
reaction, sorption and reactivity, for predicting the fate and transport of one of the important radionuclide of interest to consider for the trans-
actinides under environmentally relevant conditions [4–8]. portation and migration in geosphere.
Neptunium (Np), is one of the artificial elements produced in sig- Np can exist in variety of possible oxidation states from III to VII in
nificant quantities in nuclear reactors by α decay of 241Am and (n, 2n) aqueous solution and the relative stabilities of the same are strongly
reaction of 238U followed by β decay of 237U [9]. Neptunium is key affected by pH and the presence of complexing ligands [14,15]. Np in
constituent in spent nuclear fuel, nuclear waste [9–11] and is its higher valence states viz. NpO2+ & NpO22+ are highly soluble

⁎
Corresponding author at: Radioanalytical chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India.
E-mail address: [email protected] (N. Rawat).

https://doi.org/10.1016/j.ica.2018.06.001
Received 5 March 2018; Received in revised form 31 May 2018; Accepted 1 June 2018
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 pubs.acs.org/journal/ascecg Research Article

New Greener and Sustainable Methodology for Direct Sequestering

and Analysis of Uranium Using a Maline Supramolecular Scaffold
and Mechanistic Understanding through Speciation and Interaction
Studies
Ashutosh Srivastava,* Rama Mohana Rao Dumpala, Pooja Sahu, Ashok Kumar Yadav, Neetika Rawat,*
S. k. Musharaf Ali, Manjulata Sahu, Nimai Pathak, and Arijit Sengupta

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Cite This: ACS Sustainable Chem. Eng. 2021, 9, 7846−7862 Read Online



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ABSTRACT: Research, based on the development of an economical innovative





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green technology, is the quintessential requirement for the advancement of the

nuclear fuel cycle (NFC). The present studies show that Maline, with a


 

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preorganized supramolecular scaffold, would be considered as the workhorse for



 


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its potential efficacy in diverse facets of the NFC, specifically as an elegant metal
hijacker for processing of uranium (U) matrices, designer solvent for green





analysis of U, and a promising U chelator for a greener alternative for the

 

cleanup of U contamination. Seven U matrices (UO3, UN, UO2, Rb2U(SO4)3, U






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metal, U3Si2, and (U, Pu)O2) were dissolved in Maline without any external
additives and cyclic voltammetry was performed to investigate the redox

speciation, viz., redox thermodynamics (Ep and Ef) and kinetic (D0, k0, and αn)

parameters and mechanistic electron transfer of the dissolved U species. To get

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an insight into the molecular speciation, the structural analysis on UO3 dissolved




in Maline was conducted by extended X-ray absorption fine structure, which

indicates an interesting observation of the formation of UO22+ kind of species with malonic acid and H2O at equatorial coordination.



 





Molecular dynamics and density functional theory simulations were carried out to acquire diffusion, optimized structure, binding
energy, and molecular orbital diagram of U species in Maline, to corroborate the experimental results and to shed light on the


hydrogen-bond network in Maline with aqueous dilution. The interaction of uranyl with Maline was probed by luminescence,


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absorption spectroscopy, and calorimetry titration. Green analysis methodology was developed based on Maline digestion followed


 

 

by voltammetric determination of U in nuclear material samples. Green chemistry metrics were evaluated to authenticate the greener

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aspects of the present methodology. The present developed methodology of direct sequestration and analysis of U matrices


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represents an appropriate replacement of the existing method, viz., hazardous acidic processing of U matrices followed by



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biamperometry analysis.


KEYWORDS: deep eutectic solvent, Maline, direct sequestering, redox and molecular speciation, green analysis methodology
&

■ INTRODUCTION the nuclear fuel cycle (NFC), viz., various stages of processing
Nuclear energy, a mature technology and low carbon energy and reprocessing of metal and metal oxides, namely,
source, is going to be one of the major sources of energy due to dissolution, solvent extraction, recovery, and analysis. In the
increasing power demands and the possibility of reducing NFC, the current approaches of reprocessing fall into two
greenhouse gas concentration in the atmosphere.1−6 Uranium major categories as PUREX and pyrochemical processes.10,11
(U) is primarily utilized as a fuel source for nuclear power Both these processes have certain complexities and result in
generation and its increasing demand as fuel material in the technical challenges, viz., poor atom and energy efficiencies,
nuclear technology activity evokes processing of metal oxides
present in naturally occurring ores as well as in spent nuclear
fuel (SNF) for complete utilization of its energy potential.4−6 Received: March 4, 2021
However, the prime concern of nuclear energy is the economic Revised: May 12, 2021
and environmental issues associated with managing the SNF Published: May 27, 2021
wastes due to their long-term radiotoxicity.4,7,8 Therefore,
reprocessing and management of SNF are crucial to the future
of nuclear energy.4−6,9 Solvents occupy a strategic place within

© 2021 American Chemical Society https://doi.org/10.1021/acssuschemeng.1c01499

7846 ACS Sustainable Chem. Eng. 2021, 9, 7846−7862
 Radiochim. Acta 2016; aop

Ashutosh Srivastava, Pranaw Kumar and Bhupendra S. Tomar*

Redox speciation of uranium with phenylphosphonic

acid (PPA) in aqueous medium
DOI 10.1515/ract-2016-2652 soil and sea water (2–4 ppm and 3 ppb, respectively) [1–4].
Received June 24, 2016; accepted August 9, 2016 The radiological and toxicological effects of uranium and
its daughter products are a matter of concern for human
Abstract: Studies on complexation of uranium with organ-
kind [5]. Therefore, it is important to investigate the migra-
ophosphorous ligands in aquatic systems are important
tion behavior of uranium in aquatic environment so as
from point of view of mobility of uranium in environment.
to evaluate its impact on living organisms. Uranium is
In the present paper, we report the results of complexation
a redox-sensitive element and its migration behavior is
of U(VI) by a model ligand for organophosphorus func-
dependent upon its speciation, which in turn is governed
tionalities in humic substances (HS), that is, phenylphos-
by the physicochemical conditions, viz., Eh, pH, presence
phonic acid (PPA), using electro analytical techniques.
of complexing anions (organic and inorganic), and inter-
The UO22+ has been found to form 1:1 and 1:2 complexes
action with micro-organisms [1–8]. Therefore, to evalu-
with mono-protonated PPA (HPhPO3−) and 1:1 complex
ate the speciation and mobility of uranium in geosphere,
with non-protonated PPA, (PhPO3)2−, with the latter com-
understanding of its redox chemistry is essential. Compl-
plex (UO2PhPO3) dominating over the other two species.
exation by organic chelating ligands can alter the redox
Cyclic voltammetry (CV) and differential pulse voltamme-
state of the metal ion and hence it is imperative to study
try (DPV) were used to investigate the redox behavior of
the speciation and structure of its complexes in the pres-
UO2PhPO3 species and to explore the kinetics of its reduc-
ence of chelating agents [9].
tion by evaluating heterogeneous electron-transfer kinetic
Recently, metal phosphonates have received increas-
(D, ks and α) parameters. The diffusion coefficient (D) value
ing attention because of their potential applications in ion
was found to be 6.76 × 10−5 cm2 s−1 and 5.03 × 10−5 cm2 s−1 at
exchange, catalysis, sorption, and intercalation chem-
pH 5 and 3, respectively, with rate constant, ks = 0.304 × 10−3
istry. Doubly ionizable phosphonate groups (–PO3H2)
cm/s. Using the DeFord and Hume formalism the stabil-
have many properties, which are unique, and promise
ity constant (log β) of UO2PhPO3 was calculated to be
more efficient separation processes for waste clean-up
(6.98 ± 0.12), which is in agreement with the literature data.
and environmental restoration [10, 11]. Organic and inor-
Electrospray ionization mass spectrometry (ESI-MS) stud-
ganic phosphorus containing ligands which are perva-
ies corroborated the existence of UO2PhPO3 complex.
sive in soil systems are known to form strong complexes
Keywords: Redox speciation, uranium, phenyl phospho- with uranium. High proportion of phosphorus exists in
nic acid, stability constant, cyclic voltammetry, differen- organic forms, as derivatives of phospholipids, phospho-
tial pulse voltammetry. nic acids, phosphoric mono- and diesters in soils rich in
organic matter [12]. Though relatively low content of P
(800–1500 mg/kg) is found in humic substances, organic
compounds containing P=O and P–OH functionalities
1 Introduction show excellent complexing tendencies towards metal
center [13–15] and are presumed to play a remarkable
Large scale mining of uranium for use in nuclear indus-
role in binding of uranyl ion by HS. The complexation
try as a fuel has resulted in its higher concentrations in
tendency of phenylphosphonic acid (PPA) for uranyl ion
mill tailing ponds compared to the natural abundance in
is stronger than that reported for the isostructural car-
boxylic acid [11, 16]. Higher stability of the phosphonate
complexes of the uranyl ion with regard to the correspond-
*Corresponding author: Bhupendra S. Tomar, Radioanalytical ing carboxylate is due to differences in net electrostatic
Chemistry Division, Bhabha Atomic Research Centre, charge and basicity between the phosphonate and the
Mumbai-400085, India, E-mail: [email protected]
carboxylate ligands [17] as well as an entropic effect of
Ashutosh Srivastava: Radioanalytical Chemistry Division, Bhabha
Atomic Research Centre, Mumbai-400085, India
the phosphonate unit having more potentially binding
Pranaw Kumar: Fuel Chemistry Division, Bhabha Atomic Research oxygen atoms than that in carboxylates [18]. Further, the
Centre, Mumbai-400085, India complexation of uranium (VI) by P-containing ligands is

Brought to you by | Bhabha Atomic Research Centre

Authenticated
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 Journal of Electroanalytical Chemistry 901 (2021) 115752

Contents lists available at ScienceDirect

Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

New deep eutectic solvents based on imidazolium cation: Probing redox

speciation of uranium oxides by electrochemical and theoretical simulations
Ashutosh Srivastava a,b, Pooja Sahu c, M.S. Murali a,b,⇑, Sk. Musharaf Ali c, Manjulata Sahu d, Jisha S. Pillai e,
Neetika Rawat a,b
a
Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai, 400085, India
b
Homi Bhabha National Institute, Anushaktinagar, Mumbai, 400094, India
c
Chemical Engineering Division, Bhabha Atomic Research Centre, Trombay, Mumbai, 400085, India
d
Radioanalytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai, 400085,India
e
Fuel Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai, 400085, India

A R T I C L E I N F O A B S T R A C T

Keywords: Two new deep eutectic solvents, different from hitherto known and based on common choline chloride, were
Deep eutectic solvents prepared. 1-methyl-3-decylimidazolium bromide mixed with hydrogen bond donors, malonic acid and digly-
Uranium oxides colic acid to form DES. Dissolution of uranium oxides (UO3 and UO2) was explored in both of them and char-
Redox speciation acterization of the resultant solutions was carried out by IR, TGA and UV–Vis spectroscopy. Redox speciation of
Cyclic voltammetry
dissolved uranium oxides was probed in these redox-active DES through cyclic voltammetry, differential pulse
In situ Spectroelectrochemistry
Theoretical simulations
voltammetry and in situ spectroelectrochemical measurements. Interestingly, the formation of uranium oxo
species was observed through the dissolution of UO3 in both the DES. The electrochemical characteristics
viz. redox thermodynamics (peak potential and formal redox potential), transport property (diffusion coeffi-
cient D0), heterogeneous electron transfer kinetic parameters (αn and k0) and mechanistic electron transfer
of the dissolved uranium species in two DES were investigated. The speciation of uranium was decoded
through the electronic absorption spectra of uranium in its lower oxidation states [U(V) and U(IV)] acquired
through in situ spectroelectrochemical electrolysis with varying cathodic potentials. Studies were also carried
out using Molecular Dynamics (MD) and density functional theory (DFT) simulations to authenticate the elec-
trochemical outcomes and to acquire the binding energy, optimized structure and molecular orbital diagram of
dissolved uranium species. Further, the MD simulation sheds light on the probable equatorial coordinating
atoms of dissolved uranium species. This is the first report, to the best of our knowledge, on imidazolium-based
DES and actinide ions.

1. Introduction of U and Pu take place. However, a few disadvantages of this process

such as generation of large volumes of hazardous acidic wastes, hydro-
Nuclear energy, slated to be one of the cleanest energy sources with lytic and radiolytic degradation of the solvent, TBP, its inability to
minimal carbon footprints, is on the rise recently (by way of more extract trivalent actinides in normal acidic conditions of the spent fuel
reactors under construction) to meet the energy needs of the globe broth etc. These drawbacks drove us for finding alternate methods/sol-
[1]. The nuclear industry envisages the use of actinide fuels and once vents for aqueous reprocessing and for other activities at the back-end
their useful life in the reactors is over, they need to be reprocessed for of the nuclear fuel cycle (NFC). The first step in reprocessing involves
a closed fuel cycle. For the reprocessing of these fuels, a well-known the dissolution of oxide fuels (mainly uranium) and later recovery of
aqueous process called “PUREX” (Plutonium Uranium Extraction) (em- the fissile materials from other fission products either by stripping
ploying an extractant, namely, tri-n-butyl phosphate (TBP) in a paraf- by chemical methods or by electrochemical means. In “PUREX” pro-
finic diluent with some modifications from the original [2]) is cess, the dissolution of oxide fuels takes place usually in very concen-
followed all over the world. In the PUREX process, the separation of trated nitric acid (∼13 M HNO3) handling of which creates operational
U from Pu and other fission products in the spent fuel and the recovery hurdles due to the generation of toxic NOx gaseous products and cor-

⇑ Corresponding author at: Radiochemistry Division, Bhabha Atomic Research Centre, India.
E-mail address: [email protected] (M.S. Murali).

https://doi.org/10.1016/j.jelechem.2021.115752
Received 22 March 2021; Received in revised form 10 September 2021; Accepted 30 September 2021
Available online 05 October 2021
1572-6657/© 2021 Elsevier B.V. All rights reserved.
 15th Biennial DAE BRNS Symposium Nuclear and Radiochemistry (NUCAR-2021), Feb 22-26, 2022, BARC, Mumbai

(Category – 3 (Chemistry & Spectroscopy of actinides)

Speciation of Americium in Malonic acid based Deep eutectic solvents

Ashutosh Srivastava 1,*, Jisha S. Pillai2, Sk. Musharaf Ali3, Neetika Rawat1, S. Chaudhury2,*
1
Radiochemistry Division, 2Fuel Chemistry Division, 3Chemical Engineering Division,
Bhabha Atomic Research Centre, Trombay, Mumbai – 400 085
(*Corresponding Author Email: [email protected]; [email protected])

Probing speciation of Americium (Am) in deep eutectic solvent (DES) is indispensable for the
advancement of spent nuclear fuel (SNF) reprocessing based on liquid-liquid extraction as in the case
of SESAME and SANEX processes and for the growth of analytical tools including coulometry and
redox titration for Am analysis [1]. Am separation from SNF is highly challenging due to its similar
chemical and physical properties compared to the lanthanides (Ln). Selective extraction of Am vs. Ln
through judicious ligand design is the mainstream approach for Am separation but this approach
requires multiple steps and can cause more down-stream complication. Selective oxidation of Am(III)
to its higher oxidation state is another approach which could facilitate its separation from lanthanides.
Therefore, development of electrochemical methodology for selective oxidation of Am to its higher
oxidation which could facilitate its separation from curium (Cm) as well as lanthanides has become a
recent research interest. In this context, DESs, an interesting new class of green and eco-sustainable
solvents which shown their usefulness as environmentally benign alternatives to conventional organic
solvents and ionic liquid, would be a suitable choice. DESs are a kind of eutectic mixture of hydrogen
bond acceptors (HBAs) and hydrogen bond donors (HBDs) with a considerably lower melting point
than its original components. DESs have some fascinating and tailored properties (large solubility with
metal oxides, wide potential windows, and the possibility of tuning the properties of DES by changing
the functional groups of solvent components) which make them promising electrolytes for
electrochemical processes and a good candidate for selective coordination of actinides. Owing to
unique physicochemical properties of DES, the speciation of actinides in DES might be different
compare to that in aqueous/ionic liquid medium. Literature survey indicates the use of DES as co-
solvent for Am separation [2] however, no studies have been reported on the speciation of Am in DES.
The aim of the present study is to describe the speciation of Am in two DES containing mainly oxygen
atoms as functional moiety viz., Choline dihydrogen Citrate-Malonic acid (CDHC-MA) and Choline
Chloride-Malonic acid (CC-MA). The Am-oxide was dissolved in both DES and the dissolved
solutions were characterized by UV-visible spectroscopy [Table 1]. The results indicate Am (III)-DES
complex species formation in both DES through dissolution process. In depth analysis on the
electrochemical oxidation of Am(III) in both DES were carried out by cyclic and differential pulse
voltammetry, indicates (i) one oxidative peak with one electron transfer as Am(III) to Am(IV) and
hence Am(III) can be easily oxidized to stable Am(IV), (ii) Am(IV) is a stable oxidation state in both
DES and (iii) Am(III)-Am(IV) conversion has much lower oxidation potential (~ 0.68 V) in DES
compared to that in aqueous medium (i.e., 2.6 V vs. SCE). The redox parameters (peak potential and
diffusion coefficient) of above oxidation process have been reported in Table 1. Theoretical
calculations were performed to corroborate the electrochemical results and to obtain the optimized
structure and energetic [Table 1] of Am in both DES [1:2 type
complexes formed].
Table 1. Experimentally and theoretically obtained parameters of Am in DES

Parameters CDHC-MA CC-MA

λmax Am (III) 485 nm 502 nm
E (V) [Am(III)-Am(IV)] 0.68 0.606
Diffusion coefficient (D0) 1.05x10-8 cm2/sec 1.50x10-8 cm2/sec
Free energy (Complex) -52.12 kcal/mole -50.12 kcal/mole

References: 1. S. Picart et al., ATALANTE-2004 P2-P4. Nimes, France, June 21-25 (2004).
2. G. Colombo Dugoni et al., ACS omega, 6(5), 3602 (2021).