A

Molecular Dynamics Study

on the liquid-liquid extraction of
Uranyl ions with Tri-Butyl-Phosphate

Figure 1: Structure of TBP molecule.

Mark Thomas
1. Introduction
Nuclear reprocessing is becoming an increasingly important process in a time where there is a large focus on the sustainability of power generation. Not only can it
reduce the high-level waste volume, but can improve the eciency of the cycle, by recycling unreacted fuel. The PUREX process is the most widely used method.
1) The fuel rods are dissolved in nitric acid;
3) The TBP selectively binds to uranyl nitrate;
2) This is then contacted with an organic phase containing 30% v/v 4)
These
neutral complexes readily migrate into the organic phase.
tri-butyl-phosphate (TBP) (as seen in gure 1) in dodecane;

(UO22+)aq+2(NO3-)aq+2(TBP)org ??? (UO2(NO3)2 2TBP)org

Although widely used since the 1950s , there are many aspects of the process that are not understood on a molecular level. The TBP tends to form structures called
reverse micelles around polar molecules such as water and acids due to its hydrophilic and hydrophobic properties, aggregating at the interface [1]. The particular
mechanism of the extraction around the interface is unknown. Moreover, there have been continuous improvements in the force eld models used for Molecular
Dynamics (MD) simulations, meaning that the validity of earlier results are now bought into question. The drivers for third phase formation are still unknown, an
occurrence that can seriously impair the liquid-liquid extraction.

2. Motivations & Objectives

Motivations
Increase eciency of process by gaining further understanding on rate of
mass transfer and partitioning coecients
To further understand the driving forces of third phase so it can be avoided
Objectives
Systematically and rigorously test the force eld models for TBP, water and
dodecane
Gain further insight into the kinetics, complexation and extraction
mechanisms

3. Methodology
Table 1: Force elds used for system and each molecule.
GROMACS 4.6.7
NPT 1 atm Berendsen barostat. 298.15 K
Force Field
v-rescale thermostat [2]
System
OPLS-2005 [3]
Time step of 1 ps
TBP
MNDO & DL
Energy minimisation followed by MD

Water
Dodecane
HNO3
UO2+

TIP3P & SPC/E

OPLS-AA
ESP [4]
QM [5]

4. Binary System

5. Ternary System

New TBP partial charges optimised for the description of a TBP/dodecane system, were
found to lead to TBP/water immiscibility, counter to experimental observation. It is known
that saturation point TBP:H2O is 1:1 [6].
Changing Lennard-Jones (LJ) potentials had little eect on structure
Scaling partial charges on TBP resulted in homogenous mixture and better
thermodynamic properties of system (reasonable description of TBP/dodecane also)
0.9 best match with free energy of solvation, 0.8 best match with excess enthalpy of
mixing. 0.84 OPLS-MNDO compromise was taken

A new charged dodecane model was developed to prevent liquid-gel

phase transition. Dodecane was added into the system for 3 dierent
TBP:H2O ratios. Hydrophobic dodecane avoids contact with water.
Resulted in single phase with possible reverse micelles formed.
P-OW
H2O-ddc

Figure 8: RDF of ddc-H2O & P-OW for ternary system.

Figure 7: Uncharged and charged dodecane model (PURE).

Figure 3: 0.84 MNDO TBP (PINK) & TIP3P H2O (PURPLE).

Figure 2: 0.6 MNDO TBP (PINK) & TIP3P H2O (PURPLE).

Table 2: Eect of charge of free

energy of solvation.
Systems Free energy of

2
Simulation

Excess enthaly of mixing (kJ/mol)

-1

-2

-3

-4
0.7

0.8
0.9
Scaling factor for MNDO charge

Figure 5: Eect of partial charges on enthalpy of system.

0.60 MNDO
0.84 MNDO
0.9 MNDO
LJ 1.25
LJ 1.75
LJ 2
LJ - 5

solvation of H2O
in TBP (kJ mol-1)

Experimental

0.6

Figure 4: TBP (RIGHT) & H2O (LEFT) dimer formed in system.

Experimental

-19.58112

0.60 MNDO

-6.12 0.29

0.70 MNDO

-10.14 0.79

0.80 MNDO

-15.47 0.57

0.81 MNDO

-15.18 0.25

0.82 MNDO

-16.66 0.39

0.83 MNDO

-14.38 0.52

0.84 MNDO

-17.05 0.96

0.85 MNDO

-14.54 0.15

0.86 MNDO

-17.71 0.81

0.87 MNDO

-18.99 0.61

0.88 MNDO

-20.93 1.04

0.89 MNDO

-19.29 1.50

0.90 MNDO

-19.75 0.41

1.00 MNDO

-22.84 0.92

Figure 6: RDF of OW-OW interactions. Eect of partial charges & LJ scaling.

7. Umbrella Sampling

Uranyl nitrate ion was pulled across interface,

e x p e c t e d t o l o s e 2 ( H 2 O ) a n d f o r m
(UO2(NO3)22TBP). Uranyl nitrate in fact pulled
water across interface and did not bind with TBP.
Gibbs free energy prole indicates that extrachon
process is unfavourable, with an achvahon energy
of 60 kJ mol-1. This result can not be true otherwise
the PUREX process wouldn't work, and we believe
we have seriously undereshmated the anrachons
between TBP and uranyl. Double Pull simulahon,
showed that organic phase is more favourable than
interface.

6. Quaternary System
Nitric acid was added into
the system. Emulsion like
structure observed. No H2O-
dcc interactions, but HNO3
slightly more dispersed.
Down to more negatively
charged H atom. Reverse
micelles formed protecting
polar molecules from ddc.
Figure 10: TBP (RIGHT) & HNO3 (LEFT) dimer.

Figure 11: TBP (GREEN), HNO3 (RED) H2O (BLUE).

8. Conclusion

kJ mol-1

Gibbs Free Energy Prole

Double Pull

Figure 12: Gibbs free energy curve for pulling & double pulling simulation.

The TBP scaling factor 0.6 underestimated intermolecular forces. A factor of

0.84 or 0.9 OPLS-MNDO is recommended
The unchanged OPLS-AA dodecane prevents liquid-gel phase transition
Current force eld models do not favour uranyl extraction, despite formation
of reverse micelles
Recommendations
Add polarizabilities to force eld models, in particular phosphate head
Increase LJ potential between uranyl and TBP
Carry out/compare results to additional experimental data (neutron scattering
& x-ray diraction)

Table 3: Composition of
pulling simulations.

Aq

nH2O

1247

nHNO3 35

nTBP

38

nDDC

108

nH3O+

210

nNO3-

210

10. Bibliography

9. Acknowledgements

Figure 13: Pulling of uranyl ion (RED) from the aqueous phase consisting of NO3- (GREEN), H3O+ (ORANGE) & H2O (BLUE).

The author would like to thank Junju Mu, Karl

Fairhurst and Gareth Myers for their results and
continuing cooperation, and Andrew Masters
for his limitless help and knowledge
throughout.

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Figure 9: TBP (GREEN) & H2O (BLUE) for ternary system.