Study of Actinide cations in solution through their paramagnetic behavior

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Study of Actinide cations in solution through their

paramagnetic behavior

M.-C. Illy, M. Autillo, L. Guerin, D. Guillaumont, P. Moisy, Hélène Bolvin, C.

Berthon

To cite this version:

M.-C. Illy, M. Autillo, L. Guerin, D. Guillaumont, P. Moisy, et al.. Study of Actinide cations in solution

through their paramagnetic behavior. ACS 253rd National Meeting, Apr 2017, San Francisco, United

States. �cea-02434027�

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www.cea.fr

STUDY OF ACTINIDE CATIONS

IN SOLUTION THROUGH

THEIR PARAMAGNETIC

BEHAVIOR

APRIL 6

TH

_{, 2017}

ACS 253

rd

_{National Meeting, San Francisco, CA, USA}

_|

Marie-Claire ILLY

, PhD Student, CEA MARCOULE, France

Matthieu AUTILLO, Laetitia GUERIN, Dominique GUILLAUMONT,

Philippe MOISY, Hélène BOLVIN, Claude BERTHON

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INTRODUCTION

Context of the study

1ER MARS 2017 ACS 253rd_{National Meeting, SF, CA, USA | CEA Marie-Claire ILLY | April 6}th_{, 2017}| PAGE 2

4f

5f

0 _5f

14 Goal: A better understanding of the 5f electrons behavior.

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WORKPLAN

| PAGE 3 ACS 253rd_{National Meeting, SF, CA, USA | CEA | April 6}th_{, 2017}

Magnetic Susceptibility

The Evans Method

Previous works

In this study

Modeling of An(IV) chloride complexes Magnetic Susceptibility

Study of UV-Visible Spectra

The NMR analysis with radioactive elements

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THE NMR ANALYSIS WITH RADIOACTIVE ELEMENTS

Farnan, I.; Berthon, C. SPR-Nuclear Magnetic Resonance, 2016, vol. 45, 96-141.

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MAGNETIC SUSCEPTIBILITY

The Evans Method

| PAGE 5 ACS 253rd_{National Meeting, SF, CA, USA | CEA Marie-Claire ILLY | April 6}th_{, 2017}

𝝌

_𝑴

𝒆𝒙𝒑 =

𝟑∆𝜹

𝒕𝑩𝒖𝑶𝑯

𝑪

(𝒎

𝟑 . 𝒎𝒐𝒍

−𝟏

)

Evans, D. F. Journal of the Chemical Society, 1959, 2003-2005. Grant, D. H. Journal of Chemical Education, 1995, 72(1), 39-40.

Screw Cap

Teflon Plug

5 mm bulb of the

glass

tube

Teflon tube

Work solution :

reference solution + sample

Reference solution :

HClO

4

(1M) + tBuOH

tBuOH, int tBuOH, ext H₂O, int H2O, ext Paramagnetic shift (ppm)

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0

1

2

3

4

5

6

7

8

9

10

11

12

13

0

1

2

3

4

5

6

7

8

9 10 11 12 13 14

E

ff

e

c

tiv

e

m

a

gnetic

m

ome

nt

m

e ff

a

t 25

°C

Orbital configuration 5f

U(VI)

U(IV)

_Np(IV)

Pu(III)

Am(III)

Cm(III)

Cf(III)

Pu(IV)

Np(VI)

Pu(VI)

Np(V)

Th(IV)

MAGNETIC SUSCEPTIBILITY

Previous works

| PAGE 6 ACS 253rd_{National Meeting, SF, CA, USA | CEA Marie-Claire ILLY | April 6}th_{, 2017}

Hund Equation

Van Vleck Equation for Ln(III)

An(III)

An(IV)

An(V) An(VI)

Wall, T. and al., Inorg. Chem., 2014, 53, 2450-2459.

Three PhD works : Wall T., Jan S. and Autillo M.

Magnetic Susceptibility of An(III, IV, V and VI) in aqueous media.

α and β

radioactivities

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MAGNETIC SUSCEPTIBILITY

Previous works

𝝌

_{𝒓𝒂𝒅𝒊𝒐𝒂𝒄𝒕𝒊𝒗𝒊𝒕é}

=

𝝌

_{𝒓𝒂𝒅𝒊𝒄𝒂𝒖𝒙}

+

𝝌

_𝜷

Am(III)

Autillo, M. and al., PCCP, 2014, 16, 8608-8614.

α emissions

Alpha radiolyses of water : Radicals production

OH°

O°

H°

Solutions

With UO

₂2+

₍

238

_{U /}

233

_{U) and}

Am

3+

₍

241

_Am/

243

_Am)

α radioactivity (GBq/L)

C

u

ri

e

co

n

stan

t

(10

-8

m

3

.K

/mol

)

238,233

_U

241,243

_Am

Pu(III)

β emissions

Solutions

with Nd

3+

_in

3

_H

Solvated electrons

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MAGNETIC SUSCEPTIBILITY

Previous works

1ER MARS 2017 ACS 253rd National Meeting, SF, CA, USA | CEA Marie-Claire ILLY | April 6th, 2017 | PAGE 8

1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 χM (1 0 -8 m 3/m o l)

U(IV)

Np(IV)

Pu(IV)

HClO4 HCl HNO3 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 0 1 2 3 4 5 6 7 8 9 χM (10 -8 m 3/m o l) [Cl-] (mol/L) Pu(IV) Np(IV) U(IV)

Nature and concentration in anions

Ligand field

_{Quantum Mechanics (Modeling)}

Bolvin H. from Toulouse University (France)

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MODELING

An(IV)-Cl Magnetic Susceptibility

Magnetic

Susceptibility

UV-Visible

Spectrum

Electronic states

Collaboration with Bolvin, H. from Toulouse University (France)

𝝌

_𝑴

=

𝑪

𝑻

+ 𝝌

𝑻𝑰𝑷

𝝌

𝑴

(10

-8

m

3

/mol)

1/T (K

-1

₎

Between 25°C and 80°C

Curie Law

U

+IV

Np

+IV

Pu

+IV

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MODELING

An(IV)-Cl Magnetic Susceptibility

2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 0,00299 0,00319 0,00339 0,00359 0,00379 0,00399

Mol

ar

ma

gn

et

ic

su

sc

ep

ti

b

il

it

y

χ

M

(

10

-8

m

3

/mo

l)

1/T (K

-1

₎

χ

_M

= f(1/T) for U(IV)-Cl complexes (5f

2 ₎

1M

3M

6M

9M

(12)

MODELING

An(IV)-Cl Magnetic Susceptibility

2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 0,00299 0,00319 0,00339 0,00359 0,00379 0,00399

Mol

ar

ma

gn

et

ic

su

sc

ep

ti

b

il

it

y

χ

M

(

10

-8

m

3

/mo

l)

1/T (K

-1

₎

χ

_M

= f(1/T) for U(IV)-Cl complexes (5f

2 ₎

U4_Cl6

U4_Cl6_distance

U4_Cl6_angle

1M

3M

6M

9M

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MODELING

An(IV)-Cl Magnetic Susceptibility

2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 0,00299 0,00319 0,00339 0,00359 0,00379 0,00399

Mol

ar

ma

gn

et

ic

su

sc

ep

ti

b

il

it

y

χ

M

(

10

-8

m

3

/mo

l)

1/T (K

-1

₎

χ

_M

= f(1/T) for U(IV)-Cl complexes (5f

2 ₎

U4_Cl6

U4_Cl6_distance

U4_Cl6_angle

1M

3M

6M

9M

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-2 8 18 28 38 48 58 350 400 450 500 550 600 650 700 750 800 850 ε (L/ m o l/ cm ) λ (nm)

LiCl (9M)

MODELING

U(IV)-Cl UV-Visible Spectrum

U

IV

Cl

₃

(H

₂

O)

₅

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-2 8 18 28 38 48 58 350 400 450 500 550 600 650 700 750 800 850 ε (L/ m o l/ cm ) λ (nm) U4+-cl3-5h2o pos1 U4+-cl3-5h2o pos2 LiCl-9M

MODELING

U(IV)-Cl UV-Visible Spectrum

U

IV

Cl

₃

(H

₂

O)

₅

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MODELING

U(IV)-Cl UV-Visible Spectrum

U

IV

Cl

₃

(H

₂

O)

₅

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Magnetic susceptibility: Influence of different parameters

UV-Visible spectra: first calculations, better understanding

not yet completed, finalized.

Narrow temperature range for NMR analyses 278 – 333/353K

0 – 300K for Magnetism analyses

Ongoing article about

Actinide ions in solution: NMR shift probes for conformational studies.

Actinides Induced Shift (AIS) ≡ Lanthanides Induced Shift (LIS)

CONCLUSIONS & OUTLOOK

| PAGE 16

“Modeling of Magnetic Susceptibility of An(IV)-chloride complexes”

Illy, M.-C.; Autillo, M.; Guerin, L.; Bolvin, H.; Guillaumont, D.; Berthon, C.; Moisy, P.

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DEN DMRC SPDS LILA

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