Uranium tetrafluoride was synthesized using a novel method, which consists of a combination of carbochlorination reaction between a mixture of U3O8 and sucrose carbon with chlorine, and a solid-state halogen exchange reaction between the products of the carbochlorination reaction and sodium fluoride. The thermodynamic feasibility to produce the halogen exchange reaction between UCl4 and NaF was analyzed. Reactions are favorable in standard conditions, even at low temperature. We have prepared a mixture of UCl4 and UCl2O2 by U3O8 treatment in Cl2 atmosphere with presence of sucrose carbon at 900 °C. UCl4 and UCl2O2 were obtained as a condensed product, which was collected in a quartz capsule containing NaF. The capsules were sealed after several repeated stages of argon purges and mechanic vacuum. Subsequently, they were treated at 300–350 °C for 2 h. We obtained that when NaF is the limiting reagent, the solid product of the thermal treatment of the capsules consists in a mixture of UF4 and NaCl. Solid products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), fluorescence spectroscopy, and energy dispersive X-ray spectroscopy. Gaseous products were identified by Fourier-transform infrared spectroscopy.

References

References
1.
Delpech
,
S.
,
Merle-Lucotte
,
E.
,
Heuer
,
D.
,
Allibert
,
M.
,
Ghetta
,
V.
,
Le-Brun
,
C.
,
Doligez
,
X.
, and
Picard
,
G.
,
2009
, “
Reactor Physic and Reprocessing Scheme for Innovative Molten Salt Reactor System
,”
J. Fluorine Chem.
,
130
(
1
), pp.
11
17
.
2.
Forsberg
,
C. W.
,
Peterson
,
P. F.
, and
Pickard
,
P. S.
,
2003
, “
Molten-Salt-Cooled Advanced High-Temperature Reactor for Production of Hydrogen and Electricity
,”
Nucl. Technol.
,
144
(
3
), pp.
289
302
.
3.
Katz
,
J. J.
, and
Rabinowitch
,
E.
,
1951
,
The Chemistry of Uranium, Part I
,
McGraw-Hill Book Company Press
,
Ann Arbor, MI
.
4.
Okazaki
,
S.
, and
Bannai
,
N.
,
1969
, “
Fluorination of Chloroethanes With NaF
,”
J. Soc. Chem. Ind.
,
72
(
3
), pp.
630
633
.
5.
Tullock
,
C. W.
, and
Coffman
,
D. D.
,
1960
, “
Synthesis of Fluorides by Metathesis With Sodium Fluoride
,”
J. Org. Chem.
,
25
(
11
), pp.
2016
2019
.
6.
Klauke
,
E.
,
Oehlmann
,
L.
, and
Baasner
,
B.
,
1982
, “
Fluorinated Heterocyclic Compounds: Selective Chlorine/Fluorine Exchange Reactions on Pyrimidines
,”
J. Fluorine Chem.
,
21
(
4
), pp.
495
513
.
7.
Haverkamp
,
R. G.
,
2012
, “
An XPS Study of the Fluorination of Carbon Anodes in Molten NaF–AlF3–CaF2
,”
J. Mater. Sci.
,
47
(
3
), pp.
1262
1267
.
8.
Bruker AXS
,
2008
, “TOPAS Software Version 4.2,”
Bruker AXS
,
Karlsruhe, Germany
.
9.
Outokumpu Research Oy
,
2006
, “HSC 6.12 Software Chemistry for Windows,”
Outokumpu Research Oy
,
Pori, Finland
.
10.
Taki
,
T.
,
Kumoto
,
S.
,
Otomura
,
K.
,
Takenaka
,
T.
,
Sato
,
N.
, and
Fujino
,
T.
,
1995
, “
Chloride Pyrometallurgy of Uranium Ore, (I)
,”
J. Nucl. Sci. Technol.
,
32
(
9
), pp.
880
888
.
11.
Shin
,
Y. J.
,
Kim
,
I. S.
,
Shin
,
H. S.
,
Ro
,
S. G.
, and
Park
,
H. S.
,
1998
, “
Thermodynamic Analysis and Experimental Study on the Chlorination of Uranium Oxide by Gas-Solid Reaction
,”
J. Radioanal. Nucl. Chem.
,
227
(
1–2
), pp.
75
78
.
12.
Guibaldo
,
C.
,
De Micco
,
G.
, and
Bohé
,
A.
,
2016
, “
Chlorination and Carbochlorination Process of U3O8 With Cl2(g)
,”
XIII Argentine Conference of Mineral Treatments
,
Mendoza, Argentina
,
Oct. 5–7
, pp.
307
312
.
13.
Grossmann
,
K.
,
Arnold
,
T.
,
Steudtner
,
R.
,
Weiss
,
S.
, and
Bernhard
,
G.
,
2009
, “
Visualizing Different Uranium Oxidation States During the Surface Alteration of Uraninite and Uranium Tetrachloride
,”
Sci. Nat.
,
96
(
8
), pp.
963
974
.
14.
Wu
,
S.
,
Li
,
X.
,
Zhang
,
P.
,
An
,
X.
, and
Xie
,
L.
,
2018
, “
Thermodynamic Evaluation of NaF-MFn(M=Be, U, Th) Systems for Molten Salt Reactor
,”
Chem. Res. Chin. Univ.
,
34
(
3
), pp.
457
463
.
15.
Savage
,
A. W.
, and
Browne
,
J. C.
,
1960
, “
The Solubility of Uranium (IV) Fluoride in Aqueous Fluoride Solutions
,”
J. Am. Chem. Soc.
,
82
(
18
), pp.
4817
4821
.
16.
Yemel'yanov
,
V. S.
, and
Yevstyukhin
,
A. I.
,
1969
,
The Metallurgy of Nuclear Fuel: Properties and Principles of the Technology of Uranium, Thorium, and Plutonium
,
Pergamon Press
,
New York
, p.
549
.
17.
Malm
,
J. G.
,
1979
, “
The Reaction of Cesium and Sodium Metals With Uranium Hexafluoride
,”
J. Inorg. Nucl. Chem.
,
41
(
11
), pp.
1573
1575
.
18.
Korenko
,
M.
,
Straka
,
M.
,
Uhlíř
,
J.
,
Szatmáry
,
L.
,
Ambrová
,
M.
, and
Šimurda
,
M.
,
2014
, “
Phase Analysis of the Solidified KF-(LiF-NaF-UF4)-ZrF4 Molten Electrolytes for the Electrowinning of Uranium
,”
J. Radioanal. Nucl. Chem.
,
302
(
1
), pp.
549
554
.
19.
Quy Dao
,
N.
,
Chourou
,
S.
, and
Heckly
,
J.
,
1981
, “
The Crystal Structure and Some Physico-Chemical Properties of the Compound Na3(UO2)2F7·6H2O
,”
J. Inorg. Nucl. Chem.
,
43
(8), pp.
1835
1839
.
20.
Davidovich
,
R. L.
, and
Zemskova
,
L. A.
,
1977
, “
Reaction of Uranyl Fluoride With Sodium Fluoride in Aqueous Solution
,”
Inorg. Chem.
,
27
(
8
), pp.
1492
1497
.
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