Fluoride volatility

Fluoride volatility is the tendency of highly fluorinated molecules to vaporize at comparatively low temperatures. Heptafluorides, hexafluorides and pentafluorides have much lower boiling points than the lower-valence fluorides. Most difluorides and trifluorides have high boiling points, while most tetrafluorides and monofluorides fall in between. The term "fluoride volatility" is jargon used particularly in the context of separation of radionuclides.

Volatility and valence

Blue elements have volatile fluorides or are already volatile; green elements do not but have volatile chlorides; red elements have neither, but the elements themselves are volatile at very high temperatures. Yields at 10 years after fission, not considering later neutron capture, fraction of 100% not 200%. Beta decay Kr-85→Rb, Sr-90→Zr, Ru-106→Pd, Sb-125→Te, Cs-137→Ba, Ce-144→Nd, Sm-151→Eu, Eu-155→Gd visible.

Valences for the majority of elements are based on the highest known fluoride. However, elements with high valence tend to reach higher oxidation state in compounds with oxygen rather than fluorine.

Roughly, fluoride volatility can be used to remove elements with a valence of 5 or greater: uranium, neptunium, plutonium, metalloids (tellurium, antimony), nonmetals (selenium), halogens (iodine, bromine), and the middle transition metals (niobium, molybdenum, technetium, ruthenium, and possibly rhodium). This fraction includes the actinides most easily reusable as nuclear fuel in a thermal reactor, and the two long-lived fission products best suited to disposal by transmutation, Tc-99 and I-129, as well as Se-79.

Noble gases (xenon, krypton) are volatile even without fluoridation, and will not condense except at much lower temperatures.

Left behind are alkali metals (caesium, rubidium), alkaline earth metals (strontium, barium), lanthanides, the remaining actinides (americium, curium), remaining transition metals (yttrium, zirconium, palladium, silver) and post-transition metals (tin, indium, cadmium). This fraction contains the fission products that are radiation hazards on a scale of decades (Cs-137, Sr-90, Sm-151), the four remaining long-lived fission products Cs-135, Zr-93, Pd-107, Sn-126 of which only the last emits strong radiation, most of the neutron poisons, and the higher actinides (americium, curium, californium) that are radiation hazards on a scale of hundreds or thousands of years and are difficult to work with because of gamma radiation but are fissionable in a fast reactor. Americium finds use in ionization smoke detectors while californium is used as a spontaneous fission based neutron source. Curium has only very limited uses outside nuclear reactors. Fissionable but non-fissile actinoids can be used or disposed of in a subcritical nuclear reactor using an external neutron source such as an Accelerator Driven System.

Reprocessing methods

Uranium oxides react with fluorine to form gaseous uranium hexafluoride, most of the plutonium reacts to form gaseous plutonium hexafluoride, a majority of fission products (especially electropositive elements: lanthanides, strontium, barium, yttrium, caesium) form nonvolatile fluorides. Few metals in the fission products (the transition metals niobium, ruthenium, technetium, molybdenum, and the halogen iodine) form volatile (boiling point <200 °C) fluorides that accompany the uranium and plutonium hexafluorides, together with inert gases. Distillation is then used to separate the uranium hexafluoride from the mixture. ^{[1] [2]}

The nonvolatile alkaline fission products and minor actinides fraction is most suitable for further processing with 'dry' electrochemical processing (pyrochemical) non-aqueous methods. The lanthanide fluorides are difficult to dissolve in the nitric acid used for aqueous reprocessing methods, such as PUREX, DIAMEX and SANEX, which use solvent extraction. Fluoride volatility is only one of several pyrochemical processes designed to reprocess used nuclear fuel.

The Řež nuclear research institute at Řež in the Czech Republic tested screw dosers that fed ground uranium oxide (simulating used fuel pellets) into a fluorinator where the particles were burned in fluorine gas to form uranium hexafluoride. ^[3]

Hitachi has developed a technology, called FLUOREX, which combines fluoride volatility, to extract uranium, with more traditional solvent extraction (PUREX), to extract plutonium and other transuranics. ^[4] The FLUOREX-based fuel cycle is intended for use with the Reduced moderation water reactor. ^[5]

Some fluorides are water soluble while others aren't (see the solubility table) and can be separated in aqueous solution. However, all aqueous processes that take place without complete removal of tritium (a common product of ternary fission) ^{[6] [7]} prior to addition of water will contaminate the water with tritiated water which is difficult to remove from water. ^{[8] [9] [10]} Some elements which form soluble florides form insoluble chlorides. Addition of a suitable soluble chloride (e.g. sodium chloride) will salt out those cations. One example is silver (I) fluoride (water soluble) which forms silver chloride precipitate upon addition of a soluble chloride.

AgF + NaCl → AgCl↓ + NaF

Some fluorides react aggressively with water and may form highly corrosive hydrogen fluoride. This needs to be taken into account if aqueous processes involving fluorides are to be used. ^[11]

If desired, a series of further anion-additions similar to the de:Kationentrennungsgang can be used to separate out different cations for disposal, further processing or use.

Table of relevant properties

Fluoride	Z	Boiling °C	Melting °C	Key halflife	Yield
HF	1	19.5	−83.6	T:12y	Common reagent
BF3	5	-100.3	−126.8	none over 0.8 s	Neutron poison used for control
SeF6	34	−46.6	−50.8	79Se:65ky	.04%
TeF6	52	−39	−38	127mTe:109d
IF7	53	4.8 (1 atm)	6.5 (tripoint)	129I:15.7my	0.54%
MoF6	42	34	17.4	99Mo:2.75d
PuF6	94	62	52	239Pu:24ky
TcF6	43	55.3	37.4	99Tc:213ky	6.1%
NpF6	93	55.18	54.4	237Np:2.14my
UF6	92	56.5 (subl)	64.8	233U:160ky
RuF6	44	200 (dec)	54	106Ru:374d
RhF6	45	73.5 [12]	70	103Rh:stable
ReF7	75	73.72	48.3	Not FP
BrF5	35	40.25	−61.30	81Br:stable
IF5	53	97.85	9.43	129I:15.7my	0.54%
XeF2	54	114.25 (subl)	129.03 (tripoint)
SbF5	51	141	8.3	125Sb:2.76y
RuOF4	44	184	115	106Ru:374d
RuF5	44	227	86.5	106Ru:374d
NbF5	41	234	79	95Nb:35d	low
PdF4	46			107Pd:6.5my
SnF4	50	750 (subl)	705	121m1Sn:44y 126Sn:230ky	0.013% ?
ZrF4	40	905	932 (tripoint)	93Zr:1.5my	6.35%
AgF	47	1159	435	109Ag:stable
CsF	55	1251	682	137Cs:30.2y 135Cs:2.3my	6.19% 6.54%
BeF2	4	1327	552	10Be:1.4my
RbF	37	1410	795
UF4	92	1417	1036	233U:160ky
FLiBe		1430	459	stable
FLiNaK		1570	454	stable
LiF	3	1676	848	stable
KF	19	1502	858	40K:1.25Gy
NaF	11	1704	993	stable
ThF4	90	1680	1110
CdF2	48	1748	1110	113mCd:14.1y
YF3	39	2230	1150	91Y:58.51d
InF3	49	>1200	1170
BaF2	56	2260	1368	140Ba:12.75d
TbF3	65	2280	1172
GdF3	64		1231	159Gd:18.5h
PmF3	61		1338	147Pm:2.62y
EuF3	63	2280	1390	155Eu:4.76y
NdF3	60	2300	1374	147Nd:11d
PrF3	59		1395	143Pr:13.57d
CeF3	58	2327	1430	144Ce:285d
SmF3	62	2427	1306	151Sm:90y	0.419% ?
SrF2	38	2460	1477	90Sr: 29.1y	5.8%
LaF3	57		1493	140La:1.68d

See also

• FLiNaK
• Molten salt reactor

Notes

• Missing top fluorides: ^[13]
  • PrF₄ (because it decomposes at 90 °C)
  • TbF₄ (because it decomposes at 300 °C)
  • CeF₄ (because it decomposes at 600 °C)
• Without stable fluorides: Kr ^[14]

References

1. Uhlir, Jan. "An Experience on Dry Nuclear Fuel Reprocessing in the Czech Republic" (PDF). OECD Nuclear Energy Agency. Retrieved 2008-05-21.
2. Uhlir, Jan. "R&D of Pyrochemical Partitioning in the Czech Republic" (PDF). OECD Nuclear Energy Agency. Retrieved 2008-05-21.
3. Markvart, Milos. "Development of Uranium Oxide Powder Dosing for Fluoride Volatility Separation Process" (PDF). Archived from the original (PDF) on November 17, 2004. Retrieved 2008-05-21.
4. "Fuel Cycle：Hitachi-GE Nuclear Energy, Ltd".
5. "Next-generation Nuclear Reactor Systems for Future Energy : HITACHI REVIEW". www.hitachi.com. Archived from the original on 19 February 2013. Retrieved 17 January 2022.
6. https://inldigitallibrary.inl.gov/sites/sti/sti/5581212.pdf
7. https://nucleus.iaea.org/sites/htgr-kb/HTR2014/Paper%20list/Track8/HTR2014-81096.pdf
8. "Our Modular Detritiation System (MDS®) to Remove Tritium".
9. https://www.researchgate.net/publication/336994234_A_COMPACT_LOW_COST_TRITIUM_REMOVAL_PLANT_FOR_CANDU-6_REACTORS
10. "Contract for Cernavoda tritium removal facility".
11. Zakiryanova, Irina D.; Mushnikov, Petr N.; Nikolaeva, Elena V.; Zaikov, Yury P. (2023). "Mechanism and Kinetics of Interaction of FLiNaK–CeF3 Melt with Water Vapors and Oxygen in the Air Atmosphere". Processes. 11 (4): 988. doi: 10.3390/pr11040988 .
12. "Nitrogen Trifluoride Based Fluoride Volatility Separations Process: Initial Studies" (PDF). p. 1. Retrieved 2024-08-22.
13. CRC Handbook of Chemistry and Physics, 88th Edition Archived 2010-07-04 at the Wayback Machine . (PDF). Retrieved on 2010-11-14.
14. Precious metal refining with fluorine gas – Patent 5076839. Freepatentsonline.com. Retrieved on 2010-11-14.

External links

• Study of Electrochemical Processes for Separation of the Actinides and Lanthanides in Molten Fluoride Media (PDF)
• "Separation and purification of UF₆ from volatile fluorides by rectification" (PDF). Archived from the original (PDF) on 13 January 2005.
• Low-pressure distillation of a portion of the fuel carrier salt from the Molten Salt Reactor Experiment (PDF)
• Use of the Fluoride Volatility Process to Extract Technetium from Transmuted Spent Nuclear Fuel (PDF)
• A Peer Review of the Strategy for Characterizing Transuranics and Technetium Contamination in Depleted Uranium Hexafluoride Tails Cylinders (PDF)
• PHYSICAL CONSTANTS OF INORGANIC COMPOUNDS (PDF)