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Procedia Chemistry 15 (2015) 154 – 159

16th International Scientific Conference “Chemistry and Chemical Engineering in XXI century”
dedicated to Professor L.P. Kulyov, CCE 2015

Obtaining sulfur from sulfur hexafluoride and studying the sulfur

isotopes properties by using vibrational spectroscopy
Nikolay Egorov a*, Dmitry Akimov a, Nikolay Zhuravlev a
a
National Research Tomsk Polytechnic University, Tomsk, 634050, Russia

Abstract

Scheme of isotopically enriched SF6 to elemental sulfur with orthorhombic modification conversion is offered. This scheme
includes SF6 reduction to Li2S by using lithium. The yield of isotopically enriched sulfur is not less than 97 % with chemical
purity not less than 99.9 %. The results which show the dependence of the experimental frequencies in the vibrational spectra on
the molecular weight of the sulfur isotope have been obtained.
© 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
© 2015 The Authors. Published by Elsevier B.V.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of Tomsk Polytechnic University.
Peer-review under responsibility of Tomsk Polytechnic University
Keywords: sulfur, sulfur hexafluoride, isotopes

1. Introduction

Natural sulfur consists of a mixture of stable isotopes with mass numbers 32, 33, 34 and 36, the relative content
of which is 95.04%, 0.75%, 4.20% and 0.015%, respectively 1. Isotopes of sulfur are applied in biology2, geology3,
geochemistry4,5, ecology6-8, agrochemistry9, archeology10 and medicine11.
Sulfur hexafluoride is used as a working substance in the technology of centrifugal separation of the sulfur
isotopes. Parameters of technology of centrifugal separation and properties of SF6 are known12. After obtaining SF6
we should convert this compound into elemental sulfur which is suitable for storing and selling. This process should
be done with the next requirements: to minimize the losses, to eliminate the isotope dilution and to provide
necessary chemical purity.
It is known that sulfur has a lot of allotropic modifications and crystal forms, formation of which depends on the

* Nikolay Egorov. Tel.: +7-962-784-5786

E-mail address: [email protected]

1876-6196 © 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of Tomsk Polytechnic University
doi:10.1016/j.proche.2015.10.025
 Nikolay Egorov et al. / Procedia Chemistry 15 (2015) 154 – 159 155

methods of obtaining and conditions of storage13. For this reason, it is desirable to obtain the sulfur modification, as
a commercial form which is stable at a room temperature, well packed and lossless and also capable of being the
primary form to produce other allotropic forms of sulfur and commercial products. An orthorhombic modification of
sulfur (D-S) fully meets all these requirements.
The purpose of this research was to develop the method of obtaining isotopically enriched elemental sulfur from
its hexafluoride in form D-S.
For conversion SF6 to S it is possible to use microwave or plasma-chemical methods and also reduction reactions
of SF6 by metals or their oxides and hydrides14-18. The main disadvantage of microwave and plasma-chemical
methods is the complexity of the hardware design and low productivity. While using, for the oxides (CaO, MgO,
REE2O3 and others) or calcium hydride (CaH2) reduction, the gaseous sulfur-containing products (SO2, H2S, SF4 and
other compounds of sulfur) are the result of the reaction. This will require additional steps of collecting the product
gas recovery, separation of isotopically enriched sulfur from the absorbing solution and its subsequent purification.
The increasing number of stages complicates the work of processing and does not allow to exclude losses of the
isotopically enriched sulfur which is very expensive.
In paper [20] applying a differential thermal analysis method (DTA) it was found that the vast majority of metals
reacts with SF6 at a high speed in the range of 500 - 600qС with the formation of only solid phase products - sulfides
and fluorides of metals used in the reduction reaction
We used lithium as a reducing agent for processing of the hexafluoride. This reaction is well known21. Also while
choosing its relatively low vapor pressure at the temperature of the reduction reaction and thus a smaller metal
removal from the reaction zone to the cold zone of the reactor was taken into account.
In addition, in this paper we present the IR spectra and the Raman spectra of the polycrystalline of D-32S, D-33S,
D- S, which were obtained at a room temperature.
34

2. Experimental

In this work the commercial SF6 (with content of hexafluoride not less 99.9 %), metallic Li (spectra pure), carbon
tetrachloride CCl4 (analytical grade), KJ (analytical grade), I2 (analytical grade), HCl (analytical grade), toluene
(analytical grade) were used. The experimental work used isotopes of sulfur with an isotopic purity: 32S = 99.9 %;
33
S = 99.4 %; 34S = 99.9 %.
The diffractograms were obtained by using diffractometer D8 DISCOVER (СuKD- radiation, λ = 1,54056 Ǻ).
The content of the impurities in elemental sulfur was analyzed by using atomic emission spectrometry with
inductively coupled plasma iCAP6300 Duo.
IR spectra of the samples of polycrystalline α-S in KBr tablets were obtained by using FTIR 5700 spectrometer
Nikolet at a room temperature with the resolution of 2 cm-1. Raman spectra were recorded by using spectrometer
Nikolet 5700 with the Raman module at a room temperature with the resolution of 1 cm-1. In both situations the
laser Nd:YAG (O=1064 nm, 514 mW) was used.
The laboratory unit for SF6 reduction by lithium is shown in Fig. 1. The unit consists of the reactor with the
cooling cover, the volume of the unit is 2.2 l. The unit also has the molybdenum liner with the thickness around 0.1-
0.2 mm for preventing the reactor from corrosion.

Fig. 1. The laboratory unit for SF6 reduction by lithium: 1 – lithium; 2 – rangette; 3 – molybdenum liner; 4 – capacity with SF6; 5 – vacuum
gauge
156 Nikolay Egorov et al. / Procedia Chemistry 15 (2015) 154 – 159

The amount of lithium was calculated with an excess of 30-40 %, lithium was placed in a molybdenum liner, then
the reactor was sealed and evacuated to 10-3 mm Hg. After checking the impermeability of the system 40-50 mm Hg
SF6 was placed into the reactor. This prevented the lithium sublimation during heating and also allowed to define the
beginning of the reaction. After that the reactor was heated by using the rangette.
The exothermic reduction reaction of SF6 started under heating of the reactor bottom to red heat and proceeded
with the formation of solid-phase sulfide and lithium fluoride:

8Li + SF6 o Li2S + 6LiF (1)

After starting the reaction the heating was turned off and put into the reactor SF6 at such a rate that the reaction
would not stop and the reactor would not heat to 1000 °C. The reactor was cooled after the reaction. Then the
Lugol's solution in 2 N HCl, with a 100% excess of the stoichiometric was put into the reactor using the residual
vacuum.
The mixture obtained was left for 12 hours in the reactor at a room temperature. The oxidation reaction of
sulphide sulfur proceeded with an elemental sulfur formation.

Li2S + I2 o 2LiI + S (2)

The suspension was filtered. The precipitate was dried and milled in the mortar. After that the elemental sulfur
was extracted by using CCl4 and the apparatus of Soxhlet. For obtaining chemically pure product, the elemental
sulfur was cleaned by vacuum sublimation.
The sulfur after sublimation was recrystallized from toluene for obtaining the crystals of isotopically pure
elemental sulfur with the orthorhombic modification. 250 mg of sulfur were taken for each 10 ml of toluene and
then were dissolved by heating. The D-S was crystallized under cooling to 20 0 C from the solution. The yield of
crystals D-S was not less than 99%
The roentgenogram of α-34S which was obtained by using this method is shown in Fig. 2. The roentgenogram
includes the reflections of crystallographic planes of orthorhombic sulfur. The results of elemental analysis of D-S34
are shown in table 1.

Fig. 2. The XRD pattern of isotopes α-34S

Table 1. Results of the quantitative chemical analysis of impurities in D-S34

Element Content, ppm Element Content, ppm

Al  10 Li  10
B 5 Fe 5
C 5 Mg 8
Ca 9 Na 7
Cr 5 Cu 2

Sulfur isotopes obtained in this way have a chemical purity of more than 99.9%. The yield of elemental sulfur is
not less than 97 %.
 Nikolay Egorov et al. / Procedia Chemistry 15 (2015) 154 – 159 157

Fig. 3 shows the IR spectra, obtained for the polycrystalline samples of the α-32S, α-33S, α-34S and α-natS isotopes.
According to the previous study22, the observed IR spectra absorption corresponds to the valence vibration
(stretching vibration) - Q5. Fig. 3 shows that the position of the lines of oscillation (Q5) for the α-33S and the α-34S
isotopes are shifted to the low-energy side, and the line corresponding to the α-32S isotope has a high-energy shift
with respect to the spectrum of α-natS.
This behavior can be explained by the fact that the positions of the oscillation frequencies in the spectra directly
affect the mass of the atoms oscillating around the equilibrium positions in the crystal lattice. This dependence has
the form: Q = v m-½.

Fig. 3. IR spectra of isotopes α-32S, α-33S, α-34S and α-natS

Isotopic dependence of the oscillation frequencies of α-S in the IR spectra are shown in Fig. 4. The line shows the
calculated dependence of the absorption frequency on the atomic mass of the α-S isotope (Q = 2632.9 m-½), which
correlates with experimental values.

Fig. 4. Isotopic dependence of the oscillation frequencies of α-S in the IR spectra

158 Nikolay Egorov et al. / Procedia Chemistry 15 (2015) 154 – 159

Fig. 5 shows the Raman spectra obtained for polycrystalline samples of the isotopes of α-S. In the spectra of the
isotopes all of the absorption bands that are characteristic of α-S were observed, which, according to the isotope
shift, is indicated by: Q = v m-½.

Fig. 6 shows the experimental vibrational frequencies in the Raman spectra of the atomic mass of the α-S isotope.
As shown in the figure, dependencies of the position of crest of bands in the Raman spectra of sulfur isotopes are a
linear function of the atomic masses of the isotopes.

Fig. 5. Raman spectra of the isotopes α-32S, α-33S, α-34S and α-natS

Fig. 6. Isotopic dependence of the oscillation frequencies of α-S in the Raman spectra

These linear relationships make it possible to know the frequency of isotopes α-32S, α-33S and α-34S to determine
the oscillation frequency in the IR and Raman spectra of the sulfur isotope α-36S, for which it is difficult to obtain
vibrational spectra due to its high cost connected with its low content in the natural sulfur.

3. Conclusion

1. IR spectra and Raman spectra of the polycrystalline isotopes α-32S, α-33S and α-34S have been obtained.
2. It has been found that experimental frequencies of the vibrational spectra of the isotopes of sulfur decrease in a
linear manner with an increasing mass of the isotope. From the experimental correlations, the oscillation frequencies
for the isotope α-36S have been determined.
 Nikolay Egorov et al. / Procedia Chemistry 15 (2015) 154 – 159 159

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