Multi-emitter chemiluminescence in the solid-phase interaction of xenon difluoride with uranyl hydrogen phosphate

Article abstract of DOI:10.1016/j.mencom.2016.09.013

Chemiluminescence (CL) was found in the solid-phase interaction of xenon difluoride with uranyl hydrogen phosphate; the CL emitters are *Xe, UO₂²⁺ and the singlet oxygen dimole (¹O₂)₂.

Full text of DOI:10.1016/j.mencom.2016.09.013

Mendeleev
Communications
Mendeleev Commun., 2016, 26, 405–406
Multi-emitter chemiluminescence in the solid-phase interaction
of xenon difluoride with uranyl hydrogen phosphate
Sergey S. Ostakhov,* Gul’shat A. Masyagutova, Alexander V. Mamykin and Sergey L. Khursan
Ufa Institute of Chemistry, Russian Academy of Sciences, 450054 Ufa, Russian Federation.
Fax: + 7 3472 35 6066; e-mail: ostahov@anrb.ru
DOI: 10.1016/j.mencom.2016.09.013
(1O
)
2 2
0
0
.8 Chemiluminescence
XeF
2
+ UO
powders
(1O
)
2 2
2
HPO
4
(1
2 2
O )
.6
Chemiluminescence (CL) was found in the solid-phase inter-
action of xenon difluoride with uranyl hydrogen phosphate;
0.4
2+
*UO
2
2+
the CL emitters are *Xe, UO2 and the singlet oxygen dimole
0
0
.2
1
*Xe
(
O ) .
2 2
.0
4
00 450 500 550 600 650 700 750
l/nm
The study of chemiluminescence (CL) makes it possible to reveal
the unit event of electron excitation (*) generation in chemical
and intense movement of crystals were observed due to chemo-
1
1
responsive reactions of crystals with gas products. The forma-
tion of molecular oxygen, Xe, XeF and HF was confirmed by
mass spectrometry. The reaction occurred within about 10 min,
and its kinetics is given in Figure 1. The end product was a
vitreous mass, which self-heated to 320 K in the reaction.
The visually detected CL in the solid-phase interaction of XeF2
1
,2
processes regardless of the phase state of the reaction system.
The interaction of inorganic reagents3 accompanied by CL
has not been adequately studied. Inorganic CL processes in a solid
state are much more seldom phenomena. In this context, CL in
–5
6
the solid-phase oxidation reactions of uranium(iv) hydroxide and
7
2+
hydrogen phosphate with xenon difluoride deserves attention
with UO HPO ·4H O is caused by the fact that UO is a strong
2
4
2
2
+
because the uranyl ion is both the end product and the light emitter
acceptor of fluoride anions [stability constant lgK (UO F ) =
1 2
8
12
in these reactions. Xenon difluoride is an effective oxidant, and
= 4.93], and it can initiate xenon difluoride decomposition.
Immediately after the mixing of UO HPO ·4H O and XeF
2
its reactivity sharply increased in the presence of fluoride ion
2
4
2
acceptors, in particular, SiO2.9 In the solid-phase decomposi-
,10
powders, CL was detected: a low-intensity band at about 460 nm,
bright luminescence in the green region of the spectrum with a
maximum at 520 nm, and long-wave maxima at 580, 630 and
709 nm (Figure 1, spectrum 2).
iv
tion of XeF on the surface of silica gel in the absence of U , we
2
found CL and identified gaseous electron excited products, *Xe
+
10
(
465 nm), *Xe (415, 540 and 580 nm) and singlet oxygen.
1
0,13,14
The basis of the given research was the unexpected appearance
Published data
on the radiative transitions of *Xe
of bright CL in the solid-phase interaction of xenon difluoride
with U hydrogen phosphate, which has the highest oxidation
(462–467 nm) indicate that CL at 460 nm can be assigned to
xenon atom luminescence. The spectra of *Xe emission and UO2
vi
2+
state one order of magnitude higher than that in a redox reaction
absorption overlap, and this circumstance provides both non-
radiative energy transfer and CL activation with the uranyl ion with
an intense radiative transition at 520 nm. The fluorescence (FL)
spectrum of UO HPO ·4H O is given in Figure 2. Therefore, in
iv
of XeF with U . In this work, we studied spectral-luminescent
2
properties to reveal the emitters of CL in the solid-phase interac-
tion of xenon difluoride with UO 22 + hydrogen phosphate, which
2
4
2
can optionally be both the CL activator and the initiator of XeF
this reaction, the uranyl ion is both a CL activator and the initiator
2
–
†
–
decomposition due to accepting F anions.
When the finely dispersed polycrystalline salts of UO
of XeF decomposition due to the acceptance of F anions.
2
2
+
2
–
–
–
–
(
HPO , NO , SO and F ) were mixed with xenon difluoride,
t/min
4
3
4
the CL in the green spectral region was visually detected. The
most intense luminescence was observed in the interaction of
uranyl hydrogen phosphate with xenon difluoride.
0
2
4
6
8
10
12
4
4
2
3
2
3
2
When the course of the solid-phase reaction of an equimolar
powder mixture of XeF (17 mg) and UO HPO ·4H O (44 mg)
3
2
2
4
2
was monitored by microscopy, both explosive decomposition
1
†
The CL and FL spectra were measured on a Solar CM-2203 spectro-
1
0
1
0
fluorimeter. The absorption spectra were recorded on a Specord M400
spectrophotometer, and the mass spectra were taken on a ThermoFinnigan
MAT 95XP instrument. XeF2 and UO HPO ·4H O were synthesized
according to published procedures.1
2
4
2
400 450 500 550 600 650 700 750
9,20
UO F ·2.5H O was prepared by
2 2 2
l/nm
the dissolution of a weighed portion of UO in hydrofluoric acid under
3
heating with an IR lamp. The crystal water content was determined by
thermogravimetry on a Q-1000 derivatograph. The salts of UO 22 were
purified by double recrystallization from twice-distilled water.
Figure 1 (1) CL kinetics in interaction of powders of UO HPO ·4H O
2
4
2
+
(44 mg) and XeF (17 mg). CL spectra in solid-phase reaction of XeF with
2
2
UO HPO ·4H O (2) in the beginning of reaction and (3) after 2 min (325 K).
2
4
2
©
2016 Mendeleev Communications. Published by ELSEVIER B.V.
–
405 –
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.

Mendeleev Commun., 2016, 26, 405–406
F– anion and the activator of CL according to the mechanism of
nonradiative energy transfer from electron-excited atomic *Xe.
2
2
1
1
.5
.0
.5
.0
.5
2
+
We found that Xe (460 nm), *UO (520 nm) and singlet oxygen
1
2
1
dimole ( O ) are responsible for CL in the solid-phase interac-
2
2
tion of XeF with UO HPO ·4H O.
2
2
4
2
The experiments were performed on the equipment of the
Khimiya’ Centre of Collective Use at the Ufa Institute of Chemistry
‘
0
0
2
of the Russian Academy of Sciences.
3
.0
4
50
500
550
600
650
References
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1
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(
Figure 2 FL spectra of polycrystalline powders: (1) UO HPO ·4H O;
2) reaction product of XeF with UO HPO ·4H O; and (3) UO F ·2.5H O
lex = 450 nm, 298 K).
2
4
2
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(
(
2 2 4 2 2 2 2
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of singlet oxygen dimole ( O ) . The fine correlation of the CL
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2
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1
2
2
1
17
2
2
confirms this supposition.
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9
2
4
2
1
1
XeF were mixed, the CL intensities were redistributed over the
2
entire spectral range (Figure 1, spectrum 3). When the CL at
2
+
5
20 nm due to *UO2 decreased, the radiation of *Xe (460 nm)
1
became pronounced and the luminescence in the region of ( O )
2
2
(
580–709 nm) emission increased.
Figure 2 shows the luminescence spectra of polycrystalline
specimens of UO HPO ·4H O, the reaction product of XeF
1
1
2
4
2
2
with UO HPO ·4H O, and UO F ·2.5H O, whose light sums
2
4
2
2
2
2
corresponding to the quantum yields (j) of FL are 73, 17 and 6,
respectively. Because j of FL of the reaction product of XeF2
with UO HPO ·4H O takes an intermediate position between
2
4
2
2
+
those for UO2 hydrogen phosphate and fluoride, it is reasonable
to suppose the formation of uranyl phosphate-fluoride complexes.
1
–
In turn, the complexation of the F anion with uranyl leads to
induced xenon difluoride decomposition.
1
Because the solid-phase reaction of XeF with UO HPO ·4H O
2
2
4
2
1
was carried out in a sealed quartz cell and the lifetime of O
18 C. Schweitzer and R. Schmidt, Chem. Rev., 2003, 103, 1685.
19 P. Groz, J. Kiss, A. Reverz and T. Siros, J. Inorg. Nucl. Chem., 1966, 28,
2
monomole in a gas phase was 72 min,18 the rise in CL intensity
9
09.
in the region of 580–709 nm can be explained by the accumula-
tion of singlet oxygen dimole in the bulk. Really, after depres-
surization and blowing the reactor with air, luminescence in the
2
0 J. M. Schreyer and C. F. Baes, Jr., J. Am. Chem. Soc., 1954, 76, 354.
1
region of ( O ) emission was not detected.
2
2
2
+
Therefore, UO hydrogen phosphate is both the initiator of
2
the solid-phase decomposition of xenon difluoride due to accepting
Received: 17th February 2016; Com. 16/4849
–
406 –