technetium(VII), actinides(VII), transuranium elements, Periodic Table, new species of Tc(VII), Tc(VII) conversion, crystallography, EXAFS, Moessbauer

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ФГУП «Российский федеральный ядерный центр –
Всероссийский научно-исследовательский институт экспериментальной физики»
XIII Международный семинар
ФУНДАМЕНТАЛЬНЫЕ СВОЙСТВА ПЛУТОНИЯ
XIII International Workshop FUNDAMENTAL PROPERTIES OF PLUTONIUM
Heptavalent state of transuranium and other
elements of the Periodic Table
German K.E., Grigoriev M.S., Peretrukhin V.F.
A.N. Frumkin Institute of Physical Chemistry and ElectrochemistryA.N. Frumkin Institute of Physical Chemistry and Electrochemistry
Russian Academy of Sciences
31, Leninsky prospekt, Moscow, 119071, Russia. guerman_k@mail.ru
9-13 сентября
Sarov
September 9-13
2013
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V.F. Peretrukhin, G.T. Seaborg, N..N. Krot, LNL, Berkley, 1998
Periodic Table and heptavalent
state of elements
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Period is variable : 2, 8, 8, 18, 18, 32…?
Zones of implacability exist
For huge part - It works ! ! !
VII

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• Interatomic distances in simple matter from A.Wells “Struct.Inorg.Chem.”
• Lost : P,S, Br, I, Po, At, Fr, Ra, Ac, Np, Pu, Am, Cm, Bk, Cf
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TRU
Synthesis and the types of An(VII)
• Crystalline compounds of An(VII) can be prepared by deep
oxidation of actinides in strongly alkaline conditions.
• Both interaction of solid components and also conducting the
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p g
oxidation in alkaline solutions.
• Compounds of An(VII) are stable only in strong alkali, and
rapidly decompose in neutral or acidic conditions.
• An(VII) are quite variable in composition: formally they could
be considered to contain anions AnO6
5-, AnO5
3-, [AnO4(OH)2]3-
[An2O8(OH)2]4- and AnO4
- but the latter is not supported by, [An2O8(OH)2] and AnO4 but the latter is not supported by
X-ray analyses.
• A short number of the solid compounds containing AnO6
5-,
and AnO5
3- anions were isostructural to corresponding ortho-
and meso- rhenates ReO6
5-, ReO5
3- (but no analogy in
solutions).

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MAnO4(·nH2O) (M – alkali metal)
• It was estimated by N.N.
Krot and the followers that
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Krot and the followers that
the transuranium(VII)
compounds like
MAnO4(·nH2O) (M – alkali
metal) have the structures
similar to uranates(VI) of
alkali earth metals.
• They contain shortened
linear groups AnO2
3+ and O–
bridges collecting all into
anionic layers. Structural type of BaUO4.
(Reis A.H. et al. JINC, 1976).
BaUO4 structural type
compounds
• Lattice parameters for
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• Lattice parameters for
different U(VI), Np(VI)
(lit. data) and Np(VII)
compounds (IPCE data)
• 1 – U compounds
• 2 – Np compounds
• Chemical properties of
Np(VI) and Np(VII)
compounds are different

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IR spectral data
• Evident splitting at the
CsNpO spectrum
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CsNpO4 spectrum
indicates/support the
presence of two types
of Np-O bonds:
• O=Np=O
• Np O Np• Np-O-Np
• In Li5NpO6 all the
Np-O bonds are of
the same nature
Mossbauer spectra of Np(VII)
compounds
• 1 – CsNpO41 CsNpO4
• 2 – Na3NpO4(OH)2*nH2O
• 3 – Li5NpO6
• 4 – frozen solution of
Np(VII) in 10M NaOH
• Dots - experiment, curve
– squared plotting

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In this way :
Transuranic(VII) MAnO4(·nH2O)
compounds are completely different
from Структурный тип BaUO4.
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MXO4
xnH2O (X – elements of the 7th
Group from Periodic Table, Mn, Tc, Re, n
= 0, 1, 1.5, 3)
from Tc(VII) acid
German,Peretrukhin 2003
Poineau, German 2010
f R (VII) id
(Reis A.H. et al. JINC, 1976).
(Maruk A.Ya. et al. Russ.
Coord. Chem.2011)
from Re(VII) acid
Beyer H. et all.
Angew. Chem., 1968
from I(VII) acid
from Cl(VII) acid
)
and from TcO3
+
Pertechnetyl Fluorosulfate,
[TcO3][SO3F] – ZAAC, 2007
J.Supeł, U. Abram et all.
Berlin, Freie Universität.
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Np(VII) & I(VII)
Anionic chain [(Np2O8)(OH)2]n
4n- in the structure
of Li[Co(NH3)6][(Np2O8)(OH)2]·2H2O
(Burns J., Baldwin W., Stokely J. Inorg. Chem., 1973).
• Two types of Np in Np(VII) compound while only one I in I(VII)
• One bridging O in Np(VII) while two bridging O in I(VII)
• Np(VII) is stable in alkali while I(VII) – in acids
Neutral chains in HIO4.
( Smith, T. et all. Inorg.Chem., 1968)

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The first Pu(VII)
single crystal
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Na4[AnO4(OH)2](OH)·2H2O
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Np1-O1 1.891(2) Pu1-O1 1.8824(15)
Np1-O2 1.888(2) Pu1-O2 1.8805(18)
Np1-O3 1.917(2) Pu1-O3 1.9109(15)
Np1-O4 1.880(2) Pu1-O4 1.8811(19)
Np1-O5 2.315(2) Pu1-O5 2.2952(19)
Np1-O6 2.362(2) Pu1-O6 2.339(2)
An-OH distances are
more sensible to
actinide contraction
than An=O distances
Several mixed cation compounds of Np(VII) and Pu(VII)
NaRb2[NpO4(OH)2]·4H2O (I): a = 8.2323(2), b = 13.4846(3), c = 9.9539(2) Å, β =
102.6161(12)°, sp. gr. P21/n, Z = 4, R1 [I > 2σ(I)] = 0.0179.
NaRb2[NpO4(OH)2]·4H2O (II): a = 5.4558(2), b = 12.4478(3), c = 7.9251(2) Å, β =
103.6310(13)°, sp. gr. P21/n, Z = 2, R1 [I > 2σ(I)] = 0.0218.
NaCs2[NpO4(OH)2]·4H2O (III): a = 15.0048(4), b = 9.1361(2), c = 10.6747(3) Å, β =
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2[ p 4( )2] 2 ( ) ( ), ( ), ( ) , β
129.7361(9)°, sp. gr. C2/c, Z = 4, R1 [I > 2σ(I)] = 0.0148.
NaRb5[PuO4(OH)2]2·6H2O (IV): a = 6.4571(1), b = 8.2960(1), c = 10.8404(2) Å, α =
105.528(1), β = 97.852(1), γ = 110.949(1)°, sp. gr. P-1, Z = 2, R1 [I > 2σ(I)] = 0.0189.
NaRb2[PuO4(OH)2]·4H2O (V): a = 8.2168(2), b = 13.4645(3), c = 9.9238(2) Ǻ, β =
102.6626(12)°, sp. gr. P21/n, Z = 4, R1 [I > 2σ(I)] = 0.0142.
NaCs2[PuO4(OH)2]·4H2O (VI): a = 11.1137(2), b = 9.9004(2), c = 10.5390(2) Ǻ, β =
101.0946(11)°, sp. gr. C2/c, Z = 4, R1 [I > 2σ(I)] = 0.0138.
Anion of [PuO4(OH)2]3-
in the structure of IV

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Selected interatomic distances and torsion angles
in the structures I – VI :
I II III IV V VI
Bond (Å)
An=O 1.8790(12) 2×1.8690(9) 2×1.8884(9) 1.8695(15) 1.8685(12) 2×1.8868(15)
1 8855(13) 2 1 9138(9) 2 1 8944(9) 1 8724(15) 1 8761(12) 2 1 8876(14)
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1.8855(13) 2×1.9138(9) 2×1.8944(9) 1.8724(15) 1.8761(12) 2×1.8876(14)
1.8955(13) 1.8919(15) 1.8897(12)
1.9223(13) 1.8985(16) 1.9144(12)
An-O(OH) 2.3259(13) 2×2.3750(9) 2×2.3643(9) 2.3197(16) 2.3083(13) 2×2.3236(15)
2.3382(13) 2.3556(15) 2.3229(13)
Angle (º) I II III IV V VI
H-O…O-H 145(4) 180 133(4) 39(4) 140(3) 48(5)
Recently a new way for Np(VII) compound preparation
was proposed by Fedosseev and co-workers [(2008)]:
electrochemical oxidation in acetate solutions.
The new compounds of
МNpO nH O type where М unicharged cation of
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МNpO4·nH2O type, where М – unicharged cation of
alkali metal, ammonium, silver, guanidinium or
tetraalkylammonium
and
Np(VII) with bicharged cations of alkaline earth
metals and also Cu Cd and Znmetals, and also Cu, Cd and Zn.
All these compounds have been thoroughly
characterized by means of chemical analyses, IR and
UV-vis spectroscopy. The study confirmed, that…

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Pu(VII) compounds
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( ) p
are close structural
and chemical
analogues
of Np(VII) ones
Tc(VII) & Pu(VII), Np(VII)
1000 ppm
Pu(VII) and Tc(VII) are different in (cry,ele)-structure,
ligand arrangement, stability and chemical properties !

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Periodic Table and heptavalent
state of elements
4
Period is variable : 2, 8, 8, 18, 18, 32…?
Zones of implacability exist
For huge part - It works ! ! !
VII
An(VII) - Tc&Re(VII)
• Structural and chemical data obtained in recent years by
X-ray-s-c, IR and EXAFS investigations of the new
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X ray s c, IR and EXAFS investigations of the new
compounds of
• heptavalent neptunium and plutonium,
• heptavalent technetium and rhenium
• confirm the earlier prevailing opinion about the absence
of a deep similarity in physico-chemical properties
between the heptavalent transuranic elements and thebetween the heptavalent transuranic elements and the
elements of Group VII of the short form of the Periodic
table and the formal nature of some of the structural
similarities among the considered heptavalent
compounds.

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Bessonov
Perminov
Krot,
Grigoriev
PeretrukhinPeretrukhin
German
Thank youThank you
for your
Attention!