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ФГУП «Российский федеральный ядерный центр –Всероссийский научно-исследовательский институт экспериментальной физики»

XIII Международный семинарФУНДАМЕНТАЛЬНЫЕ 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 ElectrochemistryRussian Academy of Sciences

31, Leninsky prospekt, Moscow, 119071, Russia. guerman_k@mail.ru

9-13 сентябряSarov

September 9-132013

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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 goxidation in alkaline solutions.

• Compounds of An(VII) are stable only in strong alkali, andrapidly decompose in neutral or acidic conditions.

• An(VII) are quite variable in composition: formally they couldbe considered to contain anions AnO6

5-, AnO53-, [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 AnO65-,

and AnO53- anions were isostructural to corresponding ortho-

and meso- rhenates ReO65-, ReO5

3- (but no analogy insolutions).

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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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MXO4xnH2O (X – elements of the 7th

Group from Periodic Table, Mn, Tc, Re, n= 0, 1, 1.5, 3)

from Tc(VII) acidGerman,Peretrukhin 2003Poineau, German 2010f R (VII) id

(Reis A.H. et al. JINC, 1976).

(Maruk A.Ya. et al. Russ. Coord. Chem.2011)

from Re(VII) acidBeyer 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]n4n- 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)·2H2O15

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 ( ) ( ), ( ), ( ) , β129.7361(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 VIBond (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 preparationwas 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 ofalkali metal, ammonium, silver, guanidinium ortetraalkylammonium

and

Np(VII) with bicharged cations of alkaline earthmetals and also Cu Cd and Znmetals, and also Cu, Cd and Zn.

All these compounds have been thoroughlycharacterized by means of chemical analyses, IR andUV-vis spectroscopy. The study confirmed, that…

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Pu(VII) compounds

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( ) pare 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

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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 propertiesbetween the heptavalent transuranic elements and thebetween the heptavalent transuranic elements and theelements of Group VII of the short form of the Periodictable and the formal nature of some of the structuralsimilarities among the considered heptavalentcompounds.

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BessonovPerminov

Krot,Grigoriev

PeretrukhinPeretrukhinGerman

Thank youThank youfor your

Attention!