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Recent advances in nuclear chemistry
III School of Energetic and Nuclear Chemistry
Biological and Chemical Research Centre University of Warsaw, Poland
Konstantin German
Frumkin Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences (IPCE RAS), Moscow, RussiaMedical institute REAVIZ
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Scope
• Nuclear prospects in Russia
• NMR for radioactive materials analyses
• Sync Radiation
• Actinide hypothesis verification
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Homo sapience sp. was the most efficient one in applying technologies to improving its life
Economist Kenneth Boulding (1956) : one who believes that exponential growth could be eternal in the limited world is
either mad or economist
Neand.sp. sp.
Cosmo sp.
Coal
Oil
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Petroleum energeticswiki :
• The modern history of petroleum began in the 19th century with the refining of paraffin from crude oil. The Scottish chemist James Young in 1847 noticed a natural petroleum seepage in the Riddings colliery ‐ Derbyshire. He distilled a light thin oil suitable for use as lamp oil, at the same time obtaining a thicker oil suitable for lubricating machinery.
• In 1848, Young set up a small business refining the crude oil. The new oils were successful, but the supply of oil from the coal mine soon began to fail (eventually being exhausted in 1851).
• Great sceptisism to petrolium burning was shown by D. Mendeleev…
• Once started it will once stopWHAT After… ?
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Discovery of radioactivity and estimation of its importance
Becquerel• In 1896 found out that
Uranium ore is emitting some new kind of rays.
Curie and Sklodowska
• French physicist Pierre Curie and his young Pole assistant (radio)chemist MariaSklodowska in 1898 found out that new Radium samples are more hotcompared to the environments for many months. They concluded : radioactivityis new and very important source of energy and proposed its usage for medical,pharmaceutical , …, purposes.
• Vernadsky in Russia in 1920 predicted that Ra and allied matter could be a very important key for new energetic in the World scale.
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2014 ‐ 60th anniversary of the First World NPP
• The first NPP was constructed in Obninsk, Russia , the first grid connection on June 26, 1954 providing the new city of Obninsk with electricity.
• The power plant remained active until April 29, 2002 when it was finally shut down.
• The single reactor unit at the plant, AM‐1had a total electrical capacity of 6 MW and a net capacity of around 5 MWe. Thermal output was 30 MW.
• It was a prototype design using a graphite moderator and water coolant. This reactor was a forerunner of the RBMK reactors.
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Potential of nuclear• To use the full potential of U (and Pu bred from it) requires fast‐neutron reactors
• The stock of depleted UO2 in the world when used in fast reactors will provide the energy equivalent to 4X1011 t oil
http://www.world‐nuclear‐news.org
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Fast neutron reactors
• Fast neutron reactors are a technological step beyond conventional power reactors.
• They offer the prospect of vastly more efficient use of uranium resources and the ability to burn actinides which are otherwise the long‐lived component of high‐level nuclear wastes.
• Some 20 reactors were operated and 400 reactor‐years experience has been gained in operating them.
• Generation IV reactor designs are largely FNRs, and international collaboration on FNR designs is proceeding with high priority.
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Fast reactors with diff. coolants:LLMC (Na), HLMC (Pb, LBE = Pb‐Bi) • FN types:• BN‐60• Brest‐300• BN‐600• Shevchenko• Phoenix• Superphenix• BN‐800• BN‐1200 ‐ project
• FR = the key to really closed nuclear fuel cycle
LBE = Lead‐Bismuth eutectic
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Fast reactors in Russia and ChinaBeloyarsk NPP CEFR ‐ China
• The single reactor now in operation was a BN‐600 fast breeder reactor, generating 600 MWe. (1980 – 2014)
• Liquid Sodium is a coolant.• Fuel: 369 assemblies, each
consisting of 127 fuel rods with an enrichment of 17–26% U‐235.
• It was the largest Fast reactor in service in the world. Three turbines are connected to the reactor. Reactor core ‐ 1.03 m tall , Diameter = 2.05 m.
• China's experimental fast neutron reactor CEFR has been connected to the electricity grid in 2011
•
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Fast BN‐800 with mixed UO2‐PuO2 fuel and sodium‐sodium coolant started 2014 in Russia.
Fast BN‐1200 reactor with breeding ratio of 1.2 to 1.35 for (U,Pu)O2 fuel and 1.45 for UN (nitride) fuel, Mean burn‐up 120 MWtXdXkg. BN‐1200 is due for construction by 2020 with Heavy Liquid Metallic Coolant (Pb‐Bi)
http://www.world‐nuclear‐news.org
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Generation IVreactor design
• The generation IV lead‐cooled fast reactor features a fast neutron spectrum, molten Pb or Pb‐Bi eutectic coolant.
• Options include a range of plant ratings, including a number of 50 to 150 Mwe units featuring long‐life, pre‐manufactured cores.
• Modular arrangements rated at 300 to 400 MWe, and a large monolithic plant rated at 1,200 MWe. The fuel is metal or nitride‐based containing U and transuranics.
• A smaller capacity LFR such as SSTAR can be cooled by natural convection, larger proposals (ELSY) use forced circulation in normal power operation, but with natural circulation emergency cooling.
• The reactor outlet coolant temperature is typically in the range of 500 to 600 °C, possibly ranging over 800 °C.
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• Develop and demonstrate fast reactor technology that can be commercially deployed
• Focus on sodium fast reactors because of technical maturity
• Improve economics by using innovative design features, simplified safety systems, and improved system reliability
• Advanced materials development• Nuclear data measurements and uncertainty reduction
analyses for key fast reactor materials• Work at Los Alamos focuses on advanced materials
development, nuclear data measurements, and safety analyses
Fast Reactors Program in USA
* ‐ Gordon Jarvinen VIII International Workshop ‐ Fundamental Plutonium Properties . September 8‐12, 2008
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Some of the concepts developed in the past or under development nowadays are the following:
• — In the Russian Federation, the small 75–100 MW(e) LBE cooled power fast reactor SVBR˗75/100
• — In Belgium, the 100 MW(th) multipurpose fast neutron spectrum MYRRHA facility, being designed to operate in both critical and subcritical mode
• — In Japan, a small power reactor cooled by lead‐bismuth and fuelled with metallic and nitride fuel featuring extra long life time; a 150 MW(e) lead‐bismuth cooled fast reactor concept Pb‐Bi cooled direct boiling water fast reactor (PBWFR)) featuring direct contact steam generators (‘steam‐lift effect’ of lead‐bismuth coolants); and a medium sized lead‐bismuth cooled fast reactor, lower breeding ratios in a Japanese scenario from 2030–2050 on
• — In the USA, the modular lead‐bismuth cooled STAR‐LM concept featuring natural circulation and the lead or lead‐bismuth cooled Small, Sealed, Transportable, Autonomous Reactor(SSTAR) concept rated 10–100 MW(e)
• — In Japan and the USA, the lead‐bismuth cooled encupsulated nuclear heat source (ENHS) concept, featuring natural circulation in both primary and intermediate circuits
• — In China, a lead‐bismuth cooled and thorium fuelled fast reactor concept • — In the Republic of Korea, a lead cooled fast reactor dedicated to utilization and
transmutation of long lived isotopes in the spent fuel
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Small Modular Reactors (SMRs)• Small Modular Reactors
(SMRs) are nuclear power plants that smaller in size (300 MWe or less) than current generation base load plants (1,000 MWe or higher).
• These smaller, compact designs are factory‐fabricated reactors that can be transported by truck or rail to where they are in need.
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36
7
6
13
3
65 Reactors for NPPs Under Construction ‐ by region:
Asia ‐ Far East
Asia ‐Middle East and South
EU 27
Other Europe
America
Sources: IAEA‐PRIS, MSC 2011
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NMR ‐ SRtechnics
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Nuclear MagneticResonance Spectroscopy
http://en.wikipedia.org/wiki/Nuclear_magnetic_resonance
Superconducting magnets 21.5 T Earth’s magnetic field 5 x 10‐5 T
NMR
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Now we have both 600 and 300 MHzAvance Brucker NMR spectrometers
in disposition of my laboratory
Avance‐300 BrukerAvance‐600 Bruker
D3‐12 NMR‐600MHz (12.3 AV600_CHEM)
OPERATED BY THE GROUP OF PROF. V.P. TARASOV, DR. G. KIRAKOSYAN AND V.A. IL’IN
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Nuclei in operationNucleus Spin γ, MHz/T Natural
AbundanceRelative
Sensitivity1H 1/2 42.576 99.985 1002H 1 6.536 0.015 0.963He 1/2 32.433 .00013 4413C 1/2 10.705 1.108 1.617O 3/2 5.772 0.037 2.919F 1/2 40.055 100 83.4
23Na 3/2 11.262 100 9.331P 1/2 17.236 100 6.639K 3/2 1.987 93.08 .05
99Tc 9/2 0 (99.8)
36Cl 2 0 (30)!
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•Number and type of NMR active atoms
•Distances between nuclei
• Angles between bonds
• Motions in solution
•Sternheimer const
•QQC
•Etc…
Information obtained by NMR
• Organic substances
• Radioactive materials
• Ga‐complexes
• Etc…
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99gTc‐NMR (TcO4 : O‐16, O‐17, O‐18)
99Tc NMR (67.55MHz) spectrum of 0.2 M NaTcO4 solution in recycled water containing ∼72% H2
18O at 298K.
270 280 290 300 310 320 330 340
0,40
0,41
0,42
0,43
0,44NH4Tc16O3
18O99Tc NMR H0=7.04Tл
Температура, Т К
Изотопный сдвиг Я
МР
99Тс
, м.д
.
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O‐17 NMR
• In water enriched in O‐17
280 300 320 340130,4
130,8
131,2
131,6
132,0 КССВ 17O-99Tc КССВ 99Tc-17O
NH4TcO4
H0=7.04Тл
Температура, Т К
КССВ
, Гц
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Tc‐NMR
Chem Shifts in TcO4 ‐ Puce hunting
• Solutions• Ionic pair formation• Receptor Complexes
Others• TcO4 – TcO6• Tc metal• TcO2
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99Tc ЯМР, CDCl3 UV, dichloroethane
Imine-amide macrocycle log(β11) = 3.2 log(β11) = 5.1
Cyclo[8]pyrrole·2(HCl) log(β12) = 3.8 log(β12) = 6.0
99Tc-NMR titration, Bu4N+ 99TcO4– in CDCl3
99Tc-NMR strengths
• Clear signal
• Good correlation with
UV
Kolesnikov G.V., German K.E, Kirakosyan G., Tananaev I.G., UstynyukYu.A., Khrustalev V.N., Katayev E.A. // Org.Biomol.Chem. ‐ 2011.
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Кривые обратного 99Tc ЯМР титрования для рецепторов L1 (а) (экспортированы из программы HYPER NMR 2006.
О – эксперимент, линии – расчетные кривые, черная – апроксимация константы, синяя – конц. TBA99TcO4,
красная – конц. комплекса хозяин – гость).
УФ‐вид
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Кривые обратного 99Tc ЯМР титрования для рецепторов L2 (б) (экспортированы из программы HYPER NMR 2006.
О – эксперимент, линии – расчетные кривые, черная – подгон константы, синяя – конц. TBA99TcO4,
красная – конц. комплекса хозяин – гость).
УФ‐вид
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Chemical shift
http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/nmr/nmr1.htm
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Chemical shift
δ = (f ‐ fref)/fref
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Intramolecular mode
• The Berry pseudorotation is a classical mechanism for interchanging axial and equatorial ligands in molecules with trigonal bipyramidalgeometry
• PF5• IF5
Intermolecular mode
• Tarasov exchange in TcO4‐TcO6 exchange spectra
Exchange spectra
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Pseudorotation via the Berry mechanism• Single‐crystal X‐ray studies indicate that the PF5 molecule has two dis nct types of P−F
bonds (axial and equatorial): the length of an axial P−F bond is 158.0 pm and the length of an equatorial P−F bond is 152.2 pm. Gas‐phase electron diffraction analysis gives similar values: the axial P−F bonds are 158 pm long and the equatorial P−F bonds are 153 pm long.
• Fluorine‐19 NMR spectroscopy, even at temperatures as low as −100 °C, fails to distinguish the axial from the equatorial fluorine environments.
• The apparent equivalency arises from the low barrier for pseudorotation via the Berry mechanism, by which the axial and equatorial fluorine atoms rapidly exchange positions. The apparent equivalency of the F centers in PF5 was first noted by Gutowsky.[2] The explanation was first described by R. Stephen Berry.
• Berry pseudorotation influences the 19F NMR spectrum of PF5 since NMR spectroscopy operates on a millisecond timescale. Electron diffraction and X‐ray crystallography do not detect this effect as the solid state structures are, relative to a molecule in solution, static and can not undergo the necessary changes in atomic position.
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Berry pseudorotation: NMR‐31P in PF5
Yellow atoms are axial Blue atoms are axial
http://fluorine.ch.man.ac.uk/pics/berry.gifhttp://pubs.acs.org/doi/pdf/10.1021/ed083p336.2
Mechanisms that interchange axial and equatorial atoms in fluxional processes:Illustration of the Berry Pseudorotation, the Turnstile, and the Lever Mechanisms via
Animation of Transition State Normal Vibrational Modes
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E
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NMR‐99Tc in 3 – 13 M H2SO4 [Tc] = 0.001M
-10
40
90
140
190
240
290
340
3 5 7 9 11 13
NM
R-9
9 Tc
shift
, pp
m
c(H2SO4), M0 ppm = 0,05M KTcO4
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99Tc‐NMR Tc(VII) in HClO4разбавление водой
C(HClO4) δ, ppm11,37 124,055
11 88,810,66 6010,33 36,2410,03 9,99,74 3,39,47 -1,449,22 -4,38,97 -6,28,74 -7,38,22 -8,457,33 -8,454,13 -3,463,07 -2,242,07 -1,13
0 0
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99Tc‐NMR Tc(VII) in HClO4разбавление водой
C(HClO4) δ, ppm11,37 124,055
11 88,810,66 6010,33 36,2410,03 9,99,74 3,39,47 -1,449,22 -4,38,97 -6,28,74 -7,38,22 -8,457,33 -8,454,13 -3,463,07 -2,242,07 -1,13
0 0
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Solid State NMR Characterization of the Structure of solid
Pertechnic Acid HTcO4
Solid state 99Tc‐NMR of HTcO4(solid)Provide some similarity to Re2O7*2H2OGives evidence for the absence of TcO4 !Charge separated structure favorable
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Solid‐State NMR Characterization of Electronic Structure in Ditechnetium Heptoxide
• Herman Cho, W.A. de Jong, A.P. Sattelberger, F. Poineau, K. R. Czerwinski ‐ J. AM. CHEM. SOC.
• NMR parameters were computed for the central molecule of a (Tc2O7)17 cluster using standard ZORA‐optimized all‐electron QZ4P basis sets for the central molecule and DZ basis sets for the surrounding atoms. • The magnitudes of the predicted tensor principal values appear to be uniformly larger than those observed experimentally, but the discrepancies were within the accuracy of the approximation methods used.• The convergence of the calculated and measured NMR data suggests that the theoretical analysis has validity for the quantitative understanding of structural, magnetic, and chemical properties of Tc(VII) oxides in condensed phases.
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• NMR spectrum of Tc metal powder obtained by FT of free induction decay accumulated after excitation of the spin system was recorded and used as a reference for analyses of technetium states supported onto the surfaces and formed in Tc‐Ru alloys/intermetalics.
• Knight shift of technetium metal is a linear function of temperature, K(ppm) = 7305 ‐ 1.52 x T. nQ(99Tc) = 230 kHz at 293 K, CQ(99Tc) = 5.52 MHz.
Typical NMR‐99Tc spectra of a ‐metal powder ( Ф 80‐150 μm) b – nano‐dimensional Tc metal Ф = 50 nm
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• 99Tc NMR study of bimetallic Ru‐Tc samples supported at different supports i.e.: g‐Al2O3 , SiO2, MgO, TiO2 has shown that for all the supports (except for TiO2), there is an intense signal at –30 – 40 ppm arising from the TcO2
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Synchrotron Radiation as a Tool
ISTR 2011 Moscow
Electromagnetic radiation generated by ultrarelativisticelectrons/positrons traveling along circular orbits in light charged particles accelerators
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Advantages compared to standard X‐ray sources
• Intensity/Brightness higher by 6‐10 orders of magnitude
• Continuum spectrum from IR to hard X‐rays• High natural collimation• Tunable polarization• Partial coherence
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EUROPEAN SR
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EUROPEAN SYNCHROTRONS incl. MOSCOW
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European synchrotron Radiation Facility,Grenoble,France
Production of X-rays in synchrotron
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European synchrotronESRF
Electron energy:6 Gev
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Bending magnets
Undulators
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• Siberian Center for Synchrotron Radiation (BINP, Novosibirsk) since 1970‐ies : Storage rings VEPP‐3 (2 GeV, 120 mA), VEPP‐4 (5 GeV, 40 mA) – both 1st generation (ε ~300 nm∙rad) 11 beamlines .
• Kurchatov Synchrotron Radiation Source (Moscow) in operatiion since early 2000‐ies Siberia‐1 (booster, 450 MeV) – 3 VUV beamlines , Siberia‐2 – dedicated 2nd generation source (2.5 GeV, 300 mA, ε ~75 nm∙rad), 16 beamlines .
• Zelenograd Synchrotron Rad. Facility (Lukin IPP) – under construction• Dubna Electron Synchrotron DELSI (JINR) – project development
• International collaboration:• Russian‐German beamline at BESSY II and Russian involvement in
ESRF consortium, • Russian part in European XFEL project (X‐ray free‐electron lasers ‐ M.
Kovalchuk (NRC "Kurchatov Institute", Moscow), A. Svinarenko (OJSC RUSNANO, Moscow) ( 4th generation source)
Synchrotron sources in Russia
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• Basics and typical applications of
‐ EXAFS/XANES‐ SAXS‐ XRD
• Combined application of X‐ray techniques to structural diagnostics of nano/materials
SR sources in Russia
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SYNCHROTRON DIAGNOSTICS OF Radioactive and Functional Materials
in National Research Center “Kurchatov Institute”
Department Head ‐ Yan Zubavichus
10 years in user mode
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ISTR 2011 Moscow
Kurchatov Synchrotron SourceLinac
Booster
Main storagering
Control room
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10.50 10.75 11.00 11.25 11.50 11.75 12.00
Pt L3
Re L2
Fluo
resc
ence
Yie
ld
Photon Energy, keV
Re L3
2. Diffraction
1. Spectroscopy
3. Imaging
Synchrotron techniques include
Especially proteinstructure solutions
Unique : Structures in solutionsand polymers
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KSRC X-ray stations1 Protein Crystallography
2 Precision X-ray Optics
3 X-ray Crystallography and Physical Materials Science
4 Medical Imaging
6 Energy-Dispersive EXAFS
7 Structural Materials Science (SMS)
8 X-ray Small Angle Diffraction Cinema (bioobjects)
9 Refraction Optics & X-ray Fluorescence Analysis
10 X-ray Topography & Microtomography
VUV stations
11 X-ray Photoelectron Spectroscopy
12 Optical spectroscopy for Condensed Matter
13 Luminescence & Optical Investigations
Technological stations
14 X-ray Standing Waves for Langmuir-Blodgett Films
15 Molecular Beam Epitaxy
16 LIGA
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Characteristics of the beamlineType Energy interval, keV ΔE/ESi(111) 5‐19 10‐4Si(220) 8‐35 10‐4Monochromator is driven by stepper motors (1‘‘ discrete steps)
• Ionization chambers + KEITHLEY 6487• Scintillation counter with NaI(Tl) crystals• Linear gas‐filled detector COMBI‐1(“Burevestnik”, St. Petersburg)• 2D‐detector ImagingPlate (FujiFilm BAS2025)• Semiconducting detector (pure Ge)
Maximum 3×3 мм2
Minimum 10×10 μm2
Step of translations ~4 μm
~ 0.5×108 photons/mm2 with energy bandwidth Δλ/λ=10‐4
Monochromators:
Detectors:
Beam dimensions:
Photon flux:
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In‐situ cell for functional materials
3‐component gas mixtures• Inerts: He, N2, Ar• Oxidation and reduction: O2, H2
• Catalytic substrate: CO, CH4, etc.• Vacuum 10 Pa
20‐550oC
Thermostabilization through the heating current & thermocouple feedback
±1oC
4 × 350 W
Cooling down to ‐130oC with a flow of cold N2 gas
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He closed‐cycle refrigerator (SHI, Japan)
Minimum temperature achieved 10.0К + precise termostabilization up to room temperature
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Combined use ofXAFS, XRD and SAXS
• XANES ‐ oxidation state of heavy atoms + coordination symmetry
• EXAFS ‐ local neighborhood of a given heavy atom
• XRD ‐ long‐range order, phase composition, size of crystallites
• SAXS ‐ size and shape of nanoparticles or pores in a range of 1‐100 nm
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X‐ray absorption spectroscopy: basics
ISTR 2011 Moscow
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FermilevelHOMO
LUMO
XANES: originVacuum
level
Core electronlevel
Valenceband
Forbidden gap
Conductionband
XANES probes the energy distribution of certain symmetry-allowed MOs or DOS features above the Fermi level
Fermi‘s golden rule:μ ~ |<f | V | i >|2 , f,i – wave functions of the final and initial states, V – dipole moment operator
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Photoionized atomNeighbor atom
Photoelectron wave
Back-scattered photoelectronwave
Single scattering
Multiple scattering
EXAFS: origin
Local-structrure parameters of the central atomcan be retrieved from EXAFS
Initial state: electron on the core levelFinal state: outgoing photoelectron wave
Interference
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)(/222
22
))(2sin(),()(
)( krkjjj
j j
j jj eekkrkfkr
NkSk λσϕπχ −−+= ∑
χ - normalized background-subtracted EXAFS-signalk – photoelectron vector modulus (≡2π/λ)S – Extrinsic loss coefficient (0.7-1.0)N – coordination number in the j-th coordination spherer – interatomic distancef – backscattering amplitudeϕ – phase shiftσ– Debye-Waller factorsλ− photoelectron mean-free path
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EXAFS/XANES: implementation at SMS
Detection modes: transmission (ion chambers)fluorescence yield ( NaI(Tl) scintillation counter,
detection limit down to 0.005 mass.%)
Data processing: IFEFFIT (Athena, Artemis, Hephaestus и др.) with ab initio theoretical phase and amplitude functions from FEFF8, GNXASAb initio XANES spectra simulation with FEFF8 , FDMNES, FitIt, etc.
Absorption edges measured over 2004‐2014
К‐edges:Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Br, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, In, Te
L3‐edges:Ba, La, Ce, Nd, Pr, Sm, Eu, Gd, Hf, Ta, W, Re, Pt, Au, Hg, Pb, Bi, U, Pu
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11525 11550 11575 11600 11625 116500.0
0.5
1.0
1.5
2.0
Nor
mal
ized
Abs
orbt
ion,
a.u
.
Photon Energy, eV
Pt Pt2+
Pt3+
Pt4+
Pt L3
6.53 6.54 6.55 6.56 6.57 6.58 6.59 6.60 6.61
Mn2+ (MnCl2 6H2O)
Mn3+ (Mn2O3)
Mn4+ (MnO2)
Mn7+ (KMnO4)
Photon Energy, keV
Mn K
16350 16400 164500.0
0.6
1.2
Nor
mal
ized
Abs
orpt
ion,
a.u
.
Photon Energy, eV
Bi0
Bi3+ (Bi2O3)
Bi3+ (Bi(NO3)3.2H2O)
Bi5+ (NaBiO3)
Bi L1
XANES
Information retrieved from XANES:• Effective oxidation state• Coordination polyhedron symmetryData analysis: “fingerpring” approach – comparison with reference spectra + theoretical simulations
1s→3d,4p 2p3/2→ 4d 2s→ 6p
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Application to TcTc K‐edge XANES
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Application to Re
Re L3‐edge XANES
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0 1 2 3 4 5 6
1.4 Tc-C 1.76Å6.0 Tc-Tc 2.72Å
TcCx
|FT(
k3 χ(k)
)|
R, Å
Tc
12 Tc-Tc 2.72Å
Tc METAL & Tc CARBIDE
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0 1 2 3 4 5 6
0.3 Re-C 2.14Å1.0 Re-C 2.46Å1.1 Re-Re 2.62Å 3.1 Re-Re 2.73Å
ReCx
|FT(
k3 χ(k)
)|
R, Å
Re
12 Re-Re 2.75Å
Re METAL & Re CARBIDE
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PYROMETALLURGY REPROCESSING OF SPENT FUEL
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Structures of Tc halogenides in solutions and melts1) fundamental studies of cluster Tc compounds
2) Analyses of possible species in PRORYV technology (chloride melts)
Tc K‐край k3‐weight EXAFS spectra and its Fourier transform for Tc (+4, +2,5, +2) halogenides
(Cl, Br)
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абв
а - Моноядерный бромидный комплекс TcK-край k3-взвешенный EXAFS спектри преобразование Фурье спектра(Me4N)2TcBr6 :
Tc-Br : N=5,8(4), R=2,51(2)Å, σ2=0,004Å2, ΔE0= -16,9(5) eV,
б - Биядерный кластер Tc K-край k3-взвешенный EXAFS и соответствующее преобразование Фурье спектра K3Tc2Cl8 EXAFS структурные параметры K3Tc2Cl8(лучшая из полученных предварительных аппроксимаций):
Tc-Tc N=1,66(3), R=2.20(2) Åσ2=0,0069 Å2 ΔE0= -1.1(9) eV
Tc-Cl N=2,2(4), R=2,46(2) Åσ2=0,0107 Å2,
в - Спектр и Tc K-край k3-взвешенный EXAFS для полиядерного хлоридного кластера (Me4N)3[Tc6(μ-Cl)6Cl6]Cl2, для которого не удалось получить удовлетворительного преобразования Фурье в рамках FEFF-5 приближения
Spectra EXAFS of complex Tc halogenides
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XAFS analysis of electrode surface after corrosionDetermination of eventual Tc oxide: ‐ In 1 M HCl (E= 800 mV)
‐In 1 M NaCl, pH= 2.5 (E= 700 mV)
XAFS measurement of: NH4TcO4, TcO2, Tc metal for comparison
Layer carefully removed and analyzed by XAFS.
SEM x 50Before After
pH =2.5, 1 M NaCl, E = 700 mV during 1 hour
M. Ferrier, F. Poineau, G.W. Chinthaka Silva, E. Mausolf and K. Czerwinski “Electrochemical Behavior of Metallic Technetium in Aqueous Media” : ISTR-2008. Port Elizabeth, South Africa.
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XANES
No pre‐edge : No TcO4‐ sorbed on electrode.
No shift of edge for 1M HCl , shifted (~1 eV) at pH = 2.5Product on electrode after corrosion : mainly Tc metal.
1 M NaCl, pH = 2.5 1M HCl
First deriv.
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EXAFS analysis also confirm presence of Tc metal on surface electrode after corrosion . No oxide detected.
EXAFS after corrosion XRD [5]
C.N R (Å) C.N R( Å)
Tc0-Tc1 10 2.72 12 <2.71>
Tc0-Tc2 6 3.83 6 3.85
Tc0-Tc3 8 4.76 8 4.73
pH =2.5
EXAFS
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NEXT :
•SAXS
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X‐ray detector (0D, 1D, 2D)
I(s)
Scattering vector s = k1 ‐ k0s = 4π sin θ / λ = 2π / d
Sample in the transmission geometry
2θ
k0
k1
s
Point/Linear collimation
Monochro‐matic X‐ray source
SAXS: Basics
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ISTR 2011 Moscow
Indirect FT
I(s) – experimentalscatteringcurve
P(r) – volumedistribution
of hard spheres
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ISTR 2011 Moscow
SAXS: implementation at SMS
Sample-to-detectordistance, mm
2θmin - 2θmax, ° qmin - qmax, nm-1
E = 25 keVqmin - qmax, nm-1
E = 6 keV
120 0.95 - 45.00 4.2 – 179 1 – 43
500 0.23 - 13.50 1 – 59 0.24 – 14.2
1000 0.11 - 6.84 0.5 – 30 0.12 – 7,1
2390 0.05 - 2.87 0.2 – 12.7 0.05 - 3
Only transmission geometry (no GISAXS for the moment)Scattering vector is oriented vertically;sample‐to‐detector distance up to 2.5 m; Photon energy 5‐30 keV (the possibility to employ anomalous scattering)
Treatment of experimental data: GNOM, MIXTURE, DAMMIN, SAXSFIT, IsGISAXS, Fit2D (for preliminary data processing of 2D images)
Simulation:
Single size distribution of
spherical particlesR=20±4 Å
IsGISAXS GNOM
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1 . Small‐angle diffraction on mesostructured materials
2 . SAXS application: aqueous colloids p.e. ‐ of Tc sulfide nanoparticles
3 . Quantitative interpretation of the SAXS curve for not‐interacting particles and aggregates (DAMMIN)
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Examples of combined structural studies
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E
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E
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E
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E
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Сдвиг ЯМР сигнала в нанодисперсном образце 20% Tc/g‐ Al2O3 (Рис. 4а) составляет7406 м.д., что на 600 м.д. превышаетзначение сдвига в порошке металлическоготехнеция с диаметром частиц 50–100 μм. Линия с шириной на половине высоты ~1 kHzимеет Лоренцевский вид и не имеет саттелитной структуры, связанной с квадрупольными взаимодействиями первогопорядка, типичными для ГПУ решеток. Для технециевой фольги толщиной 20μм спектр99Tc ЯМР показывает, что позиция центральной
компоненты очень близка к аналогичной позиции в образце микродисперсного порошка, хотя 8 саттелитов практически не выражены в результате высокой дефектности решетки кристаллитов фольги, связанной с многократными последовательными механическими обработками (прокаткой).
Отсутствие квадрупольной структуры в нанодисперсном образце ясно указывает на кубическую решетку фазы металличекого технеция. Значительное увеличение сдвига Найта в нандисперсном образце может отражать изменение плотности состояний на уровне Ферми по сравнению с микродисперсным образцом металлического технеция с ГПУ решеткой [7].
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• 99Tc ЯМР спектр образцы 5% Tc/γ‐Al2O3 при 295 K;
• (a) SW 1.7 МГц, число сканов 250000, (b) SW 250 кГц, число сканов 64000
•99Tc ЯМР спектры: (a) образца 20% Tc/γ‐Al2O3 при 295 K; SW 500 кГц, число сканов191000, D0 0.5s ; (b) порошка металлическогоTc с диаметром частиц 50–100 μм, SW 2.5 мГц, число сканов 50000, D0 0.5s.
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V.F. Peretrukhin, G.T. Seaborg, N..N. Krot, LNL, Berkley, 1998
3
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Periodic Table and heptavalent state of elements
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 metals/simple matter A.Wells “Struct.Inorg.Chem.”• Lost : P,S, Br, I, Po, At, Fr, Ra, Ac, Np, Pu, Am, Cm, Bk, Cf
TRU
5
Detailed fig In: Jarvinen et all
Plutonium
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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 theoxidation 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
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 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).
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BaUO4 structural type compounds
• 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
• LiReO4*1.5H2O contra LiTcO4*3H2O
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IR spectral data indicates Np‐O and Np=O difference
Evident splitting at the CsNpO4 spectrum indicates/supports the presence of two types of Np‐O bonds:
• O=Np=O• Np‐O‐Np
In Li5NpO6 all the Np‐O bonds are of the same nature
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Mossbauer spectra of Np(VII) compounds
• 1 – 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 :
fromMXO4
xnH2O (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 2010from Re(VII) acidBeyer H. et all.Angew. Chem., 1968
from I(VII) acid
from Cl(VII) acid
Структурный тип BaUO4.(Reis A.H. et al. JINC, 1976).
(Maruk A.Ya. et al. Russ. Coord. Chem.2011)
and from TcO3+
Pertechnetyl Fluorosulfate, [TcO3][SO3F] – ZAAC, 2007J.Supeł, U. Abram et all.Berlin, Freie Universität.
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Isostructural:LiBrO4 ∙ 3H2OLiClO4 ∙ 3H2OLiMnO4 ∙ 3H2O
LiTcO4 ∙ 6/2H2O 6/2=3
LiReO4 ∙ 1.5H2OLiReO4 ∙ H2O‐Analogous are absent
More diffused 4d electrons in Re compared to 3d electrons in Tc
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Isostructural pertechnetate salts withcation : anion = 1:1
CationAnion
ClO4- MnO4
- ReO4-
[Li · 6/2Н2O]+ + + *
Na+ – * +
K+ – – +
Rb+ – – +
Cs+ – – +
NH4+ – – +
Ag+ – – +
[(CH3)4N]+ + – +
[(C3H7)4N]+ – * +
[(C4H9)4N]+ * * *
[(C6H5)3PNH2]+ * * +
[C7H14N3]+ * * +
[C7H10N3(C3H5)4]+ * * +
[C7H10N3(C6H5)4]+ * * *
[C6H8N]+ – * +
[C4H10NO]+ – * +
[CN3H6]+ + * +
* Not determined. \ doesn’t exists– No similarity to Tc+ Isostructural
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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).
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Np(VII) & I(VII)
• 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
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
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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 = 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 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) 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)
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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
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 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 are close structural and
chemical analoguesof Np(VII) ones
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Tc(VII) & Pu(VII), Np(VII)
Pu(VII) and Tc(VII) are different in (cry,ele)‐structure, ligand arrangement, stability and chemical properties !
1000 ppm
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Periodic Table and heptavalent state of elements
Period is variable : 2, 8, 8, 18, 18, 32…?
Zones of implacability exist
For huge part ‐ It works ! ! !VII
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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 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 theheptavalent transuranic elements and the elements of Group VIIof the short form of the Periodic table and the formal nature ofsome of the structural similarities among the consideredheptavalent compounds.
• Principally one can attend the formation of Pu(VIII) but it is notthe aqueous media that could stand its oxidizing power.
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BessonovPerminov
Krot,Grigoriev
PeretrukhinGerman
CzerwinskiPoineau
Thank you for your Attention!
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ISTR‐2014
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Thank you for your attention !