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Moscow Stateuniversitythem. M.V. LomonosovMaterialsInternational conferenceundergraduate and

graduate studentsin basic sciences"LOMONOSOV-2005"(April 12-15, 2005)chemistry sectionVolume 2

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Materials of the International Conference of Students andpostgraduate students in fundamental

sciences "Lomonosov-2005".Section "Chemistry", vol. 2. M .: 2005.From 12 to 15 April 2005, the
Internationalconference of undergraduate and graduate students on fundamental sciences "Lomonosov-
2005".The purpose of the conference is to develop the creative activity of students and graduate
students,involving them in solving urgent problems of modern fundamental science,preservation and
development of a single scientific and educational space, the establishmentcontacts between future
colleagues. Working languages: Russian and English.Undergraduate and Postgraduate Student
International Conference in Fundamental Science"Lomonosov-2005". Moscow State University. April 12-
15, 2005.The purposes of the conference are: developing the creative activities of
undergraduatestudents, attracting them to solutions of the modern fundamental science actual
problems,maintenance and developing the common space of science and education, establishing
thecontact between colleagues. Working languages are: Russian and English.© Faculty of Chemistry,
Moscow State University, 2005Computer layout: Timoshin S.E.2

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Organizing committee of the section "Chemistry" of the conference "Lomonosov-2005"thanks for the
help in organizing and holding the conference:• "ChemBridge Corporation"• Company "Akzo Nobel"•
International Charitable Science Foundationthem. K. I. Zamaraeva• Russian branch of the Society of
Information Displays(Society of Information Display - SID)• International Foundation "Scientific
Initiative"4

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Branch "Catalysis"Jury:Smirnov A.V.Art. n. researcher, Ph.D. - chairmanPonomareva O.A.Art. n.

researcher, Ph.D. - deputy. chairmanE.V. Golubinan. researcher, Ph.D. - secretaryIvanova I.I.led. n.
Researcher, Doctor of ChemistryE.S. LoktevaArt. n. researcher, Ph.D.Romanovsky B.V.professor, doctor of
chemical sciencesRostovshchikova T.N.led. Researcher, Doctor of ChemistryChernavsky P.A.professor,
doctor of chemical sciencesChukhrai E.S.led. n. Researcher, Doctor of ChemistryAs part of the work of
the "Catalysis" department,student research papers competition for scholarshipsInternational Charitable
Scientific Fund named afterAcademician K.I. Zamaraeva. Scholarships are awardedauthors whose reports
were noted at the conference,having good academic performance and not receivingthe moment of the
competition for other nominal scholarships.five

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FEATURES OF LIQUID-PHASE CATALYTICHydrogenation of 4-NitrodiphenylamineAntina L.A., Sharonov

N.Yu., Lefedova O.V.Ivanovo State University of Chemical TechnologyCurrently, technologies based on
liquid-phase processescatalytic hydrogenation, allow you to organize an environmentally friendlywaste-
free production, reduce the number of synthesis stages, increase the yield anddegree of purity of the
target product.The work is aimed at developing the synthesis of 4-aminodiphenylamine (APDA) -the
starting compound used to obtain effective stabilizersnew generation tires and rubbers. The existing
synthesis of APDA based onchemical reduction of 4-nitrosodiphenylamine with sulfur compounds,
lowcost-effective due to the high cost of the nitroso compound, multi-
stageproduction,highexpenseecologicallydangerousreductant.An alternative way to obtain AFDA is to
obtain itliquid-phase catalytic hydrogenation of 4-nitrodiphenylamine (NDPA).Hydrogenation of NDPA
was carried out in a closed-type reactor with intensivestirring the liquid phase at atmospheric pressure
of hydrogen on a skeletalnickel catalyst in aqueous solutions of 2-propanol and sodium hydroxide. INas a
control over the composition of the reaction medium at condensation operations andhydrogenation, we
used thin layer chromatography and UV–spectrometry.NDPA was obtained by condensation of 4-
nitrochlorobenzene with aniline in xylene inpresence of calcium carbonate and copper oxide, followed
by distillation of componentssolvent, isolation and purification of technical NDPA. When carrying out
synthesisvaried: solvent, ratio of reagents, catalyst, temperature, timereactions; the NDPA yield varied
from 30% to 72%.The rates of NDPA hydrogenation in a complex way depended on the
compositionsolvent 2-propanol-water, which is associated with a change in solvation andthe adsorption
capacity of the nitro compound with an increase in the molar fraction of alcohol insolution. The highest
selectivity of the reaction in relation to ADPAwas achieved in aqueous solutions of sodium hydroxide.
The quantitativecorrelation between hydrogenation rate constants and maximum shiftabsorption in UV
spectra of aqueous alcoholic solutions of NDPA.6

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DEACTIVATION OF Zn-MFI PROPANE AROMATION CATALYSTAsachenko E.V.Moscow State University M.V.

Lomonosov, Faculty of ChemistryThe aromatization of light hydrocarbons on Ga- and Zn-MFI catalysts
isan economically important process that is at the stage of industrial implementationin Russia. One of
the main problems with these catalysts is their fastdecontamination due to coke formation. The aim of
this work was:identification of the main factors affecting coke formation on Zn-MFIcatalysts, as well as
the identification of active centers responsible for thisprocess.MFI-type zeolites modifiedzinc oxide
applied by incipient wetness impregnation. Studypropane aromatization was carried out on a flow-
through catalytic unit. With the aim ofselection of optimal conditions for the study of decontamination
reaction temperaturevaried from 520 to 580 o C, and the mass feed rate of raw materials from 0.55
to2.2 g (propane) / g (cat-ra) * h. Samples of catalysts before and after the reaction werecharacterized by
chemical analysis, thermogravimetry, IR-spectroscopy of adsorbed pyridine, low temperature nitrogen
adsorption.The composition of coke deposits was studied by the method of extraction of CH 2 Cl 2 , as
well as byanalysis of the C / H ratio by the combined method of TG and mass spectrometry.Zn / MFI
Catalysts Showed High Propane Conversion And Low Velocitydecontamination. Within 15 hours of
operation, the drop in conversion was 5%. Despitefor high stability of work on the samples, significantthe
amount of coke deposits (up to 3%) with a polyaromatic character.The formation of coke led to partial
blocking of acid sites, howeverthe pore volume of the catalysts varied slightly. Increasing the feed rate of
raw materials andan increase in temperature led to an acceleration of decontamination.This work was
supported by the Russian Foundation for Basic Research, INTAS (project 03-51-5286) and NSh(project
1275.2003.3).7

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EFFECT OF NUCLEOPHILIC AGENTS ON β-GALACTOSIDASEBeregalov A.E., Pilipenko O.S.Moscow State

University M.V. LomonosovA comparison of the amino acid sequences of β-galactosidases fromvarious
sources using the AMPS program and the degreeidentity of enzymes belonging to different families of
glycosyl hydrolases.Seven regions with an identity exceeding 50% in the catalyticdomain of β-
galactosidases of family 2, the preservation of functionalamino acid residues, including ligands of Mg 2+
ions in the active center.The result obtained made it possible to use data on the mechanism of
actionbacterial enzyme from Escherichia coli (the best studied β-galactosidase) whenstudy of an enzyme
from Kluyveromyces lactis belonging to the same family andthe most demanded at present in industrial
production.A study of the effect of some alcohols and magnesium cations onactivity of β-galactosidases
of Escherichia coli and Kluyveromyces lactis . The mechanism of actionβ-galactosidase corresponds to a
three-stage kinetic scheme with the formation of twointermediates, enzyme-substrate complex and
galactosyl-enzyme[1]. Compounds with nucleophilic properties compete withmolecules of water and
should accelerate the stage of degalactosylation. Activityenzyme in the presence of methanol,
butanediol-1,4 or butanediol-2,3 by 1.5-2.5 timesabove, with methanol having the greatest effect on β-
galactosidase activity.The presence of Mg 2+ cations also activates both enzymes.The use of two
synthetic substrates of β-galactosidase: ortho-nitrophenyl-β-galactopyranoside (o-UFH) and para-
nitrophenyl-β-galactopyranoside (p-UFH) showed that the reaction with p-UFH is limited by the
galactosylation stageenzyme, and the reaction with o-UFH is the stage of degalactosylation.The binding
constants of substrates and catalytic constants were calculated forthe first reaction product, ortho- and
para-nitrophenol.1. Sinnott ML // Chem. Rev. 1990. V. 90. P. 1171-1202 / Catalytic Mechanisms
ofenzymic Glycosyl Transfer.8

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HYDROALKYLATION OF BENZENE AND ETHYLBENZENE ONCATALYSTS Ru / Ni / BetaBorodina I.B.Moscow

State University M.V. Lomonosov, Faculty of ChemistryIncreasing the thermal stability of polystyrene by
introducing it into its compositionmolecules p- and m- phenylstyrene is an important task. However,
getting the datamonomers by direct alkylation of biphenyl to 4-ethylbiphenyl followed
bydehydrogenation on an industrial scale is impossible due to the comparativehigh cost of biphenyl and
low yields of the target product.In this work, a fundamentally new scheme for obtaining para-
andmetaphenylstyrenes through the stage of benzene hydroalkylation with ethylbenzene withthe
formation of p- and m- ethylcyclohexylbenzenes (ECGB).Zeolite H-Beta was chosen as a catalyst for this
process withSiO 2 / Al 2 O 3 35, 75, and 150 modified with Ru (1 wt%) and Ni(0.5 wt%) by incipient
wetness impregnation. Physical and chemical researchproperties of the catalysts were carried out by the
method of low-temperature adsorption of nitrogen,chemical analysis, TPD of ammonia, TPR with
hydrogen, as well as IR spectroscopyadsorbed CO. The catalytic properties of the samples were studied
in a flowreactor at a temperature of 170 0 C, a pressure of 10 atm and WHSV in the range of 1 - 64 g / g *
h.Based on the kinetic data, the selectivity curves were analyzed.The main reaction route is the partial
hydrogenation of benzene andethylbenzene to cyclohexene and ethylcyclohexene, which then alkylate
ethylbenzene andbenzene respectively. Complete hydrogenation withformation of cyclohexane and
ethylcyclohexane, cracking and isomerizationcyclohexyl ring, as well as deeper alkylation to
formderivatives of di- and tricyclohexylbenzenes.Study of the influence of the acidic properties of Ru / Ni
/ H-Beta with different ratiosSiO 2 / Al 2 O 3 on activity showed that an increase in the number of acid
sitespromotes alkylation and cracking reactions, reduces the formation ofproducts of complete
hydrogenation, while the selectivity of formation of m- ECHB and o -ECGB increases, and p- ECGB passes
through a maximum. Optimalthe catalyst for obtaining the target products is Ru / Ni / H-Beta with SiO 2 /
Al 2 O 375, at which the ECGB yield was 23%.This work was supported by the Russian Foundation for
Basic Research, INTAS (project 03-51-5286) and NSh(project 1275.2003.3).nine

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FEATURES OF SYNTHESIS OF MICRO-MESOPOROUS MATERIALS,OBTAINED ON THE BASIS OF MFI ZEOLITE

CRYSTALSVoronov A.S.Moscow State University M.V. Lomonosov, Faculty of Chemistry,Moscow State
University M.V. Lomonosov, Faculty of Materials ScienceProspects for the use of mesoporous silicates
(MS) as alysators of transformations of large organic molecules are associated, first of all, withdeveloped
porous structure with 20-100Ǻ channels forming a hexagonalpackaging. The distribution of such
materials is limited by their low thermal and thermal parameters.growth stability, also low acidity.
Zeolitization of MC pore wallsidentified in scientific publications as one of the most effective
waysregulation of stability and acidity. The purpose of this work was to studyfeatures of MS synthesis
using MFI zeolite nuclei.From reaction mixtures of the same composition (Si / Al = 45), severalseries of
MS, during the synthesis of which the temperature was varied (50, 100, and 150 о С) andthe duration of
the formation of embryos (0-240 hours). The synthesized samples werestudied using methods of
chemical analysis, IR spectroscopy,low-temperature nitrogen adsorption, X-ray small-angle diffraction.
Wasalso obtained a theoretical dependence of the change in the pore volume of the MS on the
thicknesspore walls.Analysis of the chemical composition of the samples showed their identity:
regardless ofsynthesis conditions the ratio Si / Al = 48-53. IR spectra of the samples showed that the
bandabout 550 cm -1 , indicating the formation of the MFI phase, is present only inspectra of samples
subjected to treatment at 150 to C either in the step of formingembryos, or at the stage of formation of
a mesoporous structure. From literarydata, it is known that the size of the nuclei of zeolite crystals is 20-
25Ǻ, which is3 times the thickness of the pore wall of the MC obtained by traditional methods.Using
small-angle X-ray diffraction, it was shown that independing on the nucleation temperature, the
thickness of the mesopore walls insynthesized materials varies from 7 to 15 Ǻ. For samples
passedprocessing at 150 to C, it was found that the volume change of samples pore wellis consistent
with the theoretical dependence of the pore volume on the wall thickness.This work was supported by
the Russian Foundation for Basic Research, INTAS (project 03-51-5286) and NSh(project 1275.2003.3).ten
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OPTIMIZATION OF PtRu / WITH MATERIALS FORELECTROCATALYTIC OXIDATION OF METHANOLGavrilov

A.N. 1 , Simonov P.A. 2 , V.V. Zaikovsky 2 , Savinova E.R. 21 Moscow State University M.V. Lomonosov,2
Institute of Catalysis SB RASOne of the urgent problems of modern materials science is the creation
ofhigh activity stable anode for direct methanol fuel cell. INbimetallic PtRu catalysts are currently used as
anodes,deposited on carbon supports, most often Vulcan XC-72 carbon black. Conductedrecent studies
[1] have shown that the attachment of PtRu particles to the soot of Vulcan XC-72does not provide a high
degree of catalyst utilization, and have demonstratedadvantages of domestic carbon carriers of the
Sibunit class with lowspecific surface area.In this work, the influence of the percentage of metal
oncarbon carrier Sibunit-19P (S BET ~ 60 m 2 / g) in the range from 5 to 60% of the mass. on
theelectrocatalytic activity in the oxidation of methanol and adsorbed CO.The catalysts were prepared by
coprecipitation from Na 2 PtCl 6 + RuCl 3 solutions (1: 1). Forcharacteristics of adsorption and redox
behaviorthe voltammograms of the catalysts were measured in a 0.1 M H 2 SO 4 solution , as well
asvoltammograms and stationary polarization curves of electrooxidationmethanol in this environment.
The true surface of PtRu was determined by CO chemisorption,the size of the PtRu particles is
determined by transmission electron microscopy, and their composition- by elemental analysis with
lateral resolution.Found that an increase in the percentage of metal from 5 to 60% of the mass.leads to
an increase in particle size from 1.7 nm to 10 nm. Comparative analysiselectrocatalytic activity showed a
monotonic shift of the peak potentialoxidation of the CO monolayer to the cathode region with an
increase in the metal content. Whenthis is also an increase in the specific activity for the electrooxidation
processmethanol (up to 40% wt.), however, with a further increase in the metal contentthe activity of
the catalysts decreases. The increase in specific activity is accompanied bynarrowing of the hysteresis
loop when cycling the potential and slowing down the fallcurrent on chronoamperograms. The work was
carried out within the framework of the RAS-Hydrogen program.1.V. Rao, PA Simonov, ER Savinova, GV
Plaksin, SV Cherepanova, GNKryukova and U. Stimming, accepted to J. Power Sources.eleven

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AROMATIC AMINO ALCOHOLS AND THEIR COMPLEXES WITH COPPER INREACTIONS OF ADDITION OF
POLYCHLOROMETHANES TO OCTEN-1Gantman M.G., Tarkhanova I.G.Moscow State University M.V.
LomonosovInitiation of the reaction of addition of CCl 4 to octene-1 2- (N-methylamino) -1-
phenylethanol, 3- (N-methylamino) -1-phenylpropanol-1, as well as their complexes withdivalent copper
1: 1 leads to the selective formation of 1,1,1,3-tetrachlorononane with high olefin conversion.
Composition of adhesion productschloroform depends on the nature of the initiator: initiation with
amino alcohols proceedssimilar to peroxide and leads to the formation of mainly 1,1,3-
trichlorononane.When using a copper complex in addition to the specified product in a
significantamount of 1,1,1-trichlorononane is formed, a characteristic addition productchloroform to
octene-1 in the presence of transition metal complexes.In the presence of an amino alcohol, the kinetic
equation is:[] Lkw eff=... INpresence of a copper complex[] [] 5.0sixteen8HCCuLClkw eff=(L - amino
alcohol,). Suchwe explain the differences by different mechanisms of initiation in the presence
ofcomplex and amino alcohol. Based on chromatomass spectrometric datait was found that the
interaction of CCl 4 with the initiator includes the stage of dissociationone of the bonds at the benzyl
carbon atom, as evidenced by the formation inas products of chloroform, benzaldehyde, methyl phenyl
ketone. Thus,the high activity of aromatic amino alcohols may be due toformation at the initiation stage
of a relatively stable benzylradical. We explain the high selectivity of the reaction by the participation of
moleculesan initiator in the chain transfer stage.It was found by the EPR method in the spin trap
technique that thethe reaction proceeds by a radical mechanism. In a solution of initiators
(peroxidebenzoyl, aminoalcohols, N-methylphenethylamine) in CCl 4in the presence of spintrap (2-
methyl-2-nitrosopropane) formation of trichloromethylradicals at room temperature. The value of the
stationary concentration of spinTrichloromethyl trap adductor correlates with catalytic
activityinitiator.This work was supported by the RFBR grant No. 03-03-32863.12

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NEW P, N –BIDENTATE PHOSPHITES WITH CHIRALKETIMINE FRAGMENT AND P, P, N, N -TETRADENT

PHOSPHITESZheglov S.V., Konkin S.I., Tsarev V.N., Shiryaev A.A., Davankov V.A., Gavrilov K.N.Ryazan State
Pedagogical University named after S.A. YeseninPrior to the beginning of this study, phosphites with a
ketimine fragment were notare known. A new P , N -bidentate chiral arylphosphite was obtained by a
one-stepby phosphorylation of the corresponding iminophenol:POOCl+16five432N2`3`4`5`6`1`HOC 6 H 6
, Et 3 N123- Et 3 NxHCl7POO16five432N2`3`4`5`6`1`O6``3``2``4``5``1``The possibility of using these
compounds in the reactionsasymmetric allyl substitution. In particular, in palladium
catalyzedsulfonylation1,3-diphenylallyl acetatep- toluenesulfinitesodiumup to 73% ee, in the alkylation
of 1,3-diphenylallyl acetate with dimethylmalonate -up to 94% ee. Moreover, the new phosphite ligand
provides much greaterenantioselectivity than phosphine analogs described in the literature.Compounds
of the second type are interesting for their ability, depending onmolar ratio ligand / metal, realize both P,
N- and P, P- bidentatetypes of bonding with the central atom. In turn, this can providedetermining
influence on catalytic activity and enantioselectivity.Ligands 4 and 5 obtained by direct
phosphorylationONMeEtFeONMeEtfiveONMeEtFeONMeEt4NNPMeOMeMeOMePNNPMeOMeMeOMeP
the corresponding imino alcohol in benzene solution, were tested in Pd -catalyzed reactions of formation
of C * -C, C * -N and C * -S bonds.PhPhOAcPhPhNu+ HNuPd / L, baseTHF or DCM, rt, 48 hNu = SO 2 p Tol
- ,0% ee (2), 81% ee (3)CH (COOMe) 2, 84% ee (2), 90% ee (3)pyrrolidine 15% ee (2), 85% ee (3)13

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NEW CATALYTIC SYSTEMS Pt-CeO x OBTAINEDOXIDATION OF INTERMETALLIDESZosimova P.A.Moscow

State University M.V. Lomonosov, Faculty of ChemistryPt-CeO x systemsare active catalysts for a number
ofindustrial processes. It is noted that the interaction of platinum with cerium oxideincreases its stability
against poisoning with sulfur compounds. To prepare suchsystems use the impregnation method, which,
however, does not allow controlhomogeneity of the distribution of phases over the surface of the carrier
and ensuredirect contact of platinum with cerium oxide.In this work, we propose a new method for the
preparation of Pt-CeO xfrom their intermetallic compounds, consisting in the selective oxidation of
cerium and the formationhighly dispersed platinum particles in direct contact with the oxidecerium. The
catalytic properties of the samples were studied in a model hydrogenation reactiontoluene in the
presence of H 2 S. Physicochemical properties are characterized by methodsIn situ XRF , SEM / EDS, TEM,
TPR N 2 and XPS.It was found by in situ XRD that the oxidation of cerium begins already at300 ° С, a
further increase in temperature to 600 ° С does not lead to changesphase composition of the system;
however, this leads to an increase in the particle sizeplatinum from 6 to 11 nm.It has been shown by SEM
and TEM / EMF that Pt is in two states: in the formplatinum metal and Pt-CeO 2 joint structures .
Presence of two typesactive sites are also confirmed by catalytic data. On curvesdecontamination,
reflecting the dependence of the conversion of toluene on the amount suppliedH 2 S, two linear sections
are observed. At the first stage, there is a sharp decreasecatalytic activity, but upon reaching toluene
conversions of 20-30%, a dropthe activity of the samples slows down significantly. According to the
energy-dispersiveanalysis of samples deactivated by hydrogen sulfide, sulfur accumulation occursmainly
on particles of platinum metal, while on the surfacein the joint structures of Pt-CeO 2, the presence of
sulfur is practically not detected.This work was supported by the Russian Foundation for Basic Research,
INTAS (project 03-51-5286) and NSh(project 1275.2003.3).fourteen

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KINETIC FEATURES OF HYDROCARBON ISOMERIZATIONON ZEOLITE CATALYSTSA.A. Kabkov, I.V.

KozhemyakinSaratov State University N.G. ChernyshevskyGreening motor fuels limits the content of
aromatichydrocarbons (no more than 55% by weight) and benzene (no more than 5% by weight) and
requiresensuring their high octane number.The solution to this problem is possible by improving the
processreforming and the use of catalysts with high isomerizingabilities, since hydrocarbons of
isostroenia increase the octane numbergasoline.The work investigated the catalytic reforming of n-
hexane and fraction 85-180 ° C intemperature range 300-400-500 ° C, volumetric feed rate 1 h -1 ,
atatmospheric pressure without circulation of the hydrogen-containing gas. Exploredregularities of the
course of the main reforming reactions on alumoplatinoreniumand zeolite catalysts. It was found that on
these catalystsformation of iso-structure hydrocarbons, the content of which is maximum atТ = 300 ° С
and the selectivity for isomerization at CVC-III is almost 2 times higher than atZSM-5. With increasing
temperature, the amount of isomers in the catalysis is significantlydecreases due to the predominance of
reactions leading to the formation of aromatichydrocarbons and gaseous products of the conversion of
n-hexane.Kinetic patterns of n-hexane conversion on zeolite catalystscalculated by several methods: by
the Frost equation, and by the calculation methodthe observed activation energy proposed by G.M.
Panchenkov. and Yu.M. Zhorov,based on the use of experimental depth curvestransformation (x) on the
feed rate of the reactant (n 0 ). Received bythe Frost and Panchenkov method, the values of the
apparent activation energy of n-hexanepractically coincide with each other. The activation energy of the
total transformation of n-hexane is the same for both calculation methods (97.28 and 83.22 for CVC-III-
895 and ZSM-5respectively), according to the dehydrocyclization reaction they still differ from each other
- according tothe Frost method is slightly larger than the curves x = f (n 0 ).Thus, ways of greening motor
fuels by increasingisomerizing activity of catalysts. Kinetic patterns establishedconversion of n-hexane on
high-silica zeolite catalysts.15

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INTERACTION OF METALS IN BIMETALHYDRODECHLORINATION CATALYSTSKachevsky S.A., Golubina E.V.,

Lokteva E.S.Moscow State University M.V. Lomonosov, Faculty of Chemistry,
kachevskysa@kge.msu.ruPalladium-based bimetallic catalysts with the addition ofbase metal (Ni, Fe, Co)
are used for a wide range ofchemical transformations such as hydrocarbon isomerization,
hydrogenationolefins, hydrodechlorination, CO oxidation. Adding a second metal likeusually leads to an
increase in catalyst activity. Finding true reasonsthis phenomenon is given great attention in the scientific
world.We studied multiphase hydrodechlorination (HDC) of polychlorinatedbenzenes in the presence of
Pd-containing catalysts with the addition of a second metal(Ni, Fe, Cu, Co) deposited by impregnating the
support with nitrate solutionscorresponding metals to activated carbon (total metal content10% at ratios
4: 1, 1: 1 and 1: 4), as well as for ultrafine diamond (UDD)(metal content 10%, metal ratio 1: 1).All
studied bimetallic catalysts were found to be active inmultiphase HDC of trichlorobenzene. From
catalysts deposited on activatedcoal, the most active were bimetallic catalysts Pd-Ni / C. Whenan
increase in the concentration of palladium in the samples from 2% to 5% and 8%, the degreeconversion
of TCB after 150 min. the reaction increased from 86% to 92% and 100%,respectively. It was shown that
in some cases it is possible to replace up to 40% Pdto another metal without significant loss of activity.
Hydrodechlorination rateTCB in the presence of catalysts supported on UDD was found to be very high.
TOFor example, the conversion rate of TCB in the presence of 5% Ni5% Pd / UDD reached 100%already
after 50 min. reactions.The activity of catalysts is strongly influenced by the acidity of
impregnatingsolutions of precursors. Based on thermal programmed recovery dataand measurements of
magnetization, it was shown that the pH of the solution during impregnation affectsthe degree of
interaction of metals in the catalyst.sixteen

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ADSORPTION OF WATER VAPORS ON MANGANESE OXIDEOZONE DECOMPOSITION CATALYSTSKireev A.S.

1 , Tkachenko I.S. 21 Russian University of Chemical Technology DI. Mendeleev2 Moscow State University
M.V. Lomonosov, Faculty of ChemistryIt is known that the best ozone destructors are manganese oxide
(MAO)catalysts, including hopcalite. However, the activity of the latter in the reactionsdecomposition of
residual ozone in the presence of water vapor is significantly reduced, i.e.water is a catalytic poison. In
this regard, the study of adsorptioninteractions in the systems "MOK-water" is of considerable interest
not onlyfrom a theoretical but also from a practical point of view.The purpose of this work is to study the
equilibrium adsorption of water vapor attemperature of 293 K. The objects of study were granular
catalysts,obtained using the method of extrusion molding. Their basiswere MnO 2 and CuO, taken in a
ratio of 4: 1. As a binder(10% wt.) Used bentonite clay (sample no. 1 - analogue of industrialhopcalite of
the GFG type) and calcium oxide (sample no. 2).The adsorption isotherms for both samples can be
classified as type II byclassification of BDDT, while arr. No. 1 exhibits a higher adsorptionability. The
experimental data are linearized within the BET model inthe range of equilibrium vapor pressures of the
adsorbate 0.02-0.3 p / p o . This allowscalculate for samples No. 1 and 2 the value of the capacity of a
monolayer: 2.1 ± 0.2 and 1.5 ± 0.1mmol / g, respectively, and the value of the constant C: 100 and 70,
respectively.The results obtained indicate that the adsorption propertiesmanganese oxide catalysts have
a noticeable effect on the binder.Bentonite clay is a fairly inert substance - weaksolid acid, while CaO is a
reactive solidbasis. It can be assumed that calcium oxide, when interacting withcatalytic base suppresses
adsorption centers to a greater extent thanbentonite clay.17

Page 18
STUDY OF PROPERTIES OF CU-CONTAINING CATALYSTSTRANSFORMATIONS OF EXPOSED
HYDROCARBONSELECTROHYDRAULIC SHOCKI. V. KozhemyakinSaratov State University N.G.
ChernyshevskyThe oil refining industry is one of the most importantindustries providing the world's
energy needs. Leading valuecatalysis in the implementation of chemical transformations of hydrocarbon
raw materialsprovides high economic efficiency, environmental friendlinessreceived energy carriers. In
this regard, the search for highly effective, active andselective process catalysts is a very urgent
problem.In order to increase catalytic activity during preparationKt catalysts use various methods of
changing the surface structure andits composition: mechanochemical activation, surface irradiation and
ultrasonicexposure, treatment in low-temperature plasma, in the glow discharge zone and underthe
action of microwave radiation. Almost all of the above physical effectsconcentrated in the
electrohydraulic effect (EHU) discovered by Yutkin. Uswork is underway to establish the impact of this
effect on the formationcopper-containing heterogeneous catalytic systems characterized by highactivity
in the process of reforming hydrocarbons.Investigated the effect of (ESP) on changes in the surface
structurecatalyst (2.5% Cu + 0.1% Pt / Al 2 O 3 ) and its composition. The results of the transformation of
n-hexane in the presence of Cu, Pt / Al 2 O 3 (EGU) are presented in the table. Determined
thatprocessing of the initial ESP catalytic system at the impregnation stage leads toan increase in the
yield of the target product - benzene from 30.8 to 64.1 wt. % at T = 550 ° C.Table. Results of n-hexane
conversion on 2.5% Cu 0.1% Pt / Al 2 O 3 catalyst(numeric) and processed by EGU (banners)T,V rev.
,Composition of transformation products, wt%° Ch -1∑С 1 -С 2∑С 1 -С 5i-C 7C 5 -DHCC 6 H 6C 6 H 14450
2.1 1.4 / 0.1 6.8 / 0.29.9 / -23.9 / 0.3 22.4 / 36.3 35.6 / 63.1500 2.4 3.3 / 0.2 10.7 / 0.4 9.5 / -22.8 / 0.5
23.9 / 50.1 29.8 / 48.8550 2.2 6.0 / 1.2 18.1 / 4.0 4.7 / -13.4 / 0.9 30.8 / 64.1 27.0 / 29.8A feature of the
obtained catalyst is a decrease in the reactionhydrocracking, which also increases the selectivity of the n-
hexane reforming processby the aromatization reaction.18

Page 19

PHOTOCATALYTIC OXIDATION OF ORGANOPHOSPHORUSSUBSTANCES IN THE RECIRCULATION

REACTORKozlova E.A.Novosibirsk State UniversityCurrently, there is an acute problem of water
purification from variouspollution. Many contaminants such as pesticides and detergents, andsome
chemical warfare agents are organophosphorus.Photocatalytic oxidation of organophosphorus
substances in aqueous suspensionstitanium dioxide is an effective and cheap method of water
purification. Ourstudies were carried out with an analogue substance for toxic
organophosphorusdimethylmethylphosphonate (DMMP).The first stage of our work was the preparation
of an active photocatalystby modifying the standard Degussa P25 TiO 2 with noble metals - Pt and
Pd,and also treatment with sulfuric acid. Platinized catalyst showed activity3 times more than the
original catalyst.The next step in our work was to study the effect of increasing the sizereactor on the
rate of oxidation of organophosphorus. We moved from research toa beaker with a suspension volume
of 150 ml to a 3 L recirculation reactor.Oxidation of DMMP in a recirculation reactor was carried out with
a catalystdeposited on a porous support and in suspension, with and without air purging.It was shown
that the maximum rate of DMMP oxidation is achieved atcarrying out the reaction with the supported
catalyst with an air purge. Previously usit was shown that the kinetic dependences of the DMMP
oxidation in aqueous suspensionstitanium dioxide obey the Langmuir-Hinshelwood equation [1].
Kineticdependenciesoxidationinrecirculatingreactoralsowellare approximated by this model. The
constants calculated for these two cases arematch. This is a good result, since when changing from
suspension to appliedthe oxidation rate may decrease on the catalyst. The applied catalyst is more
convenientfor use due to the ease of separating it from the reaction mixture and its morehigher stability
than suspension.This work was supported by the Finnish “Russia in Flux” projectNo.2088134.1.
EAKozlova, PGSmirniotis, AVVorontsov, J. Photochem. Photobiol. A: Chem.,162 (2004) 503-511.nineteen

Page 20

STUDY OF NEW GENERATION CATALYTIC PROPERTIESMICROMESOPOROUS MATERIALSKonnov S.V.,

Voronov A.S.Moscow State University M.V. Lomonosov, Faculty of ChemistryCreation of new micro-
mesoporous catalysts for oil refining andpetrochemistry, combining both the properties of zeolites (a
wide range of acid sites,high thermo- and thermo-steam stability) and mesoporous materials (poreslarge
diameter, providing transport of molecules of reagents and productsreaction) is an important and urgent
task.The aim of this work was to study the catalytic properties of a newtype of micro-mesoporous
materials obtained using germscrystals of MFI zeolite in cracking reactions of isopropylbenzene (IPB) and
1,3,5-triisopropylbenzene (TIPB).Samples of micro-mesoporous materials with different micropore
contentwere synthesized from the nuclei of MFI zeolite crystals obtained bytemperature of 50-150 ° C
for 0-120 hours. Temperature of formation of mesoporousstructure was 100-150 o C. The obtained
samples were characterized bymethods of chemical analysis, IR spectroscopy, low-temperature
adsorptionnitrogen, TPD ammonia, SEM.The catalytic properties of the samples were investigated in
model reactionscracking IPB and 1,3,5-TIPB in a flow reactor at a temperature of 300 ° С, WHSV = 1.1h -1
and molar dilution with nitrogen in the ratio IPB (TIPB): N 2 = 1: 5.Termoparoobrabotku carried out at
600 to C for 4 hours.It was shown that MFI zeolite is not active in the cracking of 1,3,5-TIPB due
toinaccessibility of acid sites of the MFI structure for large 1,3,5-TIPB molecules,whereas mesoporous
aluminosilicate is not active in cumene cracking due to its low strengthacid centers. An increase in the
proportion of micropores leads to an increase in activitymicro-mesoporous materials in the cracking
reaction of cumene and a decrease in activity incracking reactions of 1,3,5-triisopropylbenzene. It was
also found that the studiedmaterials are more resistant to thermal steam treatment compared to
mesoporousmolecular sieves.This work was supported by the Russian Foundation for Basic Research,
INTAS (project 03-51-5286) and NSh(project 1275.2003.3).20

Page 21

MULTIPHASE HYDRODECHLORINATION OF TRICHLOROBENZENE INPRESENCE Pd / (ZrO 2 + Al 2 O 3 )

Korotkov A.V., Golubina E.V., Lokteva E.S., Turakulova A.O.Moscow State University M.V. Lomonosov,
Faculty of ChemistryMany of the organochlorine compounds are harmful to healthpeople, including
carcinogenic, and decompose with difficulty in natural conditions.Therefore, the processing of halogen-
containing organic wastecontinues to be today one of the most important problemscatalysis. The most
promising method for processing halogenated wastecan be considered hydrodechlorination, or
hydrogenolysis. Along with environmentalsafety, it provides in some cases the regeneration of the
feedstock orselective production of other useful products.We used 2% Pd supported on zirconium
oxide,modified with 1, 5 and 10% Al 2 O 3 . The carriers were prepared by coprecipitation from
solutionssalts with ammonia at pH = 9, followed by calcination at a temperaturecrystallization of the
tetragonal phase. The catalysts were prepared by the precipitation methodpalladium hydroxide on the
support from the calculated amount of PdCl 2 solution . Thenthe samples were calcined at 350 ° C and
reduced with hydrogen for an hour at400 ° C.It was shown by DTA and XRD that modification with
aluminum oxide leads tostabilization of the tetragonal phase of ZrO 2 .The catalytic activity was studied
in multiphase hydrodechlorination of 1,3,5-trichlorobenzene (TCB). The reaction medium consisted of an
aqueous alkali solution,solution of TCB in isooctane, a heterogeneous catalyst, Н 2 and a phase-transfer
agenttransfer.The conversion products of 1,3,5-trichlorobenzene were dichlorobenzene, chlorobenzene
andbenzene. They were determined quantitatively by GLC using internalstandard (nonana). Based on the
experimental data obtained,kinetic curves were constructed, from which, assuming the reactions of the
firstthe rate constants of the reactions were obtained for each catalyst.It was found that the highest rate
of hydrodechlorination is observedwhen using as a catalyst 2% Pd / (ZrO 2 + 1% Al 2 O 3 ). In this case,
alreadyafter 35 min, only one product is present in the organic phase - benzene.21

Page 22

SIZE EFFECTS IN NANOSTRUCTURED PHASESIRON OXIDES IN ZEOLITE MATRICESMaerle A.A.Moscow

State University M.V. Lomonosov, Faculty of ChemistryFinely dispersed iron oxides are promising
catalystsoxidation. When the size of the active phase decreases to 1-5 nm (nanoclusters)a sharp increase
in the activity of the catalysts is observed. However, the substance innanocrystalline state is metastable
and prone to aggregation,which can be avoided when it is stabilized in the pores of an inert matrix.In this
regard, in this work, an attempt was made to synthesizeiron oxide nanoclusters directly in the pores of
the carrier NaY, MCM-41 and SiO 2 .Tricyclic iron dodecacarbonyl Fe 3 (CO) 12 was used as a precursor
,which was introduced by the impregnation method followed by drying and calcinationat 550 ° C. The
iron content in all samples was 0.1-1 wt%.The relative particle size of Fe oxides was determined by TPR-Н
2 and UV-spectroscopy. The activity of the samples was studied in a model oxidation reactionmethanol
at 250 ° C.According to TPR-N 2 data for all samples, a shift of the maxima towardshigher temperatures
compared to individual oxide, whichindicates a high dispersion of Fe oxide in the supported samples.
Assessmentthe consumption of hydrogen consumed for reduction gives a value essentiallyexceeding the
stoichiometric hydrogen consumption, and the hydrogen consumptionbecomes equal to stoichiometric
when the iron content is about 1 wt% fordifferent media. The observed effect may be due
toultradispersed state of iron oxide.The size effect also manifests itself in the catalytic oxidation of
methanol. FROMan increase in the iron content from 0.1 to 1 wt% catalytic activity related toone Fe
atom, significantly decreases, which is associated with an increase in the size of oxideparticles and, as a
consequence, with a decrease in the fraction of surface iron atoms,participating in catalytic
oxidation.This work was supported by the Russian Foundation for Basic Research, INTAS (project 03-51-
5286) and NSh(project 1275.2003.3).22

Page 23

Valence and Coordination State of Co B AtomsNANOPHASES OF LANTHANUM COBALTESMakshina

E.V.Moscow State University M.V. Lomonosov, Faculty of ChemistryMixed oxides La and Co (cobalt LaCoO
3 ) due to highstructural oxygen mobilities are promising catalystsoxidative processes. However, the bulk
phases of cobaltates with the structureperovskites have too small a surface to compete withtraditional
oxidation catalysts. In this work, an attempt is made toits significant increase by in-situ synthesis of
nanophase LaCoO 3 directlyin the pores of the MCM-41 molecular sieve.Comparison of the obtained
samples as catalysts for the oxidation of methanol showedthat the activity of the nanophase LaCoO 3 is
two orders of magnitude higher than that of the bulk one. Such a differencecannot be explained only by
an increase in specific surface area catalyticallyactive lanthanum cobaltate. In this regard, we
investigated the states of atomsCo in the composition of deposited cobaltate by EXAFS, XPS and EPR
methods.Analysis of the near fine structure of the XAFS spectrum showed that in the depositedin the
sample, the average oxidation state of cobalt is close to 2+, while in the individualperovskite it is 3+. At
the same time, the shape of the absorption peak is evidenced bythe absence of Co 3 O 4 particles in the
LaCoO 3 / МСМ-41 sample . It should be noted that inin the case of deposited cobaltate, the bands in
the spectrum are strongly broadened and this form of the spectrumdue to either too small particle size,
or significant structuraldisorder in the particles of deposited cobaltates. XPS data also showthat, in
contrast to bulk LaCoO 3 , cobalt is in the nanophase of cobaltate,mainly in the Co 2+ state , although the
presence of somethe amount of Co 3+ . Finally, the EPR spectra of the supported cobaltate indicatethe
fact that the paramagnetic Co 2+ ions in the nanophase LaCoO 3 have an octahedralcoordination to the
oxygen atom, which is characteristic of bulk perovskitestructures.This work was carried out with financial
support from the State Programsupport of the leading scientific schools of the Russian Federation (NSh
No. 1275.2003.3), L. Euler's programGerman Academic Exchange Service and HALDOR TOPSE A / O.23

Page 24

SOCATALYSIS IN THE INTERPHASE CATALYTIC REACTIONDehydrobromination of 1,2-DIBROM-1-

PHENYLETHANEMamontova Yu.V.Tyumen State UniversityElimination reactions are widely used in the
field of synthesismodern polymer materials and plastics, medicines,surfactants, chemical additives and
compositions used forenhanced oil recovery.Improving the efficiency of elimination reactions for various
substratesseems possible due to the use in interphase catalytic reactionsmixtures of various phase
transfer catalysts as well as applicationscocatalysts - organic compounds of an acid-base nature
(alcohols,phenols, amines, etc.) [1-3].In this work, the effect of lipophilic alcohol additives onthe
efficiency of the model reaction of dehydrobromination of 1,2-dibromo-1-phenylethane intwo-phase
systems "liquid / liquid" and "liquid / solid" in the presence oftetraalkylammonium bromides as the main
phase transfer catalyst.It was found that the promoting effect of alcohols increases in the following
order: n-butanol ≈isopropanol <butanediol - 1,4 <tert-butanol <dimethylethylcarbinol.
Magnificationlipophilicity of the phase-transfer catalyst facilitates the extraction of alcoholate iondeep
into the organic phase.An efficient procedure for the synthesis of phenylacetylene with a yield of at
least75% under mild conditions: t = 70 0 С, τ = 8 min, in a two-phase liquid / solid systemphase ", a
solution of 1,2-dibromo-1-phenylethane in toluene was used as a substrate,the solid phase was finely
ground potassium alkali sifted through a sieve,phase transfer catalyst - tetraoctylammonium bromide, as
a cocatalystused tertiary alcohol - dimethylethylcarbinol.1. Sirovsky FS, Mochalov VN, Panova MV. //
Advances in chemistry. - 1991 .-- T. 60. -Issue 4. - P. 714–735.2. Savelova V.A., Vakhitova L.N. // Izv. Ak.
sciences. Chemical series. - 1995. -No. 11. - P. 2108–2114.3. Shavanov S.S., Tolstikov G.A., Shutenkova
T.V., Viktorov G.A. // ZHOKH. - 1987.- T. 57. - Issue. 7. - S. 1587-1594.24
Page 25

SYNTHESIS OF HYDRAULIC TREATMENT CATALYSTS AND STUDY OF THE INFLUENCEMODIFYING

ADDITIVES ON THEIR ACTIVITYNikulshin P.A., Eremina Yu.V.Samara State Technical UniversityAt the heart
of the science of catalysis is the scientific basis of foresightcatalytic action. It is this section that should
answer the question about the roleindividual components and phases in catalysts, about their optimal
ratio,combination and distribution. However, the task of practical implementation of
suchrecommendations is extremely complex and empirically cannot be solved inoptimal performance.
This task is the basis for the section of scientific foundationspreparation of catalysts.Catalysts are the
backbone of many refining processes. thereforethe question of the development of hydrotreating
catalysts is becoming very urgent,active both in hydrodesulfurization and hydrogenation reactions. Takes
placeselection of such compounds as additives that could providestructural, so purely chemical
modification of the catalyst surface.Therefore, this work is devoted to the synthesis of hydrotreating
catalysts andstudy of the effect of modifying additives of vanadium and heteropoly compoundsMo and
W for their activity.The synthesized catalysts were tested on a laboratory flowinstallation under pressure
of hydrogen in the process of hydrotreating real raw materials - lightcoking gas oil. It was found that the
introduction of heteropoly compounds increasescatalytic activity of catalysts in comparison with
standardcatalyst: the degree of hydrodesulfurization on a catalyst prepared fromsilicomolybdic acid,
higher than the standard, by an average of 6.3%, degreehydrogenation of polycyclic aromatic
hydrocarbons is 12% higher atlow temperatures. The use of modifying additives vanadium in the
amount0.5% wt. allows to obtain a highly active hydrotreating catalyst, degreehydrodesulfurization at
which reaches 94%, and the degree of hydrogenation -57%.Thus, in the course of the work done, the
possibility of increasingthe catalytic activity of hydrotreating catalysts using the studiedmodifying
additives.25

Page 26

KINETICS OF HYDROCARBALCOXYLATION OF CYCLOHEXENEM-CRESOLE FOR CATALYSIS WITH PHOSPHINE

COMPLEXPALLADIANosova N.M., Astashina E.V.Tula State UniversityOne of the promising ways to obtain
esters is the reactionhydrocarbalkoxylation of alkenes. Despite the increased interest in thesereactions,
many aspects of the mechanism of their course remain unclear due tothe complexity of catalytic systems
and the interrelated influence of various factors. INThis communication presents the results of kinetic
studies of the reactionhydrocarbalkoxylation of cyclohexene with m-cresol, catalyzed by the systemPd
(PPh 3 ) 2 Cl 2 - p-toluenesulfonic acid - triphenylphosphine. Note that cyclohexeneas a substrate has
chemically equivalent reaction centers, which makeshydrocarbalkoxylation reactions with its
participation are convenient models forresearch.The kinetics of the hydrocarbalkoxylation reaction was
studied in an autoclave with a stirrer intemperature range 368-388 K. Analysis of the reaction mixture
was carried out by GLC.As a result of the research carried out, the first order ofcyclohexene and non-
linear dependence of the reaction rate on [Pd (PPh 3 ) 2 Cl 2 ],indicating a decrease in catalyst activity
with an increase in its concentration.It was shown that the dependences of the reaction rate on the
concentration of m-cresol are described bypower function k eff = k [m-CH 3 C 6 H 4 OH] n , and n
decreases with increasingtemperature. The data obtained were interpreted within the framework of two
modelshydride mechanism of hydrocarbalkoxylation. The first involves a changethe rate-determining
stage of the process with an increase in the concentration of m-cresol, the second -reversible
deactivation of the catalyst by ligand exchange of one ofintermediates of the catalytic cycle with m-
cresol. Shown kineticindistinguishability of these models. Based on the analysis of activation
parameters,choice in favor of the second model. A decrease in the activity of the catalyst with an
increase in itsconcentration is interpreted from the point of view of the reversible conversion of its
monomericforms into inactive polynuclear forms.26

Page 27

PROPANE ACTIVATION ON ACID AND Zn-CONTAININGZEOLITES ACCORDING TO IR AND NMR

SPECTROSCOPY IN SITUOrdomsky V.V., Kolyagin Yu.G.Moscow State University M.V. Lomonosov, Faculty
of ChemistryZn-containingzeolitesarepromisingcatalystsaromatization of propane. The study of the
conversion of propane on these catalyticsystems are devoted to a large number of works. However, the
initial stage mechanismconversion of propane is still a matter of debate. In this workthe study of the
initial stages of propane activation by IR methods was carried outspectroscopy and spectroscopy NMR
on nuclei 13 C. The studies were carried outdirectly during the catalytic reaction "in situ".MFI (Si / Al =
35), Zn / MFI andZn / silicalite, with a zinc content of 8% of the mass. Metal-containing catalysts
wereobtained by impregnating the starting zeolite MFI (35) with an aqueous solution of Zn (NO 3 ) 2
ssubsequent calcination. The kinetics of propane conversion was studied inflow reactor at a temperature
of 450 to C and weight hourly space velocities of from 1.5 to 150hour -1 . IR spectra were recorded on a
Protégé 460 FT-IR instrument in static andflowing conditions. NMR experiments were carried out in
sealed ampoules withcatalyst and adsorbed with labeled reagents on the spectrometerADVANCE-400
with an operating frequency of 13 C - 100 MHz.The obtained kinetic data indicate that the mainthe
primary process on Zn containing zeolite of the MFI type is dehydrogenationpropane, while on acidic
zeolite - cracking with the formation of methane andethylene. Study of the initial stages of propane
adsorption and activation on Zn / MFI andZn / silicalite by IR and NMR methods showed that the
dehydrogenation of propaneit is preceded by its dissociative adsorption on zinc centers with the
formation of OH-groups and zinc-propyl fragments, which are then converted into propylene,adsorbed
as a σ-complex at the same center. Comparison of receiveddata with the results of experiments on the
study of dissociative adsorptionhydrogen showed that in the dissociative adsorption of propane onlya
small part of the strongest Zn-containing centers.This work was supported by the Russian Foundation for
Basic Research, INTAS (project 03-51-5286) and NSh(project 1275.2003.3). Kolyagin Yu.G. thanks Haldør
Topsoe forgranted scholarship.27

Page 28

MECHANISM OF ACTION OF PEROXIDASE IN REACTIONS OF JOINTOxidation of potassium ferrocyanide

and dihydroquercetinPeretolchin D.V.Yakutsk State Agricultural AcademyPeroxidase is the most abundant
enzyme in living organisms.Catalyzes the reactions of oxygenase, oxidase and peroxidase
oxidationsubstrates. Participates in reactions of individual and joint oxidationinorganic and organic
compounds. Among the enzyme substrates, there arefunctionally active compounds (IAA, NADH,
ascorbic acid,flavonoids, phenothiazines, etc.). In living organisms, peroxidase is most likelycatalyzes the
reaction of joint oxidation of substrates. Experiments in vitroit was shown [1] that during the joint
oxidation of various peroxidase substratesthe effects of mutual activation and inhibition are observed.
Moreover, inhibitioneither competitive or associated with differential oxidationsubstrates in the
presence of peroxidase. Whereas substrate-substrate activationaccompanied by the acceleration of the
oxidation of the slowly oxidized substrate rapidlyoxidizable [2]. We studied the reactions of joint
peroxidase oxidationpotassium ferrocyanide and dihydroquercetin at pH 4.5-8.0. Previously it wasit was
shown that according to the data of individual oxidation reactions, they could be attributedto slowly
oxidized peroxidase substrates. However, the study of reactionscombined oxidation of ferrocyanide and
dihydroquercetin at pH 4.5-7.0 allowedto identify the activating effect of dihydroquercetin, which
manifested itself insynergistic type of activation. This type of activation is observed only in theif the
binding of the activator in the active center of the enzyme increases the affinityenzyme to the substrate,
manifested in a decrease in the value of the binding constant.Pre-binding of dihydroquercetin improved
subsequent bindingferrocyanide by 1.4-13.3 times, with a maximum at pH 6.5. Whereas at pH ≥7.5only
dihydroquercetin was oxidized, while ferrocyanide did notinfluence on the process of its peroxidase
oxidation.1. Ugarova N.N., Lebedeva O.V., Savitsky A.P. Peroxidase catalysis and itsapplication. Moscow:
Moscow State University, 1981.92 p.2. Lebedeva O.V., Ugarova N.N. // Izvestia RAN. Ser. chemical. - 1996.
- No. 1. -S. 25-32.28

Page 29

TESTING OF Pt CONTACTS OF GASOLINE REFORMING BY THE METHODMATHEMATICAL

MODELINGPoluboyartsev D.S.Tomsk Polytechnic UniversityThe platforming variant of catalytic reforming
is used inworld oil refining is already 50 years old. Its power in the structure of the worldoil refining
complex make up 12.5% of primary distillationoil, i.e. all negative gasoline fraction 85-180 o C undergoes
reforming, and inRussia - 10.7%. It is obvious that the level of technology of the process, its technical
andeconomic efficiency largely determines efficiencyrefining in general. For these reasons, it is
understandable that attention is paid toin economically developed countries to improve reforming
technologies anddevelopment of more efficient catalysts.Using a non-stationary kinetic model built on
the basis ofphysicochemical laws governing the conversion of hydrocarbons in the processreforming, the
following studies were carried out: 1) by solving the inversekinetic problem, the kinetic regularities of
thethe main reactions on their surfaces of the most common brands of catalystsreforming; 2) using the
obtained values of the rate constantschemical reactions, the main indicators of the catalytic process
forconditions of industrial installations.Studies have shown that new generation catalysts RG-582, RG-
682 and PR-51M are made with the addition of promotional elements, notactive in target reactions. For
catalysts RG-682 and PR-51M,the intensity of hydrocracking reactions is reduced, while an increase inthe
rate of dehydrocyclization of paraffins. Product yield on catalyst RG-682higher than on RG-582 and RG-
482 by 1.6 and 3.7%, respectively. In its turncatalyst PR-51M outperforms RG-682 both in yield and
octane numberreformate, and, as a consequence, has a higher selectivity and reducedhydrocracking
rate. Obviously, a quantitative assessment of such an importantparameter became possible only with the
use of methods of mathematicalmodeling.29

Page 30

PEROXIDASE AS A MODEL FOR STUDYING OXIDATION REACTIONSPhenothiazinesRogozhina T.V.Yakutsk

State Agricultural AcademyPeroxidase catalyzes the oxidation reactions of inorganic and
organiccompounds of hydrogen peroxide. The enzyme is part of the antioxidant systemliving organisms
and therefore is represented in all animal and plant cells.It is impossible to study the effect of the
enzyme in vivo without violating the integrity of the cells.Therefore, it is proposed to use peroxidase as a
model for studying reactionsperoxidase oxidation of functionally active substances, in particular
forstudying the reactions of peroxidase oxidation of drugs. We studiedstationary kinetics of peroxidase
oxidation of triftazine and thioproperazine inthe presence of horseradish peroxidase. In the pH range
4.5-7.5, the values of k cat andK m . The reactions of peroxidase oxidation of triftazine and
thioproperazine are characterized bylow values of catalytic constants 0.3-124 and 0.12-9.8 s -1,
respectively, whichallows us to classify them in the group of slowly oxidized peroxidase substrates,
suchlike NADH and potassium ferrocyanide. In this case, the quantities K mfor triftazine
andthioproperazine differed little and amounted to 10-330 and 22-196 μM independing on pH. In acidic
pH (4.5-5.5), triftazine oxidizes fasterthioproperazine by 9-12 times, while the K m values of triftazine are
1.5-3.5 times higher,than thioproperazine. However, at pH> 6.0 K mtriftazine and
thioproperazinedecrease and become comparable with K m for a rapidly oxidized substrateperoxidase -
o- dianisidine (15-30 μM). From the pH dependences of lgk cat and lgk cat / K mreactions of peroxidase
oxidation of triftazine and thioproperazine are determinedionogenic groups with pK 4.9, 5.6 and 5.4, 4.7,
respectively, the deprotonation of whichimpairs the catalytic process of peroxidase oxidation,
respectivelytriftazine by 413 times, and thioproperazine by 82 times. Low rate constantsoxidation of
phenothiazines, possibly, as in the case of NADH and ascorbic acid, inare primarily due to the fact that
their oxidation with hydrogen peroxide proceedsby one-electron mechanism, similar to the oxidation of
inorganic substratesperoxidase.thirty

Page 31

SYNTHESIS AND CATALYTIC PROPERTIES OF MESOPOROUSMATERIALS BASED ON ZIRCONIUM OXIDEA. V.

Sungurov, S. V. BaranovaMoscow State University M.V. Lomonosov, Faculty of ChemistryCreation of new
heterogeneous catalysts with high activityand selectivity in acid-catalyzed reactions, is one of the most
importanttasks of modern oil refining and petrochemistry. From this point of view, practicalof interest
are solid acids based on zirconium oxide havingdeveloped mesoporous structure.By the method of
template synthesis, mesoporous materials were obtained onbased on zirconium oxide, having a specific
surface area of 350 to 680 m 2 / g andpore diameters from 24 to 110 Å. The starting compounds for the
synthesis were sulfateand zirconium oxychloride, an oxide was used as a stabilizing agentsilicon. The
molar ratio of ZrO 2 to SiO 2 in the obtained samples, according to ICP AES data,ranges from 1: 0.1 to 1:
1.3. Based on low temperature adsorption resultsnitrogen found that the materials have a fairly narrow
pore distributionradii, that is, completely homogeneous mesopores, and the micropores in them are
practicallyabsent.Materials retain their physical and chemical characteristics when pressedat pressures
up to 500 atm., and also keep the size of the specific surface at the level80% of the initial value after
calcination in air at 800 of C.three hours, which is important when using them as carriers foracid and
bifunctional catalysts. The introduction of ammonium sulfate intothe reaction mixture at the stage of
synthesis of materials allows, within significant limits,regulate their acidic and catalytic properties.The
resulting mesoporous materials based on zirconium oxide,modified with oxo-anions, showed catalytic
activity in the reactionshydroisomerization of n-butane and alkylation of benzene with dodecene-1.31

Page 32

INFLUENCE OF pH ON THE ACTIVITY AND STABILITY OF ALKALINEPHOSPHATASEFedosov S.A., Atyaksheva

L.F.Moscow State University M.V. Lomonosov, Faculty of ChemistryThe effect of pH in the range 6.5 - 9.5
on the activity and stability of alkalinebovine intestinal phosphatase. The enzyme was inactivated at a
temperature60 0 С, we used solutions with a concentration of 1.25-2.5 * 10 -6 M in TRIS-HCl buffer.It
was shown that the pH optima for the activity and stability of the enzymeare different. The maximum
activity of alkaline phosphatase is at pH values8.5 - 9.0, and the greatest stability is in the region of
neutral pH values.Thermoinactivation of alkaline phosphatase under the studied conditions occursby the
dissociative mechanism: at the first stage, active dimers dissociate intoinactive monomers (reversible
stage), the second is irreversiblesubunit inactivation. Using the mathematical apparatusdissociative
thermal inactivation of oligomeric enzymes, kineticprocess parameters at different pH values:
dissociation rate constants,denaturation rate constants and dimer dissociation constants. Mostthe stage
of dissociation is sensitive to changes in pH.The presence of a minimum on the curve of the dependence
of the rate constant of dissociation onpH is explained in terms of the Michaelis - Dixon approach,
according to whichthe enzyme is regarded as a dibasic acid with two different acidicin groups. A kinetic
scheme of the process is proposed, according to which to dissociatetwo forms of the enzyme are
capable, and the partially ionized form is stable. Ofthe experimental dependence of the dissociation rate
constant on pH are determineddissociation rate constants for non-ionized and fully ionizedenzyme forms
and ionization equilibrium constants. The proposed model allowedclarify the pH value corresponding to
the minimum value of the rate constantdissociation of alkaline phosphatase dimer - a process that
determines instabilityenzyme.32

Page 33

Department "Inorganic chemistry - graduate students"Jury:Gorbenko O.Yu.Art. n. Researcher, Doctor of

Chemistry - chairmanGlazunova T.Yu.graduate student - secretaryAbakumov A.M.n. researcher,
Ph.D.Dolgikh V.A.led. n. Researcher, Doctor of ChemistryKnotko A.V.Art. n. researcher, Ph.D.Turova
N.Ya.Art. n. researcher, Ph.D.V. I. Shtanovled. n. researcher, Ph.D.33

Page 34

ACCOUNTING THE SPIN-ORBITAL INTERACTION IN THEMODELING RELATIVE

STABILITYOXOHYDROXOCOMPLEXES RUTHENIUM (VI) AND Osmium (VI) BDIFFERENT COORDINATION
ENVIRONMENTSAvdey A.V., Ermilov A.Yu.Moscow State University M.V. Lomonosov, Faculty of
ChemistryCompounds of platinum metals in high oxidation states and theirstabilization is of great
interest in synthetic inorganic chemistry.According to X-ray diffraction data, the structure and
composition of oxo-hydroxo complexesruthenium (VI) and osmium (VI) are different. Ruthenium (VI)
forms complex paramagneticanions of the composition [RuO 3 (OH) 2 ] 2- having a five-coordinate
environment, and osmium (VI)- coordination number 6 in the diamagnetic anion [OsO 2 (OH) 4 ] 2- . Data
onhydroxo complexes of reverse composition (CN Ru = 6 and CN Os = 5) are absent.Preliminary
calculations by the density functional and Hartree-Fock methodsshowed the stability of paramagnetic
ruthenium in a five-coordinated environment inanion [RuO 3 (OH) 2 ] 2- and six-coordinate environment
for the diamagnetic anion[OsO 2 (OH) 4 ] 2- in accordance with experimental data. However,
modelingmolecular systems containing elements of the second half of the periodicit is not enough to
carry out the tables without taking into account the spin-orbit interaction.The relativistic density
functional method taking into account the spin-orbitalinteraction (SO-DFT) modeling of relative
stabilitycomplexes in different surroundings. The exchange-correlationpotential of B3LYP. The
calculations used the pseudopotentials of the Stuttgartgroups. The atomic basis is supplemented by two
f-type functions on Ru and Os and a d-function onoxygen atoms.To model the relative stability of the
stability of the complexesthe energies of model reactions were estimated: [MO 3 (OH) 2 ] 2- + H 2 O →
[MO 2 (OH) 4 ] 2- (M = Ru, Os).Calculatedenergycomplexesingeometricconfigurations,optimized in two
different ways. In the first version, foundequilibrium configurations. Geometric parameter values are in
the bestagreement with the experimental data, rather than in calculations without taking into account
the spinorbital interaction (DFT). The energies of model reactions have different signs- +13.0 kcal / mol
(Ru) and -13.6 kcal / mol (Os) in full agreement with the experiment.The second way to find the optimal
configuration contained restrictions,imposed by the symmetry of the crystal lattice. Estimates of the
reaction energies bythis technique also have different signs, although the numerical values are
noticeablevary +22.4 (Ru) - -16.7 kcal / mol (Os). This work was supported by a grantRFBR No. 05-03-
33082.34

Page 35

ASSOCIATION AND AMORPHIZATION OF Ni-P, Cu-Zr, Al-La MeltsAlekseeva Yu.P.Moscow State University
named after M.V. Lomonosov, Faculty of ChemistryMetal alloys in an amorphous state have a number of
uniqueproperties, primarily magnetic, electrical, corrosive. In some casesthere is a combination of low
density, high strength, commensurate with thisindicator for special steels, and good ductility. However,
the whole spectrumpossible properties of amorphous metallic materials to date, according toapparently
not disclosed. This is due to the fact that from the moment of opening tothe present search for new
compositions undergoing transformation into amorphouscondition, produced mainly by trial and error
usingindirect criteria.In this work, a detailed thermodynamic study was carried outa number of metal
systems: Ni-P, Cu-Zr, Al-La, characterized by differenta tendency to amorphization. Knudsen mass
spectrometrythe vapor composition and thermodynamic properties of liquid alloys in a widerange of
compositions and temperatures. Calculation of activities of melt componentsperformed by several
independent methods. The result is a largedata array of activity values of components at different
compositions and / ortemperatures. It was found that the thermodynamic behavior of melts obeyslaws
of ideal associated solutions. Accuracy and reliabilityobtained thermodynamic values and the adequacy
of the model description,proved by calculating phase equilibria in these systems. Analysis
performedthermodynamic and kinetic factors of the transformation of liquid alloys intoamorphous state
and it was shown that all of them are directly related to the parametersassociation processes. It was
found that the amorphization interval coincides withconcentration range of dominance of associative
complexes with a largenegative entropy of education. The latter characteristic is proposed inas a basis
for the development of quantitative criteria for the amorphization of liquidmetal alloys.35

Page 36
CORROSION OF THIN COPPER FILMSBorisova N.V., Ermolaeva M.N., Titov I.V.GOU VPO "Kemerovo State
University"It was found that the absorption spectra of copper films substantially depend onthickness.
For samples with a thickness of d p > 1 • 10 -8 m, a minimum of opticaldensity at 570 nm, and for
samples d p <1 • 10 -8 m it does not appear. Afterheat treatment of copper films, their absorption
spectra undergosignificant changes in the entire investigated wavelength range.As a result of processing
the absorption spectra measured for copper filmsdifferent thicknesses before and after heat treatment
at different temperatures, forof various spectral regions, kinetic dependences of the
degreetransformation α = (D 0 -D / D 0 ) copper films. It was found that α depends on the
thicknesscopper films and heat treatment temperatures. For copper films with a thickness of d p <5 • 10
-8 m inIn the studied temperature range, α reaches 1 in τ = 1 - 3 minutes. When increasingtemperature
of heat treatment, the angle of inclination of the straight line in the coordinates α = f (τ)
increases.According to the Pilling and Bedworth criterion, which is 1.64 for copper,the formation of a
continuous oxide film was expected to significantly inhibitfurther course of the oxidation process.
However, it was found that the growth rateoxide film on the surface of copper films with a thickness of d
p <5 • 10 -8 m (up toensuring their complete oxidation) remains constant. This fact indicatesthe fact that
the thickness of the oxide film will be proportional to the oxidation time. SoThus, despite the fact that V
Ok / V Me > 1 (where V Ok is the volume of the oxide, V Me is the volumemetal) thin (d p <5 × 10 -8 m)
layers of copper, apparently, form not continuous, butloose oxide films with weak protective properties.
As you increasethickness of copper films (d p > 5 • 10 -8 m) kinetic curves of their oxidation at
differenttemperatures are satisfactorily described in terms of logarithmic orparabolic laws. Thus, for
copper films with a thickness d p > 5 • 10 -8 m inas a result of chemical corrosion, continuous oxide films
will form andthe corrosion process will be inhibited by the diffusion of copper ions through the oxide
film,further growth of which will slow down with an increase in its thickness.36

Page 37

EFFECT OF LITHIUM FLUORIDE ON THE INTERACTION INMELTED SYSTEM Li 2 O-P 2 O 5 -In 2 O 3Boyko
R.S., Kornienko Z.I., Nagorny P.G.Kiev National University. T. ShevchenkoAlkali metal fluorides are known
as depolymerizers of moltenpolyphosphates. The presence of fluorides in phosphate melts affects the
lengthpolyphosphate chains, which means on the solubility and the nature of the interactionoxides of
polyvalent metals.Preliminary research has shown the formation of Li 2 O-P 2 O 5 in the systemdouble
phosphates LiIn (PO 3 ) 4 and LiInP 2 O 7 . It was of interest to study the effect of LiF onphase formation
in the above system. Study of the influence of LiF oninteraction in the system Li 2 O-P 2 O 5 -In 2 O
3carried out by the method of isothermalsaturation of melts with indium oxide in the range of molar
ratios Li 2 O / P 2 O 5 from0.5 to 1.7 at temperatures of 800 and 850 of C. Initial concentrations were 10
and LiF20% by mass. Equilibrium liquid phases were analyzed for the In 2 O 3 content .The compositions
of the crystalline phases were determined by elemental analysis. All crystallinephases were subjected to
X-ray phase analysis, the structure of phosphate anions was establishedusing IR spectroscopic analysis. It
was found that the addition of LiF leadsto a significant increase in the solubility of In 2 O 3 in comparison
with fluoride-freesystem. In this case, with a content of 10% of the mass. LiF in the crystalline
phasedouble phosphate LiInP 2 O 7 is identified in the entire range of molar ratiosLi 2 O / P 2 O 5 , as
well as lithium diphosphate Li 4 P 2 O 7 with Li 2 O / P 2 O 5 > 0.8. With a LiF content of 20% mass. in the
range of molar ratios Li 2 O / P 2 O 5 from 0.5 to 1.0 is formedLi 3 In 2 (PO 4 ) 3 , and at ratios greater
than 1.0 in the crystalline phasea mixture of phases is identified: Li 3 In 2 (PO 4 ) 3 , Li 4 P 2 O 7 , Li 3 PO 4
.In the system with LiF, the phenomenon of thermohydrolysis takes place. This leads to a changeinitial
ratios Li 2 O / P 2 O 5 in time. Study of the kinetics of thermohydrolysis inmelts Li 2 O-P 2 O 5 - LiF at 850
o C showed that the rate of thermohydrolysis dependsboth on the Li 2 O / P 2 O 5 ratio and on the initial
content of lithium fluoride inmelt, and the end products of this process are Li 4 P 2 O 7 and Li 3 PO 4 .37

Page 38

SYNTHESIS OF CONTINUOUS SOLIDSM 1-X Ni X (H 2 PO 4 ) 2 2H 2 O, WHERE M - Co, Zn, Mn, MgViter

V.N., Nagorny P.G.Kiev National University. T. ShevchenkoA number of divalent 3-d metals - Mn, Fe, Co,
Zn, as well as Mg and Cd formdihydrogen phosphates of the composition M II (H 2 PO 4 ) 2 2H 2 O. All
these compounds are isostructuralamong themselves (monoclinic system, space group P2 1 / n), have
similar X-ray diffraction patterns andclose parameters of the unit cell. Their structural data
repeatedlyresearched and refined. A similar dihydrogen phosphate has been described for Ni [1, 2].
Howeverit was not possible to reproduce the methods of its synthesis, there are no structural data,
andthe X-ray diffraction pattern given in [2] indicates non-structuralNi (H 2 PO 4 ) 2 · 2H 2 O with the
other above-mentioned dihydrogen phosphates.We have synthesized continuous substitutional solid
solutions:M 1-X Nі X (H 2 PO 4 ) 2 2H 2 O (0≤X≤1.00), where M is Co, Zn, Mn, Mg. The resulting
solidsolutions are single-phase and correspond to the chemical composition M II (H 2 PO 4 ) 2 2H 2 O.
Theybelong to the monoclinic system (space group P2 1 / n), have close X-ray diffraction patterns andunit
cell parameters. These solid solutions are formed by the reactionH 3 PO 4 concentration 84.5% with a
mixture of Ni hydroxocarbonates and the correspondingmetal. For the starting reagents, the atomic ratio
P / (M + Ni) = 4/1, the ratioNi / (M + Ni) 100% varied from 0 to 100% (mol.), Inclusive. Interaction
timewas 2-90 days, T = 20 ºС. The extreme point M 1-X Nі X (H 2 PO 4 ) 2 2H 2 O (0≤X≤1.00)is the first
obtained Ni (H 2 PO 4 ) 2 2H 2 O. For crystallization of thiscompounds (from phosphoric acid solutions)
take a long time androom temperature, which explains the non-reproducibility of the techniques [1, 2].It
was found that Ni (H 2 PO 4 ) 2 2H 2 O belongs to the monoclinic system (sp.gr.P2 1 / n), thus, it is
isostructural with dihydrates of dihydrogen phosphates Mn, Fe, Co,Zn, Mg and Cd. For the latter, the
crystallization time from phosphate solutions is notexceeds 1-2 days. The IR spectra of the obtained solid
solutions have an intermediatecharacter between the spectra of dihydrogen phosphates of the
corresponding metals andnickel dihydrogen phosphate. IR spectra of Ni (H 2 PO 4 ) 2 2H 2 O and Co (H 2
PO 4 ) 2 2H 2 O are close.1. Thilo E., Grunze H. // Ztschr. Anorg. Allgem. Chem. 1957. Bd. 290,No. 5-6. S.
209-222.2. Shchegrov L.N., Pechkovsky V.V., Dzyuba E.D. // IPC 1972. T. 14, No. 4. C. 713-719.38

Page 39

SYNTHESIS AND STUDY OF SOLID SOLUTIONS Sn 2-2X M X Al X O 4 COSTRUCTURE OF RUTILGovorov V.A.,

Abakumov A.M., Rozova M.G., Antipov E.V., Tsirlina G.A.Moscow State University named after M.V.
Lomonosov, Faculty of ChemistryMaterials based on SnO 2 doped with various elements are
recognizedone of the most promising for creating a low-wear anode forindustrial production of
aluminum. We have obtained solid solutions onbased on tin oxide composition Sn 2-2x M x Al x O 4
(where M = Sb, Nb). They were investigatedregions of homogeneity, crystal structures, dependences of
resistance ontemperature and degradation in cryolite-alumina melt at a temperature of 950 0 С.The
synthesis of compounds was carried out in air at a temperature of 1100 -1500 0 С inwithin 150-200
hours. SnO 2 , Sb 2 O 3 were used as starting reagentsNb 2 O 5 and Al 2 O 3 . Compounds crystallize in a
disordered structural typerutile. Single-phase samples were obtained in the intervals 0.2≤x≤0.6 for Sn
2-2x Sb x Al x O 4and 0.2≤x≤0.4 for Sn 2-2x Nb x Al x O 4 . Samples with х <0.2 and contain oxide as an
impuritytin, samples with х> 0.6 (Sb) and 0.4 (Nb) contain Al 2 O 3 or AlNbO 4 impurities .The crystal
structure of the obtained compounds was determined usingX-ray powder diffraction. Unit cell
parameters are linearincrease with an increase in the content of tin in the sample, which is consistent
with the valuesionic radii of elements. The samples obtained show a semiconductortype of dependence
of resistivity on temperature. In temperatureIn the interval from 25 to 1000 0 С, the resistance decreases
by three to four orders of magnitude. Forsolid solutions Sn 2-2x Nb x Al x O 4 an increase in x leads to an
increase in resistance, andfor solid solutions Sn 2-2x Sb x Al x O 4, the resistance is practically
independent ofcomposition.Tests were carried out on the degradation of solid solution samples in
cryolitealumina melt at a temperature of 950 ° C without current load. Was found,that the concentration
of tin, niobium and antimony reaches saturation point after 3-5 hoursannealing in cryolite-alumina
melt.39

Page 40

REVERSIBLE ADDITION OF MOLECULAR OXYGEN TOO-AMIDOPHENOLATES AND CATCHOLATES OF

TRIPHENYL ANTIMONY (V)Grunova E.V., Poddel'skiy A.I., Cherkasov V.K., Abakumov G.A.Institute of
Organometallic Chemistry. G.A. Razuvaev RASMolecular oxygen activation is an important area of
chemicalresearch in order to find and use mild oxidants in variousredox transformations. Therefore, the
synthesis of metal complexeswith the potential to interact with molecular oxygen hasgreat importance.
It is known that some complexes of transition elements withsuch ligands as porphyrins, tris-pyrazolyl
borates, etc., are capable of reversiblybind molecular oxygen. However, until now it was not
knownexamples of reversible oxygen addition to non-transitional compoundselements.We found that
triphenylantimony (V) 1 o- amidophenolates are capable ofbind molecular oxygen to form cyclic spiro-
endo-peroxide -1,2,4,3-trioxastibolane derivative 2 . Interaction with oxygen isreversible. It is shown that
some of triphenylantimony (V) catecholates, derivativesweakly acceptor o- quinones, also capable of
reversible additionmolecular oxygen with the formation of endo-peroxides ( 3 , 4 ). The structure of the
originalcompounds of antimony (V) and their oxygen-related derivatives are characterizedmethods of IR,
NMR spectroscopy, the molecular structure is established usingXRD method.OOSbPh 3OOOBu tOSbPh
3OOButMeO12RROBu tBu tNSbPh 3OORRONBu tBu tSbPh 3R = Pri, MeO 234This work was supported by
the Russian Foundation for Basic Research (grants No. 04-03-32409, 04-03-32413),the grant of the
President of the Russian Federation for the support of leading scientific schools (NSh - 1649.2003.3)
andFoundation for the Promotion of Russian Science.40

Page 41

SOLUBILITY AND POROSITY OF HEAT-TREATED PRODUCTSHYDRATED

ALUMOSILICOPHOSPHATESGubaidullina G.M., Zhakitova G.U.Institute of Chemical Sciences named after
A.B. Bekturova MES RK, AlmatyAluminosilicopolyphosphate sorbents were obtained by mixing
solutionsaluminum sulfate with phosphoric acid and solutions of sodium silicates in variousratios
followed by precipitation with ammonium hydroxide at pH 5.0, 7.0, 11.4,filtration, washing, drying and
heat treatment at a temperature of 500 0 Сthe resulting sediment. The composition of the synthesized
samples was identifiedIRS (Specord-80) and XRF (DRON-3).It has been established that the solubility and
total pore volume of porousaluminosilicopolyphosphates depend on the ratio of metal oxides to
pentoxidephosphorus, pH of the coprecipitation process and the presence of a silicon-containing
component. Whenthe absence of a modifier in an alkaline medium and the ratio Al 2 O 3 / P 2 O 5 =
0.35a water-soluble crystalline ammonium-aluminum diphosphate is formed, whichconfirmed by XRF
data (main reflections at interplanar distancesd = 2.93; 5.6; 3.90; 4.1 Ǻ). With a decrease in pH to 5 and
an increase in the ratio of oxidealuminum to phosphorus pentoxide, in addition to ammonium-aluminum
diphosphate, in productsheat treatment discovered cyclotetraphosphate and aluminum polyphosphates,
inas a result of which their solubility decreases. In the process of coprecipitation of hydroxides
andaluminum phosphates with the introduction of a modifier - sodium silicate in an acidic mediumthe
aluminum cation replaces some of the silicon in the formed silicic acid gel withformation of
aluminosiloxane bonds (absorption band in the region of 680-730 cm -1on IR spectra), which prevents
the formation in the products of heat treatmentsoluble ammonium-aluminum diphosphate and, as a
result, the total solubility of the samplesdecreases. In an alkaline medium, with an increase in the ratio
of aluminum oxide to pentoxidephosphorus silicic acid gel is not formed and the solubility of heat-
treatedsamples is rising.The total pore volume of the heat treatment products, as well as the
solubility,essentially depends on the ratio Al 2 O 3 / P 2 O 5 and the pH of the precipitation.It has been
found that for the synthesis of sorbents with minimal solubility andthe maximum total pore volume is
optimal: precipitation pH 5.0 andthe ratio Al 2 O 3 / P 2 O 5 in the range of 0.35-1.2.41

Page 42

TO THE QUESTION ABOUT THE RELIABILITY OF MEASURING THE ELECTRIC CONDUCTIVITYGeSe-GeI

SYSTEMS 2Danilov D.N. 1 , Leushina A.P. 1 , Avdeeva E.V. 1 , Zlomanov V.P. 21 Vyatka State University,
Kirov,2 Moscow State University named after M.V. Lomonosov, Faculty of ChemistryThe conductometric
study of binary systems is sufficientsimple and at the same time highly informative method of obtaining
data onelectrical conductivity, the presence and width of the region of solid solutions,
temperatureboundaries of a region with a different character of conductivity and the nature of the
defectstructures. If measurements are used with alternating current, then its frequency shouldbe large
enough to measure volume resistivitysample, not the resistance of the electrode-sample interface.
Therefore, an important criterionthe reliability of the obtained conductometric data is
knowledgeminimum frequencies at which the resistance becomes frequency-independent.Such
information can be obtained by impedance research.Impedance study of the GeSe-GeI 2 system(graphite
electrodes)showed that starting from a frequency of 7.9 * 10 2 Hz, the resistance becomes
frequencyindependent. Therefore, the application for conductometric studies of thisgermanium-
containing AC system with a frequency of 1 kHz isreasonable [1]. The impedance measurements were
carried out on a digital correlationanalyzer "Solartron" in the frequency range 1-10 6Hz with data
processingsoftware package ZView 2.The pycnometric and radiographic density of the samples should
becomparable for the reliability of conductometric research. Whenof GeSe-GeI 2 systems, the
pycnometric density is about 80 - 85% ofX-ray diffraction, and the highest value is achieved for a
composition of 2 mol%GeI 2 , which has the best transport characteristics in the field of solidsolutions.1.
Leushina A.P., Danilov D.N., Zlomanov V.P. Dependencies on the composition andcomparison of the
electrolytic properties of some germanium-containingquasi-binary systems // Tez.Report VII Int.
meetings"Fundamental problems of solid state ionics". Chernogolovka,2004 .-- S. 27.42

Page 43

DIFFERENT REE (III) C HEXAFLUOROACETYL ACETONATES4-CYANOPYRIDINE-N-OXIDE: SYNTHESIS,

CRYSTALLINESTRUCTURE AND PHOTOLUMINESCENT PROPERTIESEliseeva S.V.Moscow State University
named after M.V. Lomonosov, Faculty of ChemistryComplexes of REE (III) with organic ligands are
promisingmaterials of emission layers when creating electroluminescent (EL)devices due to the high
quantum yield of luminescence (theoretically, itcan reach 100%), small half-width of the emission band
(~ 10-20nm),the ability to obtain colors of the entire visible range. Using the techniquemixed-ligand
complexation opens up the possibility of changingthermal, chemical stability, electron transport,
luminescentproperties of coordination compounds, improving the quality of thefilm coatings, etc.In this
work, synthesized and characterized by elemental, IR-spectroscopic, thermal and photoluminescent
analyzes newcomplexes of the composition Ln (hfa) 3 (cpo) n (Ln = Sm (III), Eu (III), Gd (III), Tb (III), Dy
(III), Tm (III),hfa - = hexafluoroacetylacetonate ion, cpo - 4-cyanopyridine-N-oxide, n = 1, 2).
Structurecomplexes in the gas phase was studied by mass spectrometry usingKnudsen cells by the
example of Eu (hfa) 3 (cpo) n . According to XRD data, crystallinethe structure of Tb (hfa) 3 (cpo) contains
two types of crystallographically independentcentrosymmetric dimeric molecules [Tb (hfa) 3 (cpo)] 2 , in
which two terbium ionslinked to each other by two bridging ligands of 4-cyanopyridine-N-oxide.Thus, the
central terbium ion (CN = 8, coordination polyhedron -distorted square antiprism) coordinates six oxygen
atoms of threehexafluoroacetylacetonate ligands, and two oxygen atoms of the N-oxide groups of
twoligands sro. The energy of the triplet levels of the ground (hfa - ) andadditional (cpo) ligands by
phosphorescence spectra of gadolinium complexescomposition Gd (hfa) 3and Gd (NO 3 ) 3 (cpo),
respectively. Based on comparisonthe mutual arrangement of the energy levels of the central REE (III)
ion,the main and additional ligands proposed a possible mechanismphotoluminescence.43

Page 44

INTERCONNECTION OF SENSOR AND CATALYTIC PROPERTIESSnO 2 -Fe 2 O 3 BY THE EXAMPLE OF

INTERACTION WITH ETHANOLV.V. Kovalenko, E.V. MakshinaMoscow State University named after M.V.
Lomonosov, Faculty of ChemistryThe introduction of catalytic additives is widely used to
improveselectivity of gas sensors based on semiconductor metal oxides.Despite the large number of
works in this area, it is still controversialthe relationship between the sensory and catalytic properties of
oxides. In that workthe degree of correlation between these functional properties fornanocomposites
SnO 2 -Fe 2 O 3 . Sensory sensitivity and catalytic activitystudied by the example of interaction with
ethanol.The work investigated the pure oxides of tin and iron and nanocomposites SnO 2 -Fe 2 O 3
composition 7 and 80 mol. % Fe 2 O 3 with a crystallite size of 3-17 nm and an areaspecific surface 75-
135 m 2 / g. The catalytic properties were investigated in a flowreactor, the analysis of ethanol oxidation
products was carried out chromatographically.Acidicpropertiessurfacessamplesidentifiedmethodthermo-
programmed desorption of ammonia. Sensory properties were investigated forthick films, both in a
thermostatted cell and on microchips.Iron oxide in SnO 2 -Fe 2 O 3 nanocomposites plays the role of a
catalyst, reducingacidic properties of the surface of nanocomposites and lowering the temperature of
the totalconversion of ethanol. The greatest sensory sensitivity to alcohol is observed whentemperatures
close to the temperature of full conversion, when participationmaximum chemisorbed oxygen. Decline
observed over timethe catalytic activity of the samples indicates surface poisoningnanocomposites in
the course of interaction with high concentration ethanol vapors. howconsequence for the stable
operation of the nanocomposite as a sensor or catalystit must be periodically activated by annealing in
air at a temperature550-600 ° C.44

Page 45

APPLICATION OF ORGANOMINERAL COMPOSITIONS FOR PROTECTIONAGAINST HYDROGEN SULFUR

CORROSIONKayynbaeva R.A., Kapralova V.I.Institute of Chemical Sciences named after A.B. Bekturova
MES RK, AlmatyIssues of protecting the inner surface of pipelines from hydrogen sulfidecorrosion are
extremely topical. To one of the effective waysto combat this negative phenomenon is the use of
substances, includingphosphates, silicates and compositions based on them, capable of forming ona
protective phase film on the metal surface.Sodium polyphosphate with molarthe ratio Na 2 O / P 2 O 5 =
1.2; a solution of water glass with a silica module 2.6,activated with phosphoric acid, as well as their
mixtures with sodium humate.From the analysis of the data obtained (table) it follows that the most
effectivean inhibitor for hydrogen sulfide-containing aqueous media is an aqueous solutionsodium
silicate activated by phosphoric acid and its composition with humatesodium. The degree of protective
action for an activated sodium silicate solution withconcentration of 250 mg / l is 78.1%, and for a
composition of 50 mg / l{Na 2 O⋅2.6SiO 2 + H 3 PO 4 } + 250 mg / l sodium humate - 94.1%.The corrosion
rate of steel in solutions containing 100 mg / l hydrogen sulfide withadditives of various inhibitorsSteel
corrosion rate, mg / cm 2 dayInhibitor concentration, mg / lP / p No.Inhibitor composition205075one
hundred2501 NaPO 30.1570.1450.1320.1180.1032 Na 2 O⋅2.6SiO 2 + H 3 PO
40.1140.0970.0850.0800.0413Sodium humate0.2250.2670.1940.1720.1374Sodium humate + 100 mg / l
NaPO 30.2530.2370.2150.1960.119fiveSodium humate +50 mg / l {Na 2 O⋅2.6SiO 2 + H 3 PO 4 }
0.0680.0470.0410.0350.011Thus, the optimal compositions of compositions based on humate
andsodium silicate, providing a degree of metal protection against hydrogen sulfidecorrosion at the level
of 90% and higher.45

Page 46

KINETICS OF HIGH-TEMPERATURE INTERACTION WITH WATERBA 4 CA 2 NB 2 O 11 AND SR 6 TA 2 O

11Crown D.V.Ural State University A.M. Gorky, YekaterinburgCurrently, some of the promising research
objects aresolidelectrolytes,possessingprotonconductivity.Amonghigh-temperature proton conductors
known perovskite-like niobatesand tantalates of alkaline earth metals of composition Ме 6 М 2 О 11 (V o
) 1S (Ме - Ca, Sr, Ba; M -Nb, Ta) with structural vacancies in the oxygen sublattice.It is known that for the
indicated compositions there is a homogeneity regionMe 6 M 2 O 11 - Me 4 M 2 O 9 described by the
formula Me 6-2x M 2 + 2x O 11 + 3x (V o ) 1-3x . Availabilitystructural oxygen vacancies determines
oxygen-ion conductivity andproton conductivity in the presence of water vapor.V o••+ H 2 O + O O× = 2
(OH) O•(1)Study of kinetics and determination of diffusion coefficients along withconductivity helps to
estimate the rate at which a material is in equilibrium withworking atmosphere, which is important, for
example, when using solid electrolyte inas an electrochemical humidity sensor.As a result of a
thermogravimetric study of the kinetics of water penetration intoBa 4 Ca 2 Nb 2 O 11 , it was found that
the process is limited by the intraphase diffusion of Н 2 О
andproductnotpossessesblockingaction.Proceedingofof thisthe thermogravimetric method was used to
determine the coefficients of chemicaldiffusion of water.To calculate the coefficients of chemical
diffusion of water, experimentallymeasuredtemporarydependenciesmassesaftersharpchangesР Н2О
(partial pressure of water vapor) from one fixed value toanother. The obtained time dependences of the
mass were processed usingsolutions of the equation of Fick's second law for one-dimensional diffusion
in a thin plateat constant surface concentration. The humidity of the atmosphere was changed inseveral
stages from pH 2 O value from 3 * 10 -5 atm (dehydration Р 2 О 5 ) to 2 * 10 -2 atm (vaporswater at 25 0
С).For Ba 4 Ca 2 Nb 2 O 11 and Sr 6 Ta 2 O 11 , data were obtained on the coefficients of
chemicaldiffusion of water in the temperature range 350-500 0 С and in the range pH 2 O 3 * 10 -5 -2 *
10 -2 ,(the selected intervals correspond to the most intense interaction withwater). The nature of the
dependence of the diffusion coefficients of water on the amountmole of embedded water and their
temperature dependence.The work was carried out with the financial support of the RFBR grants (No.
02-03-32741),RFBR-URAL (No. 04-03-96094) and CRDF (ЕК-005-XI).46

Page 47

FIXATION OF FREE RADICALS BY CATCHOLATTIN AND LEAD COMPLEXESLado A.V., Piskunov A.V.,
Cherkasov V.K., Abakumov G.A.Institute of Organometallic Chemistry. G.A. Razuvaev RASIn recent years,
the attention of researchers in the field of o-quinone chemistrymetal complexes are concentrated on o-
semiquinone derivatives, due tothe possibility of studying the properties of the latter using EPR
spectroscopy. Whereincatecholate complexes based on hindered pyrocatecholsremain less studied. At
the same time, interest in metal catecholates is due to theirthe ability to one-electron oxidation with the
formation of the correspondingo-semiquinolate derivatives. This property allows you to synthesize
newo-semiquinone complexes, the preparation of which by other methods is verydifficult. In addition,
metal catecholate complexes arepromising reagents in radical particle fixation reactions.During the study
of redox processes involving o-quinone derivatives of metals, a number of new mono - anddicatecholate
complexes based on group 14 metals (tin Sn and lead Pb) and3,6-di-tert-butylpyrocatechol with the
general formula Сat n ML m(where Cat is a dianion3,6-di-tert-butylpyrocatechol; M = Sn, Pb; L = Cl, Ph,
Et, Py, THF, Et 2 O; n = 1, 2;m = 0, 1, 2). All connections have been highlighted individually
andcharacterized by IR and PMR spectroscopy and elemental analysis. ForX-ray diffraction analysis was
performed for a number of complexes.It was found that, depending on the composition and structure,
synthesizedcomplexes are capable of fixing various, both short-lived and stablefree O-, C-, S-, N-centered
radicals, while forming stable o-semiquinone derivatives:Bu tBu tOOML x+ RBu tBuOOML yRtThis work
was supported by the Russian Foundation for Basic Research (Grant No. 04-03-2413), a grant from the
PresidentRF for the support of leading scientific schools (NSh - 1649.2003.3).47

Page 48
FEATURES OF THE GEOMETRIC STRUCTURE OF THE MOLECULENi (salen) IN THE GAS PHASE AND
CRYSTALLevina Yu.S., Giricheva N.I.Ivanovo State UniversityIn this work, the mass spectrometric method
was used to determine the compositionsaturated Ni (salen) vapor, and also studied the structure of the
free moleculeNiO 2 N 2 C 16 H 14 by gas electron diffraction and quantum chemistry methods.
Experimentwas carried out using the EMR-100 / APDM-1 equipment complex. Ni (salen) preparation
evaporatedfrom a molybdenum ampoule at T = 583 (5) K. Simultaneously with the recording of electron
diffraction patternsthe mass spectrum of the studied vapors was recorded, the nature of whichtestified
to the absence of dimerization in the gas phase, whilecrystalline Ni (salen) consists of dimeric fragments
[1]. Structural Analysiselectron diffraction data was carried out under the assumption of C 2 -symmetry
of the molecule. INAs a result of the OLS analysis, the functions sM (s) (the value of the mismatch
factor5.0%), the main internuclear distances in a free molecule are given belowtogether with the
parameters of the molecule in the crystal (the latter are given in square brackets):r (CC av ) = 1.427 (3)
[1.400] Å in C 6 H 4 , r (CN) = 1.454 (15) [1.482] Å, r (N = C) = 1.286 (15) [1.283] Å,r (CO) = 1.302 (13)
[1.305] Å, r (N-Ni) = 1.889 (22) [1.858] Å, r (O-Ni) = 1.882 (21) [1.829] Å.The structure of the five-
membered C 2 N 2 Ni ring corresponds to the twist conformation withthe largest torsion angle around
the C-C bond φ (NCCN) = 38.3 ° and the smallest angleφ (NNiNC) = 12.6º around the Ni-N bond. The
torsion angle φ (CCNNi) is -32.2º.The non-flatness of the cycle is quite high (the sum of the inner angles
in the cycle is 526ºinstead of 540º for a flat figure). According to electronographic data, the
coordinationthe NiN 2 O 2 cavity has a trapezoidal structure with r α (O… O) = 2.629 (29) Å and r α (N…
N) = 2.488 (36)Å and angles NNO = 91.2 (8) º and NOO = 88.4 (8) º. All coordination bonds are N-Ni and
O-Nilie in one plane (the sum of bond angles at Ni is 360º). The fact that the fragmentNiN 2 O 2has a flat
structure, testifies in favor of a low-spinelectronic state of the molecule. Geometric structure of a free
moleculeclose to the structure of a molecule in a crystal.This work was supported by the Russian
Foundation for Basic Research (grant 04-03-32661a).1.L.M. Shkolnikova, E.M. Yutal, E.A. Shugam, V.A.
Voblikova. Journal. Structure.Chemistry, vol. 11, no. 5, 1970, 887-890.48

Page 49

SYNTHESIS AND SOME PROPERTIES OF COMPLEX CHROMATO (VI) -PHOSPHATES OF TRIQUALENT CATION
OF COMPOSITION M I2 M III (CrO 4 ) (PO 4 )E.V. LeutkinaInstitute of General and Inorganic Chemistry.
N.S. Kurnakov RAS,Moscow State University M.V. Lomonosov, Faculty of ChemistryChromato (VI)
-phosphates of composition M I2 M III (CrO 4 ) (PO 4 ) is a newgroup of complex phosphates. Their
research is of interest in fundamentalplan, and in the future the results obtained can be used forsolving
problems of an applied nature.By the example of neodymium and erbium compounds in combination
with potassium with varyingstarting reagents (R 2 O 3 , R 2 (CO 3 ) 3 * nH 2 O, R (NO 3 ) 3 * nH 2 O),
durationpreliminary annealing (70 h., 252 h.) and preparation method for annealing mixturesstarting
reagents (cryochemical, grinding in acetone), solid-phasesynthesis and the conditions necessary for the
formation of a phase of a previously unknowndouble chromato (VI) -phosphate potassium-erbium
composition K 2 Er (CrO 4 ) (PO 4 ). Was shown,that the formation of compounds of this type is
characteristic of metals with a small radiusM III = Dy-Lu, In, Sc. Using the example of a compound of
lutetium, it was found that under conditionsselected for the preparation of potassium (synthesis
temperature of 550 to C),chromato (VI) -phosphates of the composition M 2 Lu (CrO 4 ) (PO 4 ), where M
I = Li, Na, are not formed.The influence of the duration of preliminary annealing and temperature is
revealed.synthesis for the degree of crystallization of the obtained samples. Installedthe most suitable
conditions for the synthesis of complex chromato (VI) -phosphates.It was shown that complex chromato
(VI) phosphates are characterized by lowthermal stability: an increase in the duration of annealing at a
temperaturesynthesis leads to their decomposition into REE phosphate and potassium chromate.All
obtained complex rare-earth chromates are isostructural and crystallize inorthorhombic system. Their
structure is of a layered type likedouble phosphates of rare earth elements. For samples of thulium,
ytterbium and lutetium compoundsthe parameters of the unit cells are calculated.The IR spectra of
double chromato (VI) -phosphates of potassium were studied. Charactersplitting of the bands indicates a
significant distortion of PO 4 tetrahedra incrystal lattice and their strong dipole-dipole interaction,the
CrO 4 tetrahedra in the structure retain the T d symmetry .49

Page 50

NANOCOMPOSITES SnO 2 -MoO 3 : SYNTHESIS, MICROSTRUCTURE ANDSENSOR PROPERTIESE.A.

MakeevaMoscow State University M.V. Lomonosov, Faculty of ChemistryA highly dispersed system
formed by semiconductor oxide (SnO 2 ) andd-element oxide (MoO 3 ), which has catalytic activity in the
reactionsoxidation of the simplest organic molecules - nanocomposite - is a specialinterest for the
creation of sensitive elements - gas sensors of resistivetype. In such systems, the microstructure, redox
and acidthe main properties depend on the molar ratio of the oxides included in it:the minor component
can either form a solid solution in a crystallinethe lattice of the main component, or segregate on the
surface of crystallites,forming a monolayer, or forming its own phase.SnO 2 -MoO 3
nanocompositessynthesizedinrangecompositions0 ÷ 82 mol. % MoO 3by the method of chemical
precipitation from solutions. Composition andmicrostructurenanocompositesinvestigatedmethodslocalX-
ray spectral analysis, transmission electron microscopy,Raman spectroscopy and X-ray diffraction.
Specific areasurface was determined by the method of low-temperature adsorption of nitrogen from the
isothermBET. The average crystallite size in the obtained samples is 2--20 nm forphase SnO 2 (cassiterite)
and 25 ÷ 40 nm for the phase MoO 3 (orthorhombic modification).It was shown that the specific surface
area of the synthesized nanocompositescorrelates with their phase composition, and its maximum value
- 120 ÷ 148 m 2 / g -corresponds to single-phase samples based on tin dioxide. At the same time, the
introductionMoO 3 stabilizes the microstructure of SnO 2 under thermal annealing conditions.Sensory
properties of SnO 2 -MoO 3 nanocompositestowardslow-molecular alcohols C n H 2n + 1 OH (n = 1 ÷ 4)
and to NH 3 were studied in situ bymeasurements of electrical conductivity. The set of experimental data
obtainedinterpreted within the framework of a model that takes into account possible
mechanismsinteractions occurring on the surface of oxide materials, as well asacid-base properties of
the nanocomposite surface.50

Page 51

PHASE TRANSFORMATIONS IN THE INTERACTION OF NATURALTANTALONIOBATES WITH

CARBONMansurova A.N., Chumarev V.M., Maryevich V.P.Institute of Metallurgy, Ural Branch of the
Russian Academy of SciencesX-ray phase analysis using a DRON-2.0 diffractometer,equippedhigh
temperatureprefixGPVT-1500andx-ray spectralmicroanalysisresearchedphase formationatreduction of
natural monominerals of tantalum and niobium with carbon. Basedthermogravimetric studies revealed a
temperature range (1723-2000K)reduction of tantaloniobates to carbides, it was found that the
reducibilitytantaloniobates increases in the order: microlite, struverite, vodzhinite, tantalite,columbite.It
is known that the reduction of tantalum and niobium from natural ironmanganese-containing
tantaloniobates, as well as from their oxides, proceeds in stages [1,2].In the initial period of the recovery
process, the transition of tantaloniobates(columbite and tantalite), having an orthorhombic crystal
lattice, intetragonal phase, isostructural niobium dioxide - tapiolite, which thenreduced to a carbide
phase. At the initial stage, the carbide phaseenriched with niobium. It has been established that the
most likely mechanism of formationtapiolite is not caused by a rearrangement of the crystal lattice of
columbite, but occursby dissolving the original tantaloniobate in niobium dioxide [3].It is possible that
the reduction of vodzhinite and struverite with carbon proceedsalso through the formation of an
intermediate phase - tapiolite.1. Shveikin G.P. Features of the mechanism for the reduction of refractory
metalscarbon. // Physical foundations and mechanism of reactions in solids.Sverdlovsk: UC AS USSR.
1976. Issue. 33, p. 172.2. Kolchin O. P. Chemistry of reduction of niobium from its pentoxide with
carbon //Non-ferrous metals. 1970. No. 7. S. 46-48.3. Marievich V.P., Chumarev V.M., Krasikov S.A. Phase
transformations atthe interaction of niobium dioxide with iron oxides, columbite andtapiolite. //
Inorganic materials. 1993. vol. 29, no. 12, pp. 1656-1659.51

Page 52

SYNTHESIS AND PROPERTIES OF NEW PHOTO- AND ELECTROACTIVEPOLYMER BASED ON THE Ni (II)
COMPLEX WITH 8-OXYQUINOLINEMasalovich M.S., Ardasheva L.P., Shagisultanova G.A.Russian State
Pedagogical University. A.I. HerzenBy the method of electrochemical oxidation, we for the first time
obtained a polymer onbased on a complex of Ni (II) trans-structure with bidentate ligand 8-
hydroxyquinoline(qol).NONi2+NOThe choice of this ligand is due to the presence of an aromatic
system,activated by conjugation with functional heteroatoms N and O.the polymer based on the [Ni (qol)
2 ] complex contains a qualitatively new type of monomer incomparison with those previously used for
the synthesis of nanosized supramoleculescomplexes with Schiff bases [1]. It was found that the optimal
conditionelectrochemical polymerization [Ni (qol) 2 ] is the anodic oxidation of the complex
inpotentiodynamic conditions when scanning a potential from 0.0 to 1.3 V. AtIn this case, cathodic ( E pc
= 0.5 V; I pc = 100 μA) andanode waves ( E pa = 1.0 V; I pa = 130 μA). The transition from reduced to
oxidizedform is accompanied by an electrochromic effect, the result of which ischanging from green to
pink, respectively. Coefficient valuecharge diffusion in the polymer is equal to 1.4 · 10 -12 cm 2 · s -1 .
Maximum film thicknessis 0.17 μm. The studied polymer is photoelectrochemically active. INbackground
electrolyte solution under continuous irradiation with polychromaticlight potential of an electrode with a
polymer film applied to its surfacereaches 80 mV. The report discusses the properties of a new polymer
witha number of practically important properties: electrical conductivity, electrochromism
andphotoelectricity.1. G.A. Shagisultanova., L.P. Ardasheva, I.A. Orlova. “Electric andphotoelectric
activity of thin-layer film polymers based oncomplexes [NiSalen] and [NiSalphen] ”// J. Appl. chem.,
2003, vol. 76, no. 10,S. 1675-1681.52

Page 53
SURFACE MORPHOLOGY, COMPOSITION AND MECHANISMFUNCTIONING OF CHALCOGENIDE
ELECTRODESLOW TEMPERATURE H 2 S SENSORSV.S. Neudachina 1 , Levchenko A.V. 2 , Tikhonov E.V. 11
Moscow State University M.V. Lomonosov, Faculty of Chemistry,2 Institute of Problems of Chemical
Physics, Russian Academy of Sciences, ChernogolovkaInexpensive portable sensors for determining the
concentration of hydrogen sulfide ingas and liquid media are of great interest to various industries of the
miningand the processing industry. Newsolid state electrochemical sensors type Na x WO 3 / solid
electrolyte / MeS x(MeS x= CdS, PbS, MoS 2 ), which have high sensitivity andselectivity with respect to
H 2 S. Such sensors work under normal conditions(temperature - 40 ÷ + 60 0 С, relative humidity 10-95%)
without thermal andhydrostation.In this work, we studied sensors with working electrodesbased on PbS.
The aim of the work was to study the effect of the method of applyingworking electrode on the
characteristics of the sensor, as well as studying the mechanismfunctioning of working electrodes and
their surface morphology. Workerselectrodes were pressed onto a solid electrolyte or deposited from a
solution.Electrochemical measurements show that the performance of sensors withPbS electrodes
deposited from a solution significantly exceed those forsensors with pressed electrodes. Worker surface
morphologyelectrodes deposited from a solution depends significantly on the deposition conditions.
Byimpedance data, not only EMF, but also the resistance of the PbS / NaSiCON boundarychanges
reversibly with a change in the concentration of H 2 S.Experimental data obtained using the X-ray
methodphotoelectron spectroscopy, indicate that the adsorption of H 2 S occursreversible partial
recovery of the PbS surface. Quantum chemical calculations,carried out within the framework of the
electron density functional theory (B3LYP) withusing the cluster approach, show that the mechanism of
action of sensorsmay be associated with reversible proton transfer from sulfur to oxygen atadsorption of
H 2 S on the oxidized surface of the PbS working electrodes.53

Page 54

SYNTHESIS AND STUDY OF COMPOUNDS IN ALKALINE SYSTEMSMETAL - Ru (Pd) - OPanin R.V.Moscow

State University named after M.V. Lomonosov, Faculty of ChemistryDouble oxides of alkali metals and
ruthenium or palladium at presentare considered as starting materials for the manufacture of
electrodesfuel cells. The aim of this work was to synthesize and studydouble oxides in alkali metal - Ru
(Pd) - O systems.RuO 2 was preliminarily synthesized by annealing ruthenium oxychloride in airat 800 ° C
for 15 hours. PdO was obtained by dissolving palladium metal in"Aqua regia" followed by evaporation of
the reaction mixture with an excess of NaNO 3 ,then the melt was treated with water and the separated
PdO was dried at 600 ° C. Receivedthe oxides were reacted with the corresponding alkali metal
carbonate.The syntheses were carried out in air, as well as in a stream of oxygen and nitrogen at
variousmodes of heat treatment.Depending on the annealing conditions,several phases previously
described in the literature are characterized. In a stream of nitrogensynthesized NaRuO 2 (950-1000 ° C),
NaRuO 2 * xH 2 O (950-1000 ° C), NaRu 2 O 4 (1000-1100 ° C) KRu 4 O 8 (850 ° C), Li 2 RuO 3 (800-850 °
C), K 2 RuO 3 (OH) 2 (650-700 ° C) and Li 2 PdO 2 (770 ° C), and in a stream of oxygen - Na 2 RuO 4 (780 °
C).X-ray diffraction pattern of the NaRu 2 O 4 phasewas indexed in orthorhombicsystem with unit cell
parameters a = 9.2641 (7) Å, b = 2.8249 (2) Å,c = 11.1496 (7) Å, space group Pnma. This compound is
isostructurally NaTi 2 O 4and contains in the structure of the ribbons connected through common edges
of ruthenium-oxygenoctahedrons.54
Page 55

PREPARATION, PROPERTIES OF Pt (II) MACROCYCLIC COMPLEXES,Pd (II) WITH 2,2-BIPYRIDIL, O-

PHENONTRALINE, 4,4-BIPYRIDILPanova A.G., Balashev K.P.Russian State Pedagogical University. A.I.
HerzenA new class of cationic, tetranuclear, macrocyclic complexes of Pt (II) andPd (II) presents a new
material with as yet undiscovered uniqueproperties. The use of these macrocycles is possible as carriers
intheir cavities "guests" due to the non-covalent nature of the interaction, as well asnano-scaling of
these molecules into sensor devices [1].We have obtained square macrocyclic complexes of Pt and Pd
based onreactions of self-organization of mononuclear complexes МbipyCl2 and МphenCl2 (М = Pt,Pd,
bipy-2,2'-bipyridyl, phen-o-phenontroline) in the presence of a bridging 4,4-bipyridyl. Substances were
identified using 1 H-NMR spectroscopy,which showed the formation of flat-square structures. So, two
signals from 4,4-bipyin the spectrum differed from the signals of the uncoordinated 4,4-bipy starting
materials,strong-field shift-β-effect, as well as the presence of an orthogonal positionpyridine rings 4,4-
bipy.The optical and electrochemical properties of these macrocycles have been studied. So,absorption
spectra showed an increase in absorption intensity overcompared with the original complexes and the
presence of a hypsochromic shift, which is associated with4,4-bipy coordination and the corresponding
influence on the electronic transitionM → ligand. Luminescence confirms the assumption about the
participation of peripheralligands in electron transitions and energy emissionintensity due to the
tetranuclear structure. Electrochemical analysis showedthe existence of one-electron, reversible waves
in the reduction region,which are characteristic of the bridging 4,4-bipy ligand.A set of data from NMR
spectroscopy, electron spectroscopy andelectrochemistry confirms the self-assembly of Pt (II) and Pd (II)
complexes into tetranuclearstructures based on bidentate, bridging ligand 4,4-bipy.1. Peter J. Stang. Self-
Assembly of Cationic, Tetranuclear, Pt (II) and Pd (II)Macrocyclic Squares // J. Am. Chem. Soc. 1995, 117,
6273-6283.55

Page 56

ELECTRICAL SURFACE TRANSFER AND CONNECTED PROCESSESON HETEROPHASE BOUNDARIES MeWO 4

│WO 3 (Me = Ca, Sr, Ba)Pestereva N.N.Ural State University A.M. Gorky, YekaterinburgThe nature and
mechanism of solid-phase electrosurface phenomena in manythe outline remains unclear. First of all,
this applies to the outwardly mosta simple process - field-stimulated retraction of WO 3 onto the
internalsurface of ceramic CaWO 4 , which occurs in the cellWO 3 →(-) Pt│WO 3 │CаWO 4 │WO 3 │Pt (+)
(1)The results of this work for the MeWO 4 │WO 3 eutectic systems (Me = Ca, Sr, Ba):1. In the absence of
a potential difference, contact interaction occurredbetween MeWO 4 and WO 3 , the mass of MeWO 4
decreased, the near-surface region of WO 3turned dark green. The XRF of the MeWO 4 surface showed
WO 3 lines .2. In the electric field, for all systems, the WO 3 retraction describedhigher. The mass of WO
3 transferred to ceramics MeWO 4 increases proportionallythe last charge, briquette WO 3(-) turns dark
green, RFA WO 3(-) commitslines МеWO 4 . The coefficient of entrainment of WO 3 by the electric field
is close for allMeWO 4 - χ = 0.42 ± 0.02. It is shown that the polarization mode (potentiometer
orgalvanostatic) does not affect the transfer parameters.3. Based on the new data, the process
mechanism model has been modified. On thecontact MeWO 4 │WO 3a surface non-autonomous phase
MeW-s withelectrolytic conductivity ( t ion = 1) and high surface mobility( D MeW-s → MeWO4 ≈ D
MeW-s → WO3 ) . The surface energy ( α ) of MeW-s is lower than MeWO 4 andWO 3( α MeW-s < α WO3
< α MeWO4 ) . Therefore, MeW-s is distributed internally.ceramic surfaces of both MeWO 4 and WO 3 .
Energy of adhesion of the MeW-s phase to MeWO 4and WO 3 depends on a number of environmental
and experimental parameters. When passing currentthe film of the MeW-s phase acts as a medium
through which WO 3 is drawn into MeWO 4 to(+) electrode, and at the grain boundaries of the electronic
conductor WO 3goeselectrochemical process detectable (SEM) by the release of new phases.The work
was carried out with the financial support of RFBR grants (04-03-32614),programs "Universities of
Russia" UR.06.01.027 and CRDF (EK-005-XI).56

Page 57

THEORETICAL MODELING OF STRUCTURE AND PROPERTIES3d - 4f HETEROBIMETAL

COMPLEXESRogachev A.Yu.Moscow State University M.V. Lomonosov, Faculty of ChemistryIn recent
years, interest in the synthesis of coordination 4f-3d -heterobimetallic compounds, since the
combination in one molecule of twometals of different nature can lead to the appearance of such
complexesunique functional properties. One possible way to combinetwo metals in one molecule is the
use of a 3d metal complex asadditional neutral ligand saturating the coordination sphere of the ionREE.
However, for the targeted synthesis of such heterobimetallic complexesknowledge of the laws of their
formation and stability is necessary. The most completethe solution to this problem lies in combining
theoretical and experimentalapproaches.In this work, a theoretical study of the structure and properties
ofheterobimetallic complexes of the composition [La (dik) 3 M (salen)], where Hdik
=pivaloyltrifluoroacetone (Hpta), trifluoroacetylacetone (Htfa), M = Ni (II), Cu (II),H 2 (salen) = Schiff base
obtained by condensation of one mole of ethylenediamine andtwo moles of salicylic aldehyde.
Theoretical modeling was carried outby the method of electron density functional theory with exchange-
correlationfunctional B3PW91. To describe the electronic structure of metal ionsrelativistic core
potentials of the Stuttgart group (Stuttgart-Bonn group RECP) with recommended baselines. To describe
atomsorganic ligands, the 6-31G basis was used. detailing the electronic structurewas carried out within
the framework of the method of natural bonded orbitals (NBO). During workthe distribution of natural
charges on atoms was investigated, and alsobinding energy La (dik) 3- M (salen). Comparison of the
receivedtheoretical data on the thermodynamic stability of heterobimetalliccomplexes with
experimental.Within the framework of this work, a study of the applicability of the theoryboundary
orbitals (Frontier Molecular Orbital) for describing patternsthe formation of heterobimetallic complexes
containing 4f -elements.57

Page 58

RESEARCH OF IRON-CONTAINING ACID PHOSPHATESM I FE (НPO 4 ) 2 (M I = K + , RB + , CS + )Rusakov

D.A. 1 , Filaretov A.A., Komissarova L.N.1 Institute of General and Inorganic Chemistry named after N.S.
Kurnakov,Moscow State University M.V. Lomonosov, Faculty of ChemistryComplex acid phosphates are
characterized by the formation of a large numbercompounds of various compositions. To date, the most
studied acidicphosphates and arsenates of the composition M I M III (HEO 4 ) 2 , where M I = Li + , Na + ,
K + , Rb + , Cs + , H 3 O + and NH 4+ ,and M III = s , p - and d -elements. The change in the composition of
the cationic part causesa variety of structural forms and physical and chemical properties.Compounds of
the composition M I Fe (HPO 4 ) 2 (M I = K + , Rb + , Cs + ) were obtained by hydrothermalmethod ( p =
20 atm., τ = 48 - 120 hours, Т = 160, 180, 200 Сº, 0 <pH <2.5). For synthesisused different molar ratios of
ternary mixtures,including Fe 2 O 3or FeCl 3 * 6H 2 O, M I2 CO 3(M I = K + , Rb + , Cs + ), H 3 PO
4(85%).The phase composition of the sediments was determined by the XRD method. Acid phosphatesM
I Fe (HPO 4 ) 2(M I = K + , Rb + , Cs + ) isolated as polycrystalline sedimentsbrick-red. Crystals suitable for
structural studies,found only for β –RbFe (HPO 4 ) 2 . Acid phosphates M I Fe (НPO 4 ) 2(M I = K + , Rb + ,
Cs + ) polymorphism is inherent. The Rietveld method refined the modelscrystal structures α –M I Fe
(НPO 4 ) 2(M I = K + , Rb + , Cs + ) and β –KFe (HPO 4 ) 2 .The compounds were characterized by SHG LI,
IR- and Mesbauerspectroscopy. Thermal stability has been investigated.The metric of the unit cells of the
triclinic modifications α –M I M III (HPO 4 ) 2 (M I = K + ,NH 4+ , Rb + , Cs + , M III = V 3+ , Fe 3+ ; space
group P-1, Z = 3) structural type α –KbV (HPO 4 ) 2 : a ~ 8Ǻ,b ~ 9Ǻ, c ~ 7Ǻ, α ~ 110º, β ~ 110º, γ ~ 65º.
Monoclinic unit cell metricmodifications β –M I M III (HPO 4 ) 2 (M I = K + , NH 4+ , Rb + , Cs + , M III = V
3+ , Fe 3+ , Sc 3+ , In 3+ ;Gr. P 2 1 / c , Z = 4) structural type (H 3 O) Fe (HPO 4 ) 2 : a ~ 5Ǻ, b ~ 8Ǻ, c ~ 14Ǻ,
β ~ 95º.Like the known acid phosphates M I M III (HPO 4 ) 2researchedrepresentatives of this group are
characterized by the formation of a mixed pseudo-frame{M III (HPO 4 ) 2 } -3∞ , a feature of which is the
division of only three verticesPO 4 tetrahedra with M III O 6 octahedra , while the fourth vertex is
associated with a proton.The negative charge of the framework is compensated by M I cations located
inlarge cavities.58

Page 59

LITHIUM OXOIRIDATES: SYNTHESIS AND DEINTERCALATION PROCESSESSergeev R.V.Institute of General

and Inorganic Chemistry RASThe process of intercalation / deintercalation of lithium from transition
metalateselements is the basis for the operation of lithium current sources. At the same time, the
processlithium migration is accompanied by a change in the chemical composition and structureinitial
phases, and, in principle, can serve as a method for the synthesis of new compounds.This method is
especially attractive when applied to the problem of stabilizationunusual oxidation states (s.r.) of
elements. An example of similar processesis the production of metastable Co IV O 2and Ni IV O 2from
LiCo III O 2and LiNi III O 2 ,respectively.In this work, a solid-phase method for the synthesis of
oxoiridateslithium and processes of delithiation of the obtained compounds. Diagnostics of the initial,
andalso delithium samples were carried out by coulometry methods,powder X-ray, magnetochemistry.
To confirm S.O. iridium usedmethod of X-ray photoelectron spectroscopy.Solid phase by annealing using
IrO 2 and Li 2 O 2 were synthesized iridatlithium composition Li 2 Ir IV O 3monoclinic structure, as well as
previously undescribedcubic and hexagonal modifications. It is shown that the decisive influence onthe
structure of this iridate is exerted by the nonstoichiometry with respect to lithium and the
degreeordering / disordering of the metal sublattice. Iridate synthesizedlithium composition Li 8-x Ir IV +
x O 6 , where x = 0 - 2.The processes of lithium deintercalation from the obtained compounds
intogalvanostatic mode. The experiments were carried out according to a three-electrode scheme,
inlithium electrochemical cells. It was shown that lithium deintercalation is possiblefor all structural
modifications we obtained. Moreover, delithiationLi 2 IrO 3 is accompanied by an increase in s.d. iridium
up to +5 - +6. Process researchdelithiation for Li 8-x IrO 6 is not completed at the moment, however
preliminarydata indicate the possibility of obtaining iridium in oxidation states, morehigher than +6.59
Page 60

SYNTHESIS AND STUDY OF PROPERTIESNA 2 [H 6 GEMO (W) 10 O 36 ]Sidorenkova I.V., Chernov

E.B.Tomsk State UniversityCurrently, heteropoly compounds are finding more and moreuse as
multifunctional materials such as sensors,phosphors, proton conductors, etc. However, compounds of
composition XY 10 , where X -Ge, Y - Mo (W) c are poorly studied, there is no description of the synthesis
of suchcompounds and their properties. The synthesis of heteropoly compounds (HPC) was carried out
withinpH 8 - 6, when the initial solutions of GeO 2 and sodium tungstates (molybdates) are merged .The
charge and shape of the GPA anion [H 6 GeY 10 O 36 ] 2- was determined by the method of isomolar
series .The obtained compounds in solutions form precipitates with ions of such alkalinemetals such as K
+ , Rb + , Cs + and d - and f - metal ions, for example, Co 2+ , Ni 2+ ; and Ln 3+ . INsolid state substances
are fine crystallinepowders that dissolve well in ethylene glycol, 1,4-dioxane. Investigatedoptical, thermal
and kinetic and luminescent properties of GPS.The obtained IR spectra of sodium decamolybdo
(tungsten) - germanates were compared withspectra of sodium decatungstenocerate (IV), which have
similar frequenciesfluctuations, which indicates the identity of the structures of the obtained
compounds. SolutionsGPS gives electronic spectra in the UV region. The synthesized compounds are
capable ofeasy to form heteropolysini under the action of reducing agents such as ascorbatecalcium. The
absorption spectra of blue are in the region of 400 nm. Kinetics studiedformation of blue Na 2 [H 6
GeMo 10 O 36 ], which obeys the reaction equations of the firstorder and flows in parallel. Analysis of
kinetic data indicatesthe existence of three HPC isomers, which are reduced with differentspeeds: 55.2%
of the first is restored with a rate constant of 6.5⋅10 -3 s -1 ; 35.2%the second is restored with a rate
constant of 1.56⋅10 -3 s -1 , and 9.6% of the thirdis restored with a much lower constant, which we have
not determined.These HPCs form complex compounds with Co 2+ ionscomposition 1: 1.Formation is
confirmed by a shift of the spectrum of aqua - ions Co 2+ to shortwavearea (hypsochromic shift). Studies
have shown that GPS hasantitumor mechanism of action of scientific interest in the development of
newbioactive compounds for oncological purposes.60

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INFLUENCE OF THE TRANS EFFECT ON CHEMICAL ACTIVITYSALTS OF 3d METALS IN COORDINATION

REACTIONSToldina O.V., Berezin D.B., Berezin B.D.Institute of Solution Chemistry RAS, Ivanovo,* Ivanovo
State University of Chemical TechnologyThe effect of trans- influence, as a special case of the
manifestation of the theory of mutualthe influence of atoms in molecules, is well studied by the example
of flat-squarecomplexes, for example, Pt (II) and Pd (II), octahedral complexes Pt (IV), Co (III).At the same
time, some literature datatestify to its manifestation in complexesCu (II) [1-3].We have studied the
influence of the nature of mixedsolvent based on DMSO, DMF and Py ina wide range of its compositions
for kineticspecificationsreactionscoordinationtetraphenyltetrabenzoporphine(I)andN-
methyloctaethylporphine (II)acetatecopper.Discovered catalytic effect of mixedsolvent on the reaction
rate is explained inthe framework of the theory of trans- influence. in the reportreactivity issues are
discussedsolvates of 3d-metal salts of composition [MX 2 (S) 4 ] and[MX 2 (S 1 ) m(S 2 ) 4-m ] in reactions
with porphyrinsdifferent structures (chlorophyll ligand (H 2 Chl),meso- tetraphenylporphine(H 2 TPP),N-
methyloctaethylporphine (H (N-Me) (β-Et) 8 P), meso -tetraphenyltetrabenzoporphine(H 2 TBP (Ph)
4 )).Mechanismtrans- influencesconsidered at the level of the transition state of reactions. During our
researcha strong dependence of the trans effect on the nature of the metal and porphyrin was
revealed .HNNNNEtEtEtEtEtEtEtEtCH 3HNNNHNIII1. Yatsimirsky KB Thermochemistry of complex
compounds. M., 1951.p. 303.2. Bersuker I.B., Ablov A.V. Chemical bond in complex compounds.Chisinau,
1962, p. 208.3. Kukushkin Yu.N. Chemistry of coordination compounds. M., 1985. p. 455.61

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SYNTHESIS AND CRYSTALLINE STRUCTURE OF NEW COMPLEXESSc (III), La (III) AND Gd (III) WITH
KUKURBIT [6] URILTrypolskaya A.A.Institute of Inorganic Chemistry. A.V. Nikolaeva SB RASCurrently,
supramolecular complexes onbased on cucurbit [6] uril (C 36 H 36 N 24 O 12 , Q6 ). This is a cavitand
with a toughmacrocyclic structure, able to coordinate oxophilic metalsdue to the presence of 12
polarized carbonyl groups. Using Q6 aspolydentate ligand is effective for isolating kinetically
labilecomplexes of lanthanides (III) from aqueous solutions. We have previously synthesized andthe
complexes with cations La 3+ , Ce 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Ho 3+ ,Yb 3+ with different metal / Q6 ratios
. In this work, we reportobtaining and crystal structure of newcompounds of scandium (III), lanthanum
(III) and gadolinium (III)fromQ6 : [Sc (NO 3 ) (H 2 O) 4 Q6 ] (NO 3 ) 2 ⋅8.5H 2 O ( 1 ),[La (NO 3 ) (H 2 O) 6
(0.5C 5 H 5 N⊂ Q6) ] (NO 3 ) 2 ⋅8H 2 O( 2 ),[{Gd (NO 3 ) (H 2 O) 5 } 2 Q6 ] (NO 3 ) 4 ⋅6.5H 2 O( 3 ),[{Gd (NO
3 ) (H 2 O) 5 } 2 (C 5 H 5 N⊂ Q6) ] (NO 3 ) 4 ⋅8H 2 O( 4),{[Gd (NO 3 ) (H 2 O) 7 ] (C 5 H 5 N⊂ Q6) } (NO 3 ) 2
⋅10H 2 O( 5 )Cationic complex in 4.Crystal structure of compounds 1 - 4is a package of cation
complexesmetals with Q6 . The metal atom coordinates two CO groups Q6 , 4 - 6 water molecules,
andbidentate nitrate anion. In compounds 1 - 2, only one portal of the Q6 moleculeclosed with a “lid”
from the aqua complex, and in compounds 3 - 4 , which are obtained athigher concentrations of metal
cations, both portals are closed. In allcompounds, the macrocycle cavity is occupied by water or pyridine
molecules. INcompound 5, the gadolinium atom is not directly linked to Q6 , but coordinated to itwater
molecules form hydrogen bonds with the oxygen atoms of the macrocycle.Compound 5 was obtained at
higher pH 6. Further increase in pHshould lead to the formation of polynuclear lanthanide aqua
complexes. INCurrently, work is underway to separate them into the solid phase using Q6 .62

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SYNTHESIS OF ANORTITE CERAMICS WITH INCREASEDMECHANICAL PROPERTIESFedorov N.V., Golovin

E.P., Kukhtin B.A.Vladimir State UniversityOn the basis of anorthite CaO · A1 2 O 3 · 2SiO 2 , the
composition of industrial ceramics was developedAS-10 with high dielectric properties: ε = 7 ... 7.5; tg δ
=(2 ... 3) · 10 -4 ; σ mfd = 100 MPa. The chemical composition of AS-10 is described by the ratio0.8CaO
0.2BaO A1 2 O 3 2SiO 2 . The main disadvantage of this material is itsrelatively low mechanical strength
and chemical resistance.We investigated the compositions of (1-x) CaO · xBaO · A1 2 O 3 · 2SiO 2 . Raw
materialanorthite composition (x = 0) at the burning temperature was 1400 ° C σ mfd = 94 MPa
andwater absorption W = 0%.Substitution of the Ca 2+ cation for Ba 2+ resulted in the following changes
in properties:x = 0.1t ff = 1380 ºСσ mfd = 114 MPaW = 0%x = 0.2t ff = 1360 ºСσ mfd = 100 MPaW = 0%x =
0.3t ff = 1360 ºСσ mfd = 100 MPaW = 0%x = 0.4t ff = 1360 ºСσ mfd = 70 MPaW = 0%Al 3+ cations can be
in coordination 4 with respect to oxygen and formtetrahedra [AlO 4 ] are stable only if near the
tetrahedron [AlO 4 ]the cation Ca 2+ is locatedor Ba 2+ . In this case, stable groups are formed[(AlO 4 )
Ca 0.52+ ] or [(AlO 4 ) Ba 2+0.52+ ], in which the Ca 2+ and Ba 2+ cations are localized ontetrahedra AlO 4
, partially compensating for their negative charge. Equimolarsubstitution of Ca 2+ on Ba 2+ sharply
deformed volume V corresponding cell Ca . Volumethe Ba 2+ cation is 2.54 times larger than the volume
of the Ca 2+ cation , respectively, upon substitution0.2 Ca 2+ by 0.2 Ba 2, the cell volume corresponding
to V Ca increases by 30.7%, and at x= 0.4 by +61.44%. Such significant deformations of the crystal lattice
leadcatastrophic drop in strength σ mfd to 70 MPa at x = 0.4.To compensate for volumetric changes in
the anorthite lattice in the composition of the materialcations Mg 2+ and Ba 2+ were introduced so that
the total volume changescells ∆V → 0. On the composition 0.7CaO · 0.05BaO · 0.15MgО · А1 2 O 3 · 2SiO
2 at the calculatedvalue ΔV = +3,1% obtained value σ mfd = 133 MPa at a firing temperature1300 ºС,
which is 33% higher than the strength of the АС-10 composition.63

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SYNTHESIS AND PHYSICO-CHEMICAL PROPERTIES OF COMPOUNDSOBTAINED IN THE SYSTEM GRAPHITE -

LITHIUMHaskov M.A. 1 , Arkhangelsky I.V. 2 , Tarasov V.P. 3 , V.V. Avdeev 11 Moscow State University
named after M.V. Lomonosov, Faculty of Chemistry,2 Institute of New Carbon Materials and
Technologies, Moscow,3 Institute of General and Inorganic Chemistry named after N.S.
KurnakovIncreased interest in carbon-lithium compounds began to appear in the 1990s .years when
SONY Corporation announced the use of carbon lithiumelectrodes in chemical current sources.
Compound of carbon with lithium - carbidelithium - proposed to be used to obtain ultrapure lithium,
nanodispersedcarbon material and even carbon nanotubes. For a rationalusing these materials, you
must have an idea of their physicalchemical properties. The purpose of this work was to synthesize and
study physicalchemical properties of intercalated compounds of graphite with lithium (Li-ICG) I, IIstages
and lithium carbide (Li 2 C 2 ). The synthesis of Li-ICG and Li 2 C 2 was carried out in reactors
fromstainless steel (Armco iron for Li 2 C 2 ) at optimal temperatures andpressures. The reactors were
assembled in a glove box in the atmosphereultrapure argon (O 2 <0.1 ppm, H 2 O <0.1 ppm, N 2 - traces).
Phase compositionproducts were monitored by X-ray phase analysis (XPA). Receivedthe values of the
crystal lattice parameters of the compounds are consistent withliterary data. After synthesis, the
substances were studied by methodsthermal analysis. Using the method of nuclear magnetic resonance
(NMR) on7 Li nuclei showed that lithium in the GIC is in an intermediate position, between
completelyionized and metallic, condition. Differential scanning methodcalorimetry (DSC) was used to
determine the phase transitions “order-disorder ”in Li-GIC and the transition from the
orthorhombohedral to cubic modificationlithium carbide. XRD, DSC, 7 Li and 13 C NMR were used to
studyprocesses of carbide formation in Li-ICG and final carbon materials,obtained after successive stages
of intercalation, carbide formation andwater treatment.64

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ELECTRONOGRAPHIC STUDY OF THE STRUCTURE OF MOLECULESSmCl 3 And HoCl 3Chernova E.V.,

Giricheva N.I.Ivanovo State UniversityQuantum-chemical studies of the structure of trihalide
moleculeslanthanides, despite the fact that many have been carried out, leavethe overall picture is
unclear. Therefore, precisionexperimental structural data for these compounds. In this workthe results of
studying the structure of SmCl 3 and HoCl 3 molecules usingsynchronous electron diffraction and mass
spectrometric method.The experiment was carried out on the EMR-100 / APDM-1 equipment
complex.SmCl 3 and HoCl 3 preparations (commercial, chemically pure) evaporated from a molybdenum
ampouleat a temperature of 1205 K, 1148 K, respectively. Simultaneously with shootingIn the electron
diffraction patterns, the mass spectra of the vapor of Sm and Ho trichlorides were recorded.Mass
spectral data show that in saturated vapor, along withmonomeric forms of LnCl 3, there is a small
amount of dimericmolecules Ln 2 Cl 6 (up to 2 mol.%). No other volatile impurities were found in the
vapor.OLS analysis of the scattering intensity molecular component functioncarried out taking into
account the presence in the pair of two molecular forms LnCl 3 and Ln 2 Cl 6 .The structural parameters
of the SmCl 3 and HoCl 3 molecules correspond to the pyramidaleffective r g -configuration:r g (Sm-Сl) =
2.501 (5) Å, ∠ g (Cl-Sm-Cl) = 116.0 (9) °r g (Ho-Сl) = 2.445 (5) Å, ∠ g (Cl-Ho-Cl) = 116.3 (9) °Moreover, the
value of the effective bond angle ∠ g ( Сl -Ln-Сl) is the same for twomolecules within the experimental
error. Changes in r g (Ln-Сl) atthe transition from Sm to Ho corresponds to a change in the radii of the
triply charged Ln 3+ ions .A smooth decrease in the ionic radii r (Ln 3+ ) upon going from lanthanum to
lutetium andthe same change in r g (Ln-Сl) in trichloride molecules indicates the
manifestationlanthanide compression and the weak influence of differences in the 4f-shell of atoms and
ionslanthanides on the geometric characteristics of LnСl 3 molecules .This work was supported by the
Russian Foundation for Basic Research (grant 02-03-33308).65

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Department "Inorganic chemistry - students"Jury:Kuzmina N.P.in. n. S., d.ch.s. - chairmanV.S.

Neudachinaasp. - secretaryDobrynina N.A.Associate Professor, Ph.D.Eremina E.A.Associate Professor,
Ph.D.Tamm M.E.Associate Professor, Ph.D.Berdonosov P.S.n. S., Ph.D.Vasiliev R.B.n. S., Ph.D.Khasanova
N.R.n. S., Ph.D.66

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TRIPLE-CORE CHALCOGENIDOMOSTIC CLUSTERCOMPLEXES Mo AND W: SYNTHESIS, STRUCTURE,

PROPERTIESAbramov P.A., Gushchin A.L.Novosibirsk State University, Faculty of Natural SciencesAn
important area of cluster chemistry of transition metals isstudy of the reactivity of chalcogenide three-
core clustercompounds of molybdenum and tungsten.This paper presents new methods for the
synthesis of triangularchalcogenide-bridged clusters of molybdenum and tungsten, theirreactivity. The
main problem in the synthesis of such complexes isextreme inertness of the initial coordination polymers
M 3 Q 7 X 4(M = Mo, W; Q = S, Se, Te; X = Br, I). The authors have developed approaches to its
solution.The first is based on the fusion of coordination polymers with potassium selenocyanate inargon
atmosphere. The synthesis products are water-soluble cyanidecomplexes. For example: Mo 3 Q 7 X 4+
KSeCN → [Mo 3 Se 7 (CN) 6 ] 2- .By adjusting the ratio between the reagents, as well as the temperature
and reaction time,it is possible to obtain cluster anions with different chalcogen composition. So,
forfusion of W 3 Te 7 Br 4 with KSeCN, taken in a ratio of 1: 3, respectively, at 200 ° Cwithin 1 h was
isolated into a solid phase and structurally characterized the compoundK 3 [W 3 (µ 3 -Te) (µ-TeSe) 3 (CN)
6 ] Br · 6H 2 O, containing a new ligand TeSe 2- . Whenthe interaction of such a cluster with potassium
cyanide in an aqueous solution occursdetachment of tellurium atoms and formation of the complex [W 3
TeSe 3 (CN) 9 ] 5- , which hasthe structure of a "cube without one vertex". Thus, a wide range of
newtriangular chalcogenide cyano complexes, characterized by IRspectroscopy, E-spray mass
spectrometry, 125 Te and 77 Se NMR spectroscopy, XRD.The second approach is based on the
mechanochemical activation of coordinationpolymers M 3 Q 7 X 4with potassium
diethyldithiophosphate (Kdtp) and potassium oxalate invibrating mill. As a result of such reactions and
subsequent extractionthe corresponding solvent were obtained and structurally characterized
newcluster complexes [M 3 Te 7 (dtp) 3 ] Br (M = Mo, W) and K 5 {[M 3 Q 7 (C 2 O 4 ) 3 ] 2 Br} nH 2 O(M =
Mo, Q = S, n = 3; M = Mo, Q = Se, n = 4; M = W, Q = S, n = 5).67

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CHEMICAL REACTIONS OF NANOPARTICLES INSIDE THE MATRIXPOLYETHYLENEAstafiev D.A.Russian

University of Chemical Technology DI. Mendeleev,Institute of General and Inorganic Chemistry. N.S.
Kurnakov RASCurrently, there is a problem of obtaining nanoparticles of a certaincomposition with a
narrow size distribution, which, for objective reasons, is not alwayspossibly. Within the framework of the
presented work, to solve the assigned task,methods of chemical modification of already obtained
nanoparticles insidehigh density polyethylene (LDPE) matrices.In this work, we studied the possibility of
chemical modification of nanoparticlesiron, copper, bismuth, mercury and lead, as well as their oxides
and chlorides usinggaseous Cl 2 and HCl, H 2 O 2 , KOH, as well as reducing agents. Were heldstudies of
the reducibility of i-PrOH in the supercritical region atexposure to composite materials containing oxide
nanoparticles andchlorides Bi, Fe, Cu.The composition and structure of the obtained nanoparticles was
established usingcomplex of physical and chemical methods (XRF, Mössbauer spectroscopy, TEM).It is
shown that chemical treatment does not significantly change the size of nanoparticles.According to the
results obtained, the impact on compositenanomaterials containing iron or its oxides, both chlorine gas
andhydrogen chloride, leads to the formation of nanoparticles of iron (II) chloride. And fornanomaterials
containing bismuth compounds, a similar treatment led tothe formation of bismuth (III) chloride.
Recovery of the obtained compositematerials, both with isopropanol in the supercritical region,
andusing other reducing agents containing nanoscale chlorides and oxidesbismuth led to the formation
of a metallic phase, and in the case of Fe 2 O 3 ,reduction to Fe 3 O 4 . Nanoparticles stabilized in the
volume of LDPE,retain high chemical activity after chemical treatment.Studies have shown the possibility
of modifying the compositionmetal-containing nanoparticles stabilized in the bulk of polymer
matricesdirected chemical reactions.68

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COMPARATIVE THEORETICAL MODELINGβ-KETOIMINATES AND β-DIKETONATES ALUMINUMBalashov

A.M., Ermilov A.Yu., Kuzmina N.P.Moscow State University M.V. Lomonosov, Faculty of ChemistryAn
important task of modern materials science is to obtain thinamorphous oxide films with a high dielectric
constant(Al 2 O 3 , ZrO 2 , HfO 2 , Ln 2 O 3 , etc.) Until now, when obtaining such films,chemical vapor
deposition (CVD) is used, and asmetal β-diketonates ( M (dik) n ) are used as precursors .
Essentialdisadvantage M (dik) nis a sufficiently high thermal stability.The use of their structural analogs -
β-ketoiminates is promising.( M (kim) n ). The stability of β-ketoiminates is lower and more can be
used.tendency to hydrolysis, realizing the CVD method with water vapor. Efficiencymodifications can be
predicted using quantum chemistry methods.Model aluminum complexes of the type Al (L ) X 2 , where L
= dik , kim , and X = F or CH 3were chosen to assess the effectiveness of replacing the diketonate
fragment withketoiminate. The comparison was carried out in a series of ligands whose structuresvaried
due to changes in the side substituents, as well as the substituent at thenitrogen in β-ketoimines.
Calculations of equilibrium geometry and total energy of complexesaluminum were carried out by the
density functional method with exchangecorrelation functional in the B3LYP form using the 6-31G **
basis.Quantification of the relative stability of β-diketonates and β-aluminum ketoiminates was obtained
on the basis of the following reaction scheme:AlX 3 + Hkim → Al (kim) X 2 + HX (E 1 )AlX 3 + Hdik → Al
(dik) X 2 + HX (E 2 )For the selected series of model complexes, it was shown that the stability of β-
diketonates are higher in all pairs of complexes Al ( kim) X 2 - Al (dik) X 2 . Stability β-ketoiminates can be
significantly increased when introduced to the nitrogen atom stronglyan acceptor group such as CF 3 .
On the contrary, with increasing degreefluorination of side substituents or when introducing a donor
substituent tonitrogen atom can significantly reduce the stability of β-ketoiminate
complexesaluminum.69

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SURFACE OXIDATION OF LEAD SELENIDE SINGLE CRYSTALSBaranova O.V.Moscow State University M.V.
Lomonosov, Faculty of Materials ScienceSemiconductor materials type A 4 B 6 are used for the
manufacture of IRphotodetectors and thermoelectric materials. Despite the activeuse in
microelectronics, the processes of oxidation of their surfaces remainpoorly studied. In this work, we
studied the features of the interactionsurfaces of PbSe single crystals with dry and wet oxygen. The
purpose of the workwas the elucidation of the change in the charge state of surface atoms in the
processoxidation using the method of X-ray photoelectron spectroscopy.For the study, we used lead
selenide single crystals grownby the "Steam-Liquid-Crystal" mechanism. The XPS spectra were recorded
atusing the ESCALAB MK II spectrometer. Bars fixed in the holdersingle crystals were placed in a
spectrometer, after which the samples were cleaved in vacuum.The spectra were recorded using
radiation AlK αatconstant transmission energy of the energy analyzer 20 eV. First registeredspectra of a
clean surface, after which the samples were kept fora certain time in an environment of dry and wet
oxygen, and then again recordedspectra. It was found that in the spectra of Pb 4 f in the process of
oxidation appearsadditional component shifted by 1.1 ± 0.1 eV towards higher binding energiesand
corresponding to the formation of a Pb-O bond. In the spectra of selenium during oxidation,two
additional components, one of which is close in energy to the Se 0(chemical shift + 2.0 ± 0.1 eV from the
main component), and the other to Se +4(chemical shift + 5.2 ± 0.2 eV).To study the change in the
composition of the PbSe surface during oxidation,samples of standards (PbSeO 3 and PbSeO 4 ) were
synthesized and studied . From their spectra werethe elemental sensitivity coefficients required
forquantitative analysis of changes in surface composition.Change in the fraction of the oxidized
component in the spectra of lead and selenium in the processoxidation indicates that the rate of surface
oxidation in wetoxygen is higher than dry. In this case, the ratio of Pb / Se concentrations onsurface
changes slightly.70

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SYNTHESIS, CRYSTALLINE STRUCTURE AND SPECTRALUMINESCENCE OF SALTS OF COMPLEX TETRAKIS-

ACIDS,FORMED BY IONS Eu 3+ AND Tb 3+ WITH ACYLPYRAZOLONESBelousov Yu.A., Semyonov S.N.,
Drozdov A.A., Troyanov S.I.Moscow State University M.V. Lomonosov, Faculty of ChemistryOrganic
luminescent materials have a significant drawback -the large half-width of the lines in the emission
spectra. Unlike them,luminescent complexes of europium and terbium, including those with 4-
acylpyrazol-5-ones,have narrow and highly intense lines in the spectra. [1].In this work, pR4 ] + 3KNO
3Conduct the reaction-alcoholic solution.Prodthe poison of salts of the general formula [NBu 4 ] [Ln (Q
R ) 4 ], where Ln isEu, Tb; R is cyclopentyl (Q 1 ), cyclohexyl. Synthesiscarried out in a water-alcohol
solution according to the general scheme:4HQ R + [NBu 4 ] I + 4KOH + Ln (NO 3 ) 3 = [NBu 4 ]
[LnQRONNOHQ R+ KI + 4H 2 O.I was in waterukta were purified and obtained in monocrystalline
formrecrystallization from ethanol.All compounds were characterized by elemental analysis, IR and H 1
-NMRspectroscopy.According to the data of X-ray structural analysis, the complexes [NBu 4 ] [LnQ 14 ]
isostructural. [NBu 4 ] [EuQ 14 ] crystallizes in the monoclinic system withunit cell parameters a = 23.606
(6) Å, b = 14.469 (2) Å, c = 23.384 (7) Å,β = 100.62 (4) ˚, R = 8.35, Z = 4, space group P 21 / c. The complex
representsis an ionic crystal in which the europium atom is surrounded by eight atomsoxygen, forming a
tetragonal antiprism.The luminescence spectrum of the europium complex contains the most
intenseband at 612 nm, it corresponds to the 5 D 0 - 7 F 2 transition . The most intense streak inthe
spectrum of the terbium complex is at 545 nm ( 5 D 4 - 7 F 5 ). Characteristica feature of the spectra is
the weak Stark splitting of the lines, which is explained byhigh symmetry of the environment of the
lanthanide ion.1.C. Pettinari, R. Pettinari, F. Marchetti, A. Drozdov, I. Timokhin, S. Semenov,and SI
Troyanov // Inorg. Chem. Commun., 2003, v. 6, p. 1423.71

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SYNTHESIS OF HAFNIUM TETRAPIVALATEBelyakov M.V.Moscow State University M.V. Lomonosov, Faculty

of ChemistryRecently, the problem of synthesis of thin amorphous filmsfrom materials with a high
dielectric constant, such as hafnium dioxide.For the synthesis of such films, methods of gas-phase
deposition usingvolatile precursors. For deposition of films of hafnium dioxide, volatilehafnium
compounds with both organic and inorganic ligands. Forobtaining an amorphous film requires not only
the volatility of the precursor, but also itsthe ability to actively interact with water. As a precursor forfor
making films, hafnium carboxylates can be selected. The purpose of the work issynthesis of hafnium
tetrapivalate Hf (Piv) 4 and evaluation of its behavior upon heating invacuum.The proposed approach
involves a two-stage synthesis. In the first stagesynthesis hafnium tetraacetate Hf (MeCOO) 4 was
obtained , and as the initialcompounds were taken stable in air hafnium oxochloride and
aceticanhydride. At the second stage of the synthesis, the resulting acetate was reacted withpivalic acid
to replace acetate groups with pivalate ones. Complete removalacetic acid from the reaction mixture
was achieved by the fact that as a solventm-xylene was taken, which forms an azeotrope with acetic
acid, boiling pointwhich is closest to the boiling point of acetic acid itself. Completesubstitution was
achieved only by taking an excess of pivalic acid. Compositionproducts of both stages of the synthesis
was confirmed by the data of elemental, IR-spectroscopic analysis and PMR spectroscopy.The resulting
Hf (Piv) 4 was subjected to vacuum sublimation at 250 ° and developedgood volatility, sublimation
without decomposition. Due to hydrolysis duringinteraction with water vapor when standing in air
reduces the volatility of the product.72

Page 73
INTERACTION IN THE VANADIUM - TELLURIUM - LEAD SYSTEMVinokurov A.A.Moscow State University
M.V. Lomonosov, Faculty of ChemistryDoping of semiconductor compounds with impurities having
severalcharge states, is an effective method for modifying theirproperties. Lead telluride, when doped
with variable valence elements,acquires fundamentally new electrophysical properties, such as:Fermi
level stabilization, delayed photoconductivity, etc.interest is the process of doping lead telluride with
vanadium, which forms stabletellurides with different charge states of the metal.The conditions for the
production of single-phase vanadium tellurides are found experimentallyVTe 2 , VTe 1.9 , V 3 Te 4 , V 4.64
Te 4 . Triangulation of VTe 1.9 - PbTe, V 3 Te 4 -PbTe and V 4.64 Te 4 - PbTe in the ternary system V-Te-Pb,
at a temperature of ≈570 ° C. Allthe cuts shown turned out to be quasi-binary. Triple connections on the
givenno sections were found. On these samples by the method of differential thermalanalysis
determined the temperature of the eutectics.Found that metallic vanadium is poorly soluble in lead
telluridewhen preparing a mixture for crystal growth. Ligature use suggestedcomposition VTe 10 for
introducing vanadium into PbTe followed by dilution with lead forobtaining the required stoichiometry of
elements in the charge. When fusing elementaryligature components metal vanadium dissolves well in
the melttellurium to form a multiphase product.A PbTe (V) crystal with a pn junction has been grown.
From Hall Effect measurementsthe distribution of the concentration of charge carriers along the length
of the crystal and theirmobility.73

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OXIDATIVE ELECTROCHEMICAL POLYMERIZATIONOF Cu (II) AND Ni (II) COMPLEXES WITH LIGANDS Salpn-
1,3, Salpn-1,2Vovk G.V., Pchelova L.G., Ardasheva L.P., Shagisultanova G.A.Russian State Pedagogical
University. A.I. Herzen,Saint PetersburgThe relevance of the study of thin-layer electrically conductive
electrochromicmetal-containing polymer films on solid carriers due toprospects for the creation on their
basis of sensory, chemotronic, photo- andelectrocatalytic devices, solid-phase light convertersenergy
[1].The report presents and discusses new data characterizing the
conditionselectrochemicalsynthesisstablepolymerelectrically conductiveelectrochromic film systems
based on the complexes [Ni (Salpn-1,3)], [Ni (Salpn-1,2)], [Cu (Salpn-1,3)] and [Cu (Salpn-1,2)] in a
solution of 0.1 M Bu 4 NСlO 4 / CH 2 Cl 2 (CH 3 CN), whereSalpn-1,3 - N, N'-propane-1,3-diyl-bis
(salicylidenimine), Salpn-1,2 - N, N'-propane-1,2-diyl bis (salicylidenimine). A comparative analysis of the
data obtained is carried out.It was found that the change in both the metal center and the ligand
environmentcauses significant differences in the synthesis conditions and properties of the
resultingpolymers. Thus, the most optimal conditions for the synthesis of poly [Ni (Salpn-1,2)],poly [Cu
(Salpn-1,3)] and poly [Cu (Salpn-1,2)] is a potentiostatic mode whenpotential +1.1 V in a CH 3 CN
solution , and for [Ni (Salpn-1,3)] - in a CH 2 Cl 2 solution .The kinetic regularities of the formation of
polymer films have been established.It is shown that with an increase in the thickness of the polymer
film, thethe charge diffusion coefficient and, consequently, the redox conductivity of the polymer.The
electrochemical stability of polymer films was studied depending onpotential, accumulation time and
potential scan interval. Establishedthat the most electrochemically stable and functionally active
arepolymers based on the [Ni (Salpn-1,2)] complex.1. GA Shagisultanova, IA Orlova, ANBorisov // J.
Photochem. Photobiol. A .:Photochem., 1997, v. 1034, p. 249-255.74

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SYNTHESIS AND RESEARCH OF COMPLEX COPPER AND ANTIMONY OXIDESGalimova A.Z.Moscow State
University M.V. Lomonosov, Faculty of ChemistryThe problem of creating a low-consumable anode (MPA)
for the production of aluminumis today one of the most urgent tasks for aluminumindustry. One of the
ways to solve this problem is to studyoxide conductive compounds as materials for ceramic anodes
orprotective coatings for cermets and metal anodes. Complex copper-containingoxides with a trirutile
structure can be considered as similarmaterials.We have synthesized new complex oxides of copper and
nickel with the structuretrirutile of the composition Cu x Ni 1-x Sb 2 O 6 (0≤x≤1). The parameters were
determined by the XRF methodelementary cells of the obtained compounds. It is shown that the volume
of unit cellsincreases slightly with increasing copper content. The LRSA method showshomogeneity of
the samples obtained and their elemental composition was determined. Measurementstemperature
dependence of the resistivity of compounds Cu x Ni 1-x Sb 2 O 6showed that resistance decreases with
increasing copper content, reachingminimum value (0.05 Ohm * m at 900 о С) for CuSb 2 O 6 . This
valuecomparable to the resistivity of the best ceramic samples for MPA.Degradation processes in
cryolite-alumina melt of the sample were investigated.Cu 0.4 Ni 0.6 Sb 2 O 6 in a no-current mode. This
compound has comparablevalues of solubility in cryolite-alumina melt for antimony oxides andnickel in
comparison with the currently investigated materials MRA andoutperforms these materials due to the
lower concentration of copper oxide, whichgives reason to consider copper-containing compounds with
a trirutile structuremost promising for ceramic MPA.In the Cu-Sb-O system, Cu 4 SbO 4.5 compounds
were obtained , the X-ray diffraction pattern of whichwas indexed in monoclinic system with unit cell
parameters:a = 7.174 (2) Å, b = 11.519 (3) Å, c = 6.625 (1) Å, β = 99.56 (2), and "Cu 2 Sb 2 O 7 ",
structurewhich was refined using single crystal data (a = 7.2912 (6) Å, b = 17.4262 (6) Å,gr. P3 1 21, R =
2.20%).75

Page 76

SEARCH AND STRUCTURAL STUDY OF NEW COMPLEXSELENITE-HALOGENIDE REE-SHMGrigoriev

I.I.Moscow State University M.V. Lomonosov, Faculty of ChemistryAmong the oxohalides of REE-Se
composition LnSeO 3 X, it is assumed the presence of twodifferent types of structures for the beginning
and end of the REE series. Connections with Ln = Tb - Ybhave a rhombic system, and for Er and Ho this is
confirmed by the literaturedata [1-3], compounds with Ln = La - Eu presumably have a layereda structure
of the Sillene phase type with a tetragonal system.In this work, an attempt was made to obtain single
crystals of the SmSeO 3 X(X = Cl, Br) in two ways: solid-phase synthesis from a mixture of SmOX powders
andSeO 2 and crystallization from the melt of this mixture using alkaline chloridesmetals as a flux.Solid-
phase synthesis of SmSeO 3 Cl and SmSeO 3 Br was carried out in sealed ampoulesat 300 and 800 ° C.
The reaction products were studied by XRD, which showed thatsamples are multiphase.Crystals were
synthesized from a melt from mixtures of SmSeO 3 Cl and 1.5- and 6.5-multiple excesses of AchMCl,
cooling from 800 to 500 ° C at a rate of 1 ° C per hour. INAs a result, crystals of new phases were
obtained. Experiments usingcations Cs, Rb and K led to the formation of crystals with similarradiographs.
The presence of ions was confirmed by EDX analysisShM in each phase. The use of NaCl as a flux has
resulted ina phase that differs in structure from phases with Cs, Rb, and K. Experiments with Nd instead
of Smshowed that phases similar to samarium are formed.A structural experiment was performed on a
crystal from a SmSeO 3 Cl melt in KCl,as a result of the refinement of which, a structure model was
obtained and it was shown thatthe resulting phase of composition K 28 Sm 44 Se 48 O 144 Cl 64 has a
structure derived fromstructure Sm8 (SeO3) 9Cl6. The paper compares these relatedconnections.1. DG
Shabalin, PS Berdonosov, VA Dolgikh et al // Russ. Chem. Bulletin,International Edition 2003, v. 52, p. 98-
102.2.PS Berdonosov, DG Shabalin, AV Olenev et al // J. Solid State Chem., 2003,v. 174, p. 111-115.3. MS
Wickleder // Z. Naturforsch., 2003, v. 57, p. 1414-1418.76

Page 77

NUCLEOPHILIC ADDITION OF 1,3-DIPHENYLGUANIDINE KORGANONITRIOL COORDINATED TO PLATINUM

(II)Gushchin P.V., Bokach N.A., Kukushkin V.Yu.Saint Petersburg State University, Faculty of ChemistryWe
have previously found that the reactions of nucleophilic addition of amidineNH = C (NHPh) Ph to nitriles
coordinated to Pt (II) and Pt (IV) lead tothe formation of complexes with imidoylamidine ligands.
Complexes with twobidentate coordinated imidoylamidines [Pt {NHC (Ph) NC (Ph) N (Ph)} 2 ] and[Pt
{NHC (CH 2 Ph) NC (Ph) N (Ph)} 2 ],havingflatstructure,possessluminescent properties. Complexes with
ligands of this type can bereceive during the addition reaction and other nucleophiles, for example, 1,3-
diphenylguanidine NH = C (NHPh) 2 . In this case, complexes should formPt (II) and Pt (IV) with
imidoylguanidine ligands.We carried out the reactions of the complex trans- [PtCl 2 (EtCN) 2 ] in a
solutionEtCN with NH = C (NHPh) 2 in a molar ratio of reagents 1: 2 and 1: 4:PtClNClNCCEtEtHN
CNHPhNHPhHN CNHPhNHPhPtClNCEtNNNHEtPhHNPhPtNNHNNHNNNHPhEtPhHNEt- (NH 2 = C (NHPh) 2
) Cl_+-2 (NH 2 = C (NHPh) 2 ) Cl_+42PhPhThe first reaction takes place at 20-25 ° C for 2 days, and the last
atheating to 75 ° C for 2 hours. The resulting compounds wereare characterized by a complex of
physicochemical methods of analysis (elementalanalysis, FAB + mass spectrometry, IR, NMR 1 H, 13 C { 1
H} and 195 Pt spectroscopy, TLC), andtheir structure in the solid phase was studied using the XRD
method.Based on the data obtained, it was found that the reaction of trans- [PtCl 2 (EtCN) 2 ] cNH = C
(NHPh) 2 , proceeds with the addition of guanidine to the coordinated nitrile,followed by the
coordination of the formed imidoylguanidine by the NHPh group to Pt (II)and cleavage of the Cl - ligand .
Thus, the nucleophilic addition of 1,3-diphenylguanidine to nitriles coordinated to Pt (II) is a
pathwaysynthesis of imidoylguanidine complexes of Pt (II).77

Page 78

BEHAVIOR OF GERMANIUM ADMINISTRATION IN LEAD TELLURIDEDedyulin S.N.Moscow State University

M.V. Lomonosov, Faculty of Materials ScienceSolid solutions Pb 1-x Ge x Te - narrow-gap semiconductors,
widelyused in optoelectronics. Understanding the fundamental aspects of behaviorimpurities will allow
you to control the properties of these solid solutions. The purpose of thiswork is the study of the
structural and energy features of impuritycenters - germanium atoms - in lead telluride using X-
rayphotoelectron spectroscopy and ab initio quantum chemical calculations .The results obtained in the
study of the solid solution Pb 1-x Ge x Te (х =0.025, 0.06, 0.07) by X-ray photoelectron spectroscopy
showed thatthat in the spectra of Ge 2p 3/2 and Ge 3d 5/2, in addition to the main component, similar
to the stategermanium in GeTe, additional ones are present.In order to explain the results obtained, a
clustermodeling the volume and surface of crystalline lead telluride within the frameworkhybrid density
functional method B3LYP usingpseudopotential LANL2 with the corresponding two-exponential basis.
Duringcalculations, various variants of the implantation of an impurity Ge atom were analyzedinto a
PbTe crystal.Three options are considered on a cluster simulating the volume of a crystalinclusion of a Ge
atom in c-PbTe - interstitial insertion, Te substitution or substitutionPb. The first two options require
significant energy costs, whilethe third does not lead to noticeable changes in the energy of the system
and, obviously, ispreferred. The cluster simulating the crystal surface hadthe substitution of Ge for Pb in
the first and second layers was considered in order to clarifypossible differences in charge state or
energy for these twononequivalent positions of the Ge atom on the surface. According to the calculation
results,for the two considered variants of the substitution of the Ge atom for the cation, noany
significant differences in both energy and effective chargesGe atoms and atoms of their nearest
environment.78

Page 79

SYNTHESIS AND STUDY OF THE CRYSTALLINE STRUCTURENEW COMPLEX OXIDES Sr 3 YCo 4-x (Fe, Ga) x O
12-yDrozhzhin O.A. 1 , Istomin S.Ya. 2 , Antipov E.V. 2 , Svensson G. 31 Moscow State University M.V.
Lomonosov, Faculty of Materials Science,2 Moscow State University M.V. Lomonosov, Faculty of
Chemistry,3 University of Stockholm, Arrhenius LaboratoryComplex oxides of transition metals with a
perovskite-like structuredue to their electrochemical and catalytic properties attractattention of
researchers as promising materials for oxygen-conductingmembranes and elements of fuel cells.We have
previously studied a compound of the composition Sr 3 YCo 4 O 10.5 (the so-called314-phase) with a
perovskite-like structure (space group I4 / mmm, a = 2a per , c = 4a per ),built of layers connected along
the vertices of CoO 6 octahedra , separated by layers,containing oxygen vacancies [1]. In this work,
solidsolutions of the composition Sr 3 YCo 1-x (Fe, Ga) x O 12-y , x = 0.5-3.5.The compounds were
synthesized by the citrate method. Phase composition and parametersThe unit cells of the obtained
compounds were determined by XRD. Cationicthe composition of the samples was confirmed by the
method of local X-ray spectral analysis(EDX).It was found that for the compositions Sr 3 YCo 1-x Fe x O
12-y , x = 0.5 - 2.0 and Sr 3 YCo 1-x Ga x O 12-y , х = 0.5 - 1.5 (with a step of 0.5), compounds with a 314-
phase structure are formed.The crystal structure of the compound Sr 3 YCo 2 Fe 2 O 10.5 was refined
based onneutron diffraction data. The iron-containing 314 phases were studied atassistance of
Mössbauer spectroscopy. The presence of three differentcoordination environments of iron
cations.According to XRD data, compounds with х = 2.5 and 3.0 in the case of Fe crystallize incubic
system, a = a per , but from the data of electron microscopy highresolution (HREM), it follows that the
crystallites of these substances consist of domainssmall size (<50 Å), within which ordering is
observedoxygen vacancies.1. S.Ya. Istomin, J. Grins, G. Svensson, OA Drozhzhin, VL Kozhevnikov,EV
Antipov, JP Attfield // Chem. Mater., 2003, v. 15, p. 4012 - 4020.79

Page 80

NEW COORDINATION POLYMERS BASED ONFour-core complexes of rhenium and Ln 3+ cationsEfremova

O.A.Novosibirsk State UniversityRecently, much attention has been paid to the problem of
obtainingpolymeric materials with a given set of crystal chemical and othercharacteristics. When
synthesizing such materials, the concept is often usedBuilding blocks that enable the successful
construction of solidbodies with a given dimension and physical and chemical properties. In this work,
inwe used quad-core cluster anionicrhenium complexes [Re 4 Q 4 (CN) 12 ] 4-(Q = S, Se, Te) and aqua
complexes of lanthanides.Due to its ambient character, the CN ligand is able to act asthe bridge between
the rhenium atom on the one hand and the REE cation on the other, resulting inmost to the formation of
polymer compounds.By varying the nature of the cluster anion [Re 4 Q 4 (CN) 12 ] 4- (Q = S, Se, Te) and
Ln 3+ , wecoordination polymers of various compositions and dimensions were obtained.
Connectionstype [{Ln (H 2 O) 5 } 3 {Re 4 Q 4 (CN) 12 } 2 ] Cl 2 ⋅ x H 2 O (Q = S, Se), having a framework
structure,are realized for the La 3+ - Gd 3+ cation series . Compounds with a general formula(Kat) [{Ln (H
2 O) 4 } Re 4 Q 4 (CN) 12 ] ⋅ x H 2 O (Q = S, Se; Kat = K + , H 3 O + ; Ln = Tb 3+ - Lu 3+ )
crystallizeinstructurelayered type. Row cationsSm 3+ - Lu 3+ when interacting withclusteranion[Re 4 Te 4
(CN) 12 ] 4-formconnectionscomposition(H 3 O) [{Ln (H 2 O) 6 } Re 4 Te 4 (CN) 12 ] ⋅ x H 2O, having a
chain structure.In chain-type connectionsdiscoveredinterestingmagnetic properties (Fig.).80

Page 81

STRUCTURAL TRANSITION IN BROWNMILLERITE-LIKE SOLIDSSOLUTIONS Ca 2 Ga x Al 1-x MnO

5Kalyuzhnaya A.S., Abakumov A.M., Rozova M.G., Antipov E.V.Moscow State University M.V. Lomonosov,
Faculty of ChemistryMn-containing brownmillerites are considered promisingstructural matrix for
creating new magnetoresistive materials. Ca 2 AlMnO 5[1] and Ca 2 GaMnO 5 [2] have similar structures
differing in spatialsymmetry ( I 2 mb and Pnma ) due to different ordering of "left" and "right"
chainstetrahedra BO 4 (B = Al, Ga). We have carried out the synthesis and study of solid solutionsCa 2 Al
x Ga 1-x MnO 5methods of radiography and transmission electronmicroscopy. The samples were
synthesized by the ceramic method from stoichiometricquantities of CaCO 3 , Mn 2 O 3 , Al 2 O 3 and Ga
2 O 3 by annealing in an Ar flow at 1000º - 1250ºC.Substitution of Al for Ga leads to the transition from
the Pnma structure (x ≤ 0.5) to the I2mb structure(x> 0.5). In the crystal structure of Ca 2 Ga 0.5 Al 0.5
MnO 5, the amounts of "left" and"Right" tetrahedral chains are in a ratio of ≈ 2: 1, in contrast to the 1: 1
ratio instructure Pnma and 1: 0 in structure I 2 mb . Transition from the Pnma structure to the I 2 mb
structureassociated with an increase in the number of defects - antiphase boundaries with a shear
vector R =1/2 [111], parallel to the plane (010), because of which instead of alternating "left" andOf
right-handed chains in the initial Pnma structure , neighboring layers of tetrahedra appear withchains of
the same type. As the number of antiphase boundaries increases with increasingthe Al content, domains
of the I2mb structure are formed and a structuraltransition, since the shift vector R = 1/2 [111] is the
translation of the unit cellphases I2mb . It can be assumed that the nature of the ordering of the chains
of Ga (Al) tetrahedra -O 4 in brownmillerites is determined by dipole-dipole interactions betweenchains.
The dipole moment of the tetrahedral chain arises from cooperativedisplacements of atoms in the Ga
(Al) O layers, with the "left" and "right" chains corresponding toantiparallel vectors of dipole moments.
Stabilization of one or anotherthe variant of ordering tetrahedral chains is determined by the possibility
of mutualcompensation of dipole moments, which depends on the displacement of atoms intetrahedral
chains and the distance between the Ga (Al) O layers.1. AJ Wright et al // J. of Materials Chemistry, 2002,
No. 12, p. 978-982.2. AM Abakumov et al // J. of Solid State Chemistry, 2001, No. 11, p. 110-111.81

Page 82

A NEW APPROACH TO SYNTHESIS OF NITROSONIUM SALTSKovalev S.V.Moscow State University M.V.

Lomonosov, Faculty of ChemistryNitrosonium salts are of interest as convenient reagents forobtaining
anhydrous salts, such as nitrates, as well as the synthesis of nitroso compounds inorganic chemistry.
However, the known methods for the preparation of nitrosonium salts are usuallyassociated with the use
of nitrosyl halides and require a rather complicatedexperimental execution. The purpose of this work
was to studythe possibility of synthesizing nitrosonium salts by keeping nitric acid solutions of a
numberacids in a desiccator over phosphoric anhydride.In the developed method, the synthesis is
carried out under reduced pressure indesiccator over P 2 O 5 . Anhydrous is used as a source of NO +
cations.nitric acid. Phosphoric anhydride is used to bind the formed inthe reaction conditions of water
and the production of nitrogen oxides N 2 O 4 and N 2 O 5 , playinga key role during synthesis. To
improve the conditions for the crystallization of saltsnitrosonium as a solvent, anhydrous acetic acid can
be used.The following acids were used as starting reagents: iodic,sulfuric, phosphoric, and para-
toluenesulfonic (TsOH). Identificationof the resulting compounds was carried out by XRD and IR
spectroscopy. AvailabilityNO + was confirmed by chemical methods (hydrolysis, reaction with KI).It was
shown that, under these conditions, nitrosonium salts form only strongnon-volatile acids. In the case of
HIO 3, no changes were observed. In the system with phosphoricacid formed a viscous solution
containing nitrogen oxides in, from whichanhydrous H 3 PO 4 crystallized . In the case of H 2 SO 4 , a
single-phasecrystalline sample of nitrosonium hydrogen sulfate NOHSO 4 .Keeping the nitric acid
solution TsOH over P 2 O 5 for 4 weeksled to the crystallization of a previously unknown 4-methyl-3,5-
dinitrobenzene sulfonatenitrosonium. Its structure was established by 1 H NMR and XRD methods .
Thusthe possibility of not only obtaining nitrosonium salts, but also nitration is shownorganic
compounds under these conditions.This work was supported by the Russian Foundation for Basic
Research, grant 04-03-32734.82

Page 83

HETEROMETALLIC CUBAN CLUSTERS [Mo 3 (MCl) Q 4 (H 2 O) 9 ] 3+(M = Pd, Ni; Q = S, Se):

REACTIVITYKovalenko K.A.Novosibirsk State University, Faculty of Natural SciencesCluster aqua
complexes with a cuban heterometallic framework[Mo 3 (MCl) Q 4 (H 2 O) 9 ] 3+ (M = Pd, Ni; Q = S, Se)
are readily available and stableconnections. Clusters show unusual reactivity inin relation to a number of
phosphorus-containing compounds. They cause isomerizationphosphorous ((HO) 2 P (O) H) and
hypophosphorous ((HO) P (O) H 2 ) acids, as well as theirphenyl-substitutedPh 2 P (O) HandPh (HO) P (O)
Hinthe correspondingthree-coordinated tautomers that are stabilized by atom coordinationpalladium
due to the liberated lone pair on the phosphorus atom. Method 31 PNMR in solutions proved the
formation of complexes with three-coordinatedtautomeric forms. Structure {[Mo 3 (NiP (OH) 3 ) S 4 (H 2
O) 8 Cl] CB [6]} Cl 3 13H 2 Odetermined by X-ray structural analysis. The driving force behind the
reactions is the high affinity of atomsNi and Pd to soft donors - phosphorus atoms. It is well known that
the P – O–H is unstable with respect to tautomerization in H – P = O. Equilibrium constants inaqueous
solutions are very small (~ 10 –11 ). However, isomerization is postulated inas the first stage in the
coordination process.It was determined spectrophotometrically that the rate of
coordinationphosphorous acid at the palladium atom for a selenium-containing cluster by 25 timesmore
than for sulfur. Coordination of phosphorous acid to nickelclusters occurs at an appreciable rate only
when heated to 50–60 ° C.Thus, the reactivity increases when going from nickel topalladium and from
sulfur to selenium. Analysis of the 31 P NMR spectra gives the following seriesactivity of phosphorus-
containing molecules:H 3 PO 2 > Ph 2 P (О) H> Ph (HO) P (О) H >> H 3 PO 3When keeping solutions of
palladium clusters with hypophosphorousacid by 31 P NMR spectra, it is easy to observe its oxidation to
phosphorous andphosphoric acid. In this case, palladium clusters act asprocess catalysts.83

Page 84

SYNTHESIS, CRYSTALLINE STRUCTURE AND PROPERTIES OF NEWCOMPLEX OXIDES LnCrGeO 5 (Ln = Nd -

Er, Y)E. S. KondakovaMoscow State University M.V. Lomonosov, Faculty of ChemistryNew complex oxides
LnCrGeO 5 (Ln = Nd - Er, Y) were obtained by annealingstoichiometric mixtures of oxides Ln 2 O 3 , Cr 2 O
3 and GeO 2 for 60 hours attemperature of 1280 ° C. All compounds are isostructural and crystallize in
the rhombicsystem (space group Pbam) with close parameters of unit cells. Connectionsinvestigated by
methods of X-ray structural analysis and electron microscopy, andalso determined the temperature
dependences of the magnetic susceptibility andheat capacity.The structures for all new phases were
refined by the Rietveld method. They containrutile-like chains of Cr +3 O 6 octahedra connected through
opposite edges, andelongated along the c axis . The Cr-Cr distances in the chain are noticeably different:
2.79 Å and 2.94 Å,but become close as the ionic radius of the REE cation decreases. Axialthe lengths of
the Cr-O bonds approach the equatorial ones also ata decrease in the radius Ln 3+ . The chains are
interconnected through structural groupsGe 2 O 8 . These groups are formed by two squares connected
through a common edge.pyramids GeO 5 , the tops of which are directed in opposite directions.The
resulting three-dimensional skeleton contains pentagonal tunnels, in whichthe REE atoms are located.
Electron diffraction and high microscopy datapermits confirmed the structural results obtained.
Subtractionintrinsic magnetic moments of Nd 3+ and Sm 3+ made it possible to calculate the
contribution of cationsCr 3+into the magnetic properties of these compounds. Short distance 2.78
Å,comparable to the distance in the metal, explains the noticeable dimerizationinteractions, as a result
of which Cr 3+ ions form alternating S = 3/2spin chains.84

Page 85

STUDY OF THE BOUNDARY OF THE YSZ - LaSrCuO 4-δ METHODLOCAL PROBE MICROANALYSISLezhepekov
A.V., Savvin S.N.Moscow State University M.V. Lomonosov, Faculty of ChemistryAt present, the object of
attention of researchers is perovskiteoxide materials with high mixed (electronic and ionic)
conductivity,since they are promising for use as cathodeshigh-temperature fuel cells, oxygen
concentration sensors, andalso as electrocatalytically active membranes with selectiveoxygen
permeability.Cuprate-based materials have high electrical conductivity.It is known that at a low
strontium content (x = 0.15, 0.30), the La 2-x Sr x CuO 4-δ phasesexhibit a metallic type of conductivity,
and with a significant increasecontent of strontium, the number of anion vacancies increases, which
allowsexpect the mobility of oxygen in the structure and the reversibility of the electrode based onof
these phases for oxygen. However, it was found that in the case of manganites La 1-x Sr x MnO 3-δan
insulating layer of zirconate may form on the electrode-electrolyte interfaceLa, which prevents the rapid
transfer of oxygen. Thus, the purpose of thiswork was the synthesis of cuprate LaSrCuO 4-δ , preparation
of dense symmetricelectrochemical cells LSCO⏐YSZ⏐LSCO (YSZ = ZrO 2 with the addition of 8 mol% Y 2 O
3 ) andstudymicrostructuresandchemicalcompositionboundariessection LaSrCuO 4-δ ⏐YSZ.Synthesis of
cuprate LaSrCuO 4-δcarried out by the ceramic method in air.According todataXRFwasreceivedsingle
phasesample(a = 0.3762 (3) nm, c = 1.326 (1) nm). Isostatic hot pressinga symmetric cell LaSrCuO 4-δ |
YSZ | LaSrCuO 4-δ was prepared , representingis a tablet with a diameter of 9 mm and a thickness of
each layer ≈1 mm. Throughlocal probe microanalysis, it was found that mutual diffusionthe components
of the electrode and electrolyte does not occur and the cationic
compositionsynthesizedcupratalanthanum-strontiumanswersratioLa: Sr: Cu = 1: 1: 1 cations.85

Page 86

NEW COMPLEX COBALT OXIDES Ba (Co 1-x Y x ) O 3-y (0.15 <x <0.33)Lomakov M.V., Istomin S.Ya., Antipov
E.V.Moscow State University M.V. Lomonosov, Faculty of Materials ScienceOxygen-deficient complex
oxides of cobalt and iron with perovskite-likestructure attract the attention of researchers as
promisingmaterials for obtaining oxygen-conducting membranes, electrodes for fuelcells, etc.Samples Ba
(Co 1-х Y х ) O 3-y (0.05 <x <0.4) were obtained in air at a temperature1100 about C using the citrate
synthesis method.X-ray phase analysis showed that the samples Ba (Co 1-x Y x ) O 3-y (0.15 <x
<0.33)have a cubic perovskite structure, the parameter a of which varies from 4.1299 (3) Åup to 4.1804
(3) Å. Samples Ba (Co 0.95 Y 0.05 ) O 3-y and Ba (Co 0.9 Y 0.1 ) O 3-y are non - single - phase and
containimpurity of a hexagonal phase of unknown composition. In the Ba (Co 0.6 Y 0.4 ) O 3-y sample, in
addition tothe main cubic phase contains an impurity Y 2 O 3 .Single-phase samples were studied using
electron diffraction, inas a result, cubic symmetry was confirmed. The presence of stripesdiffuse
intensity in electron diffraction images indicatesthe presence of local ordering of B-cations and / or O-
vacancies.It was found that as a result of annealing at a lower temperature thansynthesis temperature,
decomposition of Ba (Co 1-x Y x ) O 3-y occurs .The iodometric titration method for single-phase samples
wasestablishedcontentoxygen:BaY 1/3 Co 2/3 O 2.55 ,BaY 0.25 Co 0.75 O 2.55 ,BaY 0.15 Co 0.85 O
2.51 .The oxygen permeability was measured for a BaY 1/3 Co 2/3 O 2.55 sample at
varioustemperatures. The measurements were carried out on a tablet 12 mm in diameter and1.5 mm In
thermostatic mode, it was 6.4 * 10 -8 mol / cm 2 / sec at 850 о С and1.4 * 10 -7 mol / cm 2 / sec at 950 o
C. With slow heating to 950 o C, the value is reached1.1 * 10 -7 mol / cm 2 / sec. The calculated value of
the activation energy is 39.9 kJ / mol.86

Page 87

STEREOISOMIC Pt (II) AND Pd (II) COMPLEXES WITH SERINEMatveeva L.M.Novosibirsk State

UniversityInterest in amino acids as ligands is due not only to their biologicalrole (amino acids are the
constituent parts of proteins), but also a variety of typescompounds formed by these polyfunctional
ligands with transitionmetals.In this work, synthesis routes are developed and solid phases are
isolated.individual stereoisomeric complexes of Pt (II) and Pd (II) with hydroxyamino acid -serine (SerH =
HOCH 2 CH (NH 2 ) COOH) of two types: [M (Ser) 2 ] (I) and [M (SerH) 2 Cl 2 ] (II),where M = Pt, Pd. In
complexes of type (I), the serinate - ion is coordinated bidentately throughNH 2 - and OCO - groups, and
in complexes of type (II) serine is monodentateligand, coordinated only through the NH 2 -
group.Synthesized compounds: cis-, trans- [Pt (S-Ser) (R-Ser)] (1,2), trans- [Pt (S-Ser) 2 ] (3), cis- [Pd (S-
Ser) 2 ] (4), trans- [Pd (S-Ser) (R-Ser)] (5) - complexes of type (I), and trans -[Pt (S-SerH) (R-SerH) Cl 2 ],
trans- [Pt (S-SerH) 2 Cl 2 ], trans- [Pd (S-SerH) (R-SerH) Cl 2 ] -complexes of type (II) (R, S are absolute
configurations of an asymmetric atomcarbon). Complexes (1) - (8) were investigated by IR and NMR
spectroscopy (onnuclei 1 H, 13 C, 195 Pt).NMR spectroscopic data of solutions of complexes
allowidentify not only geometric isomers, but also diastereomers. IR-spectra of solid samples confirm
the coordination of ligands through NH 2 - and OCO-groups in complexes of type I and through the NH 2
-group in complexes of type II.For one of the bischelates trans- [Pt (S-Ser) (R-Ser)], X-ray
diffractiondata.The research findings presented in the report include not onlydescription of the synthesis
and identification of new stereoisomeric complexes Pt (II) and Pd (II)with hydroxyamino acid - serine, but
also data on antitumor activityone of the diastereomeric Pt (II) bischelates obtained at the Institute of
ImmunologySB RAS.87

Page 88

STRUCTURAL AND CHEMICAL MECHANISM OF FORMATIONCOMPLEX OXIDE NdSr 2 Mn 2 O 7Missul

A.B.Saint Petersburg State UniversityComplex oxides containing both Mn 3+ and Mn 4+ ions are
currentlytime is being actively studied, which is associated with the effect of colossalmagnetoresistance.
An important class of these substances are layeredperovskite-like oxides, for which in many cases it is
possible to obtain the bestcharacteristics than for oxides with the structure of perovskite itself, forwhich
the effect of colossal magnetoresistance was discovered for the first time.To understand the formation of
such structures, it is necessary to take into account thatperovskite-like oxides are usually synthesized
from several (at least three)starting materials that, for topological reasons, cannot reactat the same
time. Thus, the formation of such oxides is multistage.a process in which relatively simple structures are
initially formed,which subsequently interact with each other to form the finalproduct.This work presents
the results of studying the process of formation of the oxideNdSr 2 Mn 2 O 7 , belonging to the
Ruddlesden-Popper phases A n + 1 B n O 3n + 1 (n = 2), from oxidesneodymium and manganese, as well
as strontium carbonate. The synthesis was carried out at a temperature1200 ° C, the composition of the
reaction mixture was determined by X-ray phase analysis intime interval 3 ÷ 24 hours after the beginning
of calcination.As a result of the work, intermediate products of the studied reaction were
determined.Based on this information and data obtained earlier [1] on the mechanismthe formation of
aluminates of a similar structure for the reaction was proposedstructural and chemical mechanism and
the limiting stage is established.The conclusions obtained in the study of aluminates on the preferability
offor the formation of the Ruddlesden-Popper phases at n = 2 mechanism, includingthe formation of
structures such as perovskite and K 2 NiF 4 (also related to this type), inthe case of their stability under
the conditions of synthesis.This work was supported by the Russian Foundation for Basic Research
(project No. 04-03-32176).1. I.A. Zvereva et al. // J. Society. chemistry, 2001, vol. 71, p. 1254-1258.88

Page 89

CONNECTIONS OF METAL COMPLEXES INKUKURBIT [8] URILMitkina T.V.Novosibirsk State UniversityStudy

of compounds of inclusion of metal complexes in macrocycliccavitands are a new and rapidly developing
area of supramolecular chemistry.Cucurbit [n] urils (CB [n]) (C 6n H 6n N 4n O 2n ) (n = 5 ÷ 10) are a
classmolecules with a large rigid hydrophobic inner cavity (diameter 8.8 Å forn = 8), capable of
encapsulating different guests of suitable size, likecationic and neutral.The purpose of our work is to
synthesize and study the reactivityinclusion compounds CB [8], in which Ni II complexes act as guests ,Cu
II , Co III with ethylenediamine, diethylenetriamine and cyclam.An inclusion compound of a complex of
nickel with cyclam incucurbit [8] uril {[Ni (cyclam)] @ CB [8]} Cl 2 ⋅16H 2 O (1) , stable in crystallinephase
and in aqueous solution, which is confirmed by RStA, IR- and ESP 1 .In the direct interaction of CB [8]
with trans - [M (en) 2 X 2 ] n + (M = Ni II , Cu II , Co III ; X =Cl - , H 2 O), a number of inclusion compounds
were isolated, which were characterized by XRD methods,ESI-MS, IR, ESP, 1 H-NMR and EPR
spectroscopyproves the existence of guest complexeshost both in solid phase and in solution.The
reaction of selectiveswitching on trans - [Co (en) 2 Cl 2 ] +in CB [8] from a mixture of cis and trans
isomers, withsubsequent isolation { trans - [Co (en)2Cl2] @CB [8]} Cl · 17H2About .Synthesized inclusion
compound stoichiometry guest: host = 2: 1 composition{[Cu (dien) (4,4'-bipy) (H 2 O)] 2 @ СB [8]} (ClO
4 ) 4 · 11H 2 O (2) when treated with 1 excesscomplex Cu II . According to RStA, 2 belongs to a new type
of connections"metal complex inside CB [8]", in which metal atoms are located outside the cavityCB [8],
and two 4,4'-bipy ligands are encapsulated inside the host.1. T.V. Mit'kin et al. // Izv. AN, Series of Chem.,
2004, No. 11, p. 2414-2419.89

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SYNTHESIS AND STUDY OF TIN (II) PYROPHOSPHATE Sn 2 P 2 O 7Mityaev A.S.Lomonosov Moscow State
University, Faculty of ChemistryTin pyrophosphate Sn 2 P 2 O 7 attracts the interest of researchersdue to
the prospect of its use as an anode in lithium sourcescurrent. In the course of this work, the crystal
structure of twomodifications Sn 2 P 2 O 7 .VolumetricsamplescharacterizedmethodsMössbauer
spectroscopy and DTA.X-raycleansample Sn 2 P 2 O 7receivedheatingstoichiometric mixture of SnO and
NH 4 H 2 PO 4 in a dynamic vacuum for 24 hoursat a temperature of 550 ° C. Colorless single crystals of
Sn 2 P 2 O 7 for X-ray diffractionanalyzes were obtained by keeping the sample at 580 ° C for a month.The
low-temperature modification β -Sn 2 P 2 O 7 crystallizes in the triclinic system withunit cell parameters a
= 5.2776 (5) Å, b = 11.5413 (12) Å, c = 11.6360 (12) Å,α = 102.911 (8) °, β = 99.303 (8) °, γ = 98.899 (8) °
( V = 668.2 (3) Å 3 , Z = 4). Structure β -Sn 2 P 2 O 7 contains isolated pyrophosphate groups [P 2 O 7 ] 4- ,
and tin atomsare located at the apex of triangular pyramids of oxygen atoms. Undividedthe electron pair
of tin (II) complements its coordination environment topseudotetrahedron. The position of the lone pair
is determined by calculationelectronic localization functions (ELF). On the Mössbauer spectrum, in
addition to the doubletof divalent tin, there is a low-intensity peak Sn +4 , related toapparently, to the
impurity amorphous phase. Isomeric shift for Sn +2δ = 3.37 (2) mm / s corresponds to hybridization 5s
1.4 5p 0.6 .Sn 2 P 2 O 7is undergoingreversiblephasetransitionat 370 ° C.The high-temperature
modification ( α -Sn 2 P 2 O 7 ) has a monoclinic cell withparameters α = 7.177 (2) Å, b = 9.286 (2) Å, c =
5.289 (1) Å, β = 106.05 (1) ° (V = 339.3 (2)Е 3 , Z = 2). The structure of α -Sn 2 P 2 O 7 was solved ab-initio
using high-temperature powderX-ray data (space group P2 1 / n). The main difference between high
temperaturemodifications - the equivalence of phosphate tetrahedra of the pyrophosphate group [P 2 O
7 ] 4-and, as a consequence, the appearance of an inversion center in the α - Sn 2 P 2 O 7 structure .90

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NEW COORDINATION CONNECTIONS OF 3d-METALS WITHPOLYDENTATE OXYME-CONTAINING SHIFF

BASESMoroz Yu.S., Fritskiy I.O. Sliva T.Yu.Kiev National University. T. ShevchenkoA new polydentate ligand
(2E) - (oximino) -N`- (1- (pyridine-2-yl) methylidene) propanohydrazide (POP), on the basis of which the
seriescoordination compounds with 3d-metal salts.Complexing properties of the newligand in aqueous
solutions were studied by methodspH potentiometry, spectrophotometry andEPR. Formation constants
calculatedcomplexes,researcheddistributioncomplex particles depending on pHsolution. The identity of
the synthesized coordination compounds wasconfirmed by elemental and X-ray phase analysis, ESI
massspectrometry. The complexes were investigated using IR, NMR-EPR and electron spectroscopy, and
polynuclear compounds - also bymeasurements of static magnetic susceptibility on the SQUID
magnetometer.POPROR tends to form both mono- and
polynuclearcomplexes,whatconfirmedresultsmass spectrometryandX-ray
structuralanalysisthreecoordinationconnections:[Ni 4 (POP-H) 4 (HCOO) 4 ] • 9H 2 O, [Co (POP-H) 2 ] NO
3 and [Zn (POP) Cl 2 ] ⋅H 2 O. Coordinationthe number of central atoms is 6 (Co, Ni) and 5 (Zn). In the
tetranuclear complex, the ligandscoordinated with the formation of three chelate cycles with the
participation of the oxime,azomethine, pyridine nitrogen and carbonyl oxygen.Molecular structure of [Ni
4 ( POP -H) 4 (HCOO) 4 ] 9H 2 O91

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NEW LAYERED BISMUTH OXOHALOGENIDES IN SYSTEMSPbO - BiOX - CuX (X = Cl, Br, I): SYNTHESIS AND
CRYSTALLINESTRUCTUREMoskvin D.N., Glushkov K.V.Moscow State University M.V. Lomonosov, Faculty of
ChemistryBismuth compounds with layered structures are intensively studied in connection withthe
variety of their applied properties and the richness of structural chemistry. Forobtaining compounds with
given structures and properties, knowledge is importantthe relationship between the features of
structural fragments and the resulting (orcombinations) of properties. Therefore, the search for new
structural units, the studytheir features (nonstoichiometry and boundaries of solid solutions, their
dependence onsynthesis conditions, combination with other elements, etc.).In this work, new complex
bismuth oxohalides withstructures derived from the well-known ionic conductor LaOAgS. In systemPbO,
BiOCl, CuCl at 500 - 600 ° С, five new compounds with stronglya crystal structure defective for Cu + ions :
1 . Pb x Bi 2 - x O 2 Cu x Cl 2 ( х ≈ 0.35 - 0.75 at 500 ° С), structural type LaOAgS. When600 ° C the upper
limit does not change, but at small x a compound with a new one is formed,not yet known structure
( 2 );3 . Pb 1+ x Bi 3- x Cu x O 4 Cl 3 ( x ≤ 0.7 at 600 ° С), structural type anti- La 3 O 2 Ni 4 P 4 ;4 . Pb x Bi
2- x Cu 1+ x O 2 Cl 3 ( x = 0.4 - 0.7 at 600 ° С), the probable structure of anti -Bi 2 YO 4 Cu 2 Se 2 ;5 . Pb x
Bi 4- x Cu 1+ x O 4 Cl 5 ( х = 0.5 - 0.7 at 600 ° С), the probable structure of intergrowth onbased on BiOCl
and 4 .Analogs of solid solutions 1 and 3 were obtained with other halogens: Br ( 1 and 3 ) and I(only 1 ),
while the region of homogeneity of solutions of type 1 narrows from oxochloridesand oxobromides (0.3
<x <0.7) to oxioiodide (0.3 <x <0.5).The Rietveld profile analysis method refined the details of the
crystalstructures Pb 0.6 Bi 1.4 Cu 0.6 O 2 X 2 (X = Cl and Br): P 4 / nmm , Z = 1, a = 3.9469 (1) Å, c =
8.2914 (2) Å,R p = 0.107, χ 2 = 1.50 (Cl); a = 3.9787 (1) Å, c = 8.8346 (2) Å, R p = 0.119, χ 2 = 1.60 (Br).The
existence of type 1 - 5 isostructural series is predicted with substitution of Bi 3+ notonly on Pb 2+ , but
also Ca 2+ - Ba 2+ , ½ (Li + + Bi 3+ ), ½ (Na + + Bi 3+ ), etc., the firstrepresentatives of some of them.92

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PHOTOLUMINESCENT PROPERTIES OF BENZODIOXANEβ- AMINOKETONES AND THEIR COMPLEXES WITH

ZINCMuralev A.E.Moscow State University M.V. Lomonosov, Faculty of ChemistryInterest in organic and
coordination compounds withphotoluminescence in the blue region of the spectrum is associated with
the search for newelectroluminescentmaterials.Amongconnections,possessingluminescence in the blue
region of the spectrum, zinc complexes with organicligands. Complexation, in this case, allows you to
changeluminescent properties of the ligands themselves, shifting their emission band toshortwave
region.In this work, the objects of study were selectedbenzodioxane β-amino ketones (RBAK) containing
various chemicalnature substituents (Fig. 1).OONH 2ORFigure: 1. Benzodioxane β-amino ketones (R = C 6
H 5 , CH (CH 3 ) 2 , C 3 H 8 , C 2 H 5 )Ligands were obtained according to the method [1] and
characterized by Н 1 NMR,UV spectroscopy and photoluminescence. These compounds were found to
emitin the blue region of the spectrum (λ = 460 nm). Moreover, the luminescence intensitysolutions of
ligands increases with a change in R in the series C 6 H 5 <CH (CH 3 ) 2 <C 3 H 8 <C 2 H 5 .As a model
compound with the most intense luminescence forEtBAK (C 2 H 5 BAK) was chosen for the preparation
of complexes with zinc .The complexes Zn (CF 3 COO) 2 * EtBAK and Zn (CH 3 COO) 2 * EtBAK were
obtained. INsolution, the luminescence spectra of the complex and the ligand are practically the same,
whichindicates an extremely weak complexation. However, in the spectrum of solidcomplex Zn (CF 3
COO) 2 * EtBAK detected luminescence in the green part of the spectrum.Thus, we can conclude about
the formation of weak data complexesligands and zinc, unsuitable as blue electroluminescent
materials,which, however, does not diminish interest in the ligands themselves.1. S.S. Mochalov, A.V.
Kosynkin et al. // KhGS, 1994, No. 5, p. 601-607.93

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DESIGN OF COORDINATION POLYMERS WITH ZEOLITE-LIKEBUILDINGMukha Yu.P.Kiev National University.

T. ShevchenkoSynthesis of three-dimensional coordination polymers with a microporous structureis
promising for the creation of materials with valuable ion-exchange,adsorption and catalytic properties
[1].As a ligand for the synthesis of coordination polymers, 3,4-diacetylhexanedione-2.5 (H 2 L).
Combining a non-planar bischelate ligandwith traditionally bridged 4,4'-bipyridine (bipy) can lead to the
formationlarge spiral fragments instead of loop closure, as is the case withflat bischelate ligands
[2].OOOMNOMNNNA number of compounds with the composition [ML (bipy)] and [M 2 A 2 L (bipy) 2 ]
have been synthesized and studied .(M = Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Cd 2+ ; L = 3,4-
diacetylhexanedione-2.5; A - = Cl - , NCS - , OAc - ,NO 3- , ClO 4- ).Compound with the composition [Cu 2
(NO 3 ) 2 L (bipy) 2 ] was studied by X-ray diffraction analysis. At the expense ofnon-planar structure of
the ligand (L), the formation of giantspiral formations of 12 copper atoms in one turn. The structure is
observedformation of a three-dimensional coordination polymer with a pore diameter of about 24
Å.Four identical networks are intertwined, which significantly reduces pore size.1.C. Janiak. // J. Chem.
Soc., Dalton Trans., 2003, p. 2781-2804.2. R. Robson. // J. Chem. Soc., Dalton Trans., 2000, p. 3735-
3744.94

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SYNTHESIS AND STUDY OF SOLID SOLUTIONS Ba 1-x Sr x Fe 2 O 4(0 ≤ x ≤ 0.4) WITH TRIDIMITE-LIKE
STRUCTURENikolaev I.V. 1 , Abakumov A.M. 1 , Vasiliev A.N. 21 Moscow State University M.V.
Lomonosov, Faculty of Chemistry,2 Moscow State University M.V. Lomonosov, Faculty of PhysicsBarium
monoferrite BaFe 2 O 4 has the structure of filled tridymite, in which,depending on the synthesis
conditions, different orientations of FeO 4 tetrahedra are realized ,connected through the tops. Barium
cations fill the channels in the framework,formed by FeO 4 tetrahedra . The possibility of realizing non-
centrosymmetricstructure (modification T> 1000 ° C with space group Bb2 1 m [1]), and a strong spin-
spinthe interaction between neighboring Fe 3+ cations allows us to consider thismaterial as a potential
multiferroic, where mutualinfluence of magnetic and dielectric properties. The purpose of this work
isstudy of the influence of the average radius of the A-cation on the character of distortiontridymite-like
structure of barium monoferrite.The synthesis of the samples was carried out in quartz ampoules at a
residual pressure of 10 -2mbar at 1100 ° C for 130 - 150 hours. As starting materialsused BaO, SrO and Fe
2 O 3 . Single-phase samples of solidsolutions of Ba 1-x Sr x Fe 2 O 4 with x = 0, 0.1, 0.2. For x> 0.2, the
samples contain an impurityBaSrFe 4 O 8 . The Ba 1-x Sr x Fe 2 O 4 solid solutions have the structure
BaFe 2 O 4 with space group. Bb2 1 m.The values of the parameters of the unit cells naturally decrease
with increasingstrontium content from a = 19.056 (3), b = 5.381 (2), c = 8.447 (4) for x = 0 toa = 19.039
(2), b = 5.371 (6), c = 8.427 (8) for x = 0.2For samples with x = 0, 0.1, 0.2, the dependences of the
magnetic susceptibilityand heat capacity versus temperature. The curves obtained show a sharpdecrease
in the value of the magnetic susceptibility for the composition with x = 0 at 60 K in 4times, for x = 0.1 at
100 K by 8 times, for x = 0.2 at 120 K by 12 times. The resulting curvesfor specific heats do not show the
presence of phase transitions at the giventemperatures.1. H. Mitsuda, S. Mori, C. Okazaki. // Acta
Crystallogr., 1971, v. B27, p. 1263.95

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OBTAINING AND PROPERTIES OF NEW NITRATE COMPLEXESV And Mo: VO (NO 3 ) 3 , Cs [VO 2 (NO 3 ) 2 ],
MoO 2 (NO 3 ) 2 , Cs [MoO 2 (NO 3 ) 2 ]Palamarchuk D.V. 1 , Morozov I.V. 2 , Troyanov S.I. 21 Moscow
State University M. V. Lomonosov, Faculty of Materials Science,2 Moscow State University M.V.
Lomonosov, Faculty of ChemistryBy keeping nitric acid solutions in a desiccator over P 2 O 5 ,
andoxonitrate complexes were studied by X-ray diffraction analysisvanadium (V) and molybdenum (VI).
To obtain nitrate complexes of vanadiummetallic vanadium was dissolved in anhydrous HNO 3 . The
resulting solution was placedinto a desiccator with P 2 O 5 . In the second experiment, an excess
ofcesium nitrate. After 2-3 weeks in the first experiment,oily yellow liquid hydrolyzing in air. IC
comparisonspectrum, boiling point and other properties of the resulting substance withliterature data
allowed us to conclude that this liquid is trinitratevanadyl VO (NO 3 ) 3 . In the second experiment,
hygroscopic goldencrystals. X-ray structural analysis of the obtained substance showed that a previously
unknownCs [VO 2 (NO 3 ) 2 ]. The crystal structure of Cs [VO 2 (NO 3 ) 2 ] consists of Cs + andinfinite
oxonitrate vanadate anions having a chain structure [-VO (NO 3 ) 2 -O-] nn- . Based on the data obtained
and data known fromliterature, a scheme of VO (NO 3 ) 3 hydrolysis is proposed .To obtain derivatives of
molybdenum oxonitrate as starting materialsthe compounds used ammonium paramolybdate and
molybdenum (VI) oxide. In the secondIn this case, cesium nitrate would be added to the solution. As a
result of aging in a desiccatorover P 2 O 5 in both cases, crystallization of colorless crystals occurred,
rapidlydim in air. RStA showed that in the first case dioxonitrate was obtainedmolybdenum MoO 2 (NO
3 ) 2 , in the second, previously unknown Cs [MoO 2 (NO 3 ) 3 ].The crystal structure of MoO 2 (NO 3 ) 2
consists of endless zigzagchains coinciding in composition with the chain anions of dioxovanadium
dinitrate:[-MoO (NO 3 ) 2 -O-] n . The crystal structure of Cs [MoO 2 (NO 3 ) 3 ], on the contrary, consists
ofisland anions [MoO 2 (NO 3 ) 3 ].This work was supported by the Russian Foundation for Basic
Research, Grant No. 04-03-32734.96

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HOMOCHIRAL OS 3 COMPLEXES AS NEW REAGENTS FORDEFINITIONS OF THE ENANTIOMERIC

COMPOSITION OF AMINO COMPOUNDSPogrebnyak V.M.Novosibirsk State UniversityControl over the
products of enantioselective reactions, for the enantiomericpurity of medicines and other drugs requires
the use of modernuniversal methods and reagents for determining the enantiomeric compositionchiral
compounds. The aim of the work is to develop an original methodanalysis of chiral amines 1 H NMR
using homochiralclusters (µ-H) Os 3 {µ-OC- ( R ) -NHCHMePh} (CO) 9 L (L = CO ( 1 ), NMe 3 ( 2 )).
Workingthe spectrum region during analysis is the hydride region (δ <0), free of signalsaliphatic
protons.A comparative study of physical and chemical properties in a series of 8related homochiral
complexes (µ-H) Os 3 {µ-OC- ( R ) -NHCHMePh} (CO) 9 L{L = CO ( 1 ), NMe 3 ( 2 ), R - (+) and S - (-) -
NHCHMePh ( 3 R and 3 S )}. The absoluteconfiguration of two representatives of this series. Mutual
position of µ-H signals 3 R and3 S in the 1 H NMR spectra correlates with the configuration of the amino
ligand, and ∆δ between themsufficient (0.062 ppm) to analyze the R / S composition of α-
phenylethylamine inthe form of these complexes. Two methods of enantiomeric composition analysis
have been developedNH 2 CHMePh in accordance with two methods of its binding into complexes 3 R
and 3 S :with direct substitution L = NMe 3 ( 2 ) and with oxidative substitution L = CO ( 1) inpresence of
Me 3 NO. It was shown that the formation of complexes (µ-H) Os 3 (µ-X) (CO) 9 L (X =OH, OCNHCH 2
COOEt, OCNHCHMePh; L = amine, phosphine) in the reaction(µ-H) Os 3 (µ-X) (CO) 10with Me 3 NO in the
presence of L goes through the formationcoordination-unsaturatedparticles [(µ-H) Os 3 (µ-X) (CO)
9 ],Soandbyalternative mechanism. the relative contribution of the two mechanisms depends on the
natureµ-X, solvent and does not depend on the nature of L.97

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PHASE EQUILIBRIUM SYSTEMS Sc 2 S 3 - Ln 2 S 3 (Ln = La - Lu)Razumkova I.A.GOU VPO Tyumen State

UniversityThe purpose of this work is to study phase equilibria in systems Sc 2 S 3 - Ln 2 S 3(La, Nd, Gd,
Er) and the establishment of patterns for the entire series of rare earthelements.Phase diagrams of the
Sc 2 S 3 - Ln 2 S 3 (La, Nd, Gd, Er) systems have been constructed ;preliminary forecast.In the Sc 2 S 3 - La
2 S 3 system , a compound of the composition ScLaS 3 orthorhombicstructures with unit cell parameters
(e.u.): a = 0.718 nm; b = 0.653 nm; c =0.960 nm, with a congruent melting point of 2250 K. Coordinates
of eutectics 27pier % La 2 S 3 ; 1900 K and 70 mol% La 2 S 3 ; 1800 K.Phase diagrams of state of the Sc 2 S
3 - Ln 2 S 3 (Nd, Gd) systems qualitativelyare similar and belong to the type of systems with a
congruently melting compound. INsystemsformedconnectionsstoichiometriccomposition ScLnS 3
,crystallizing in the rhombic system (space group Pnma with e.u. parameters:ScNdS 3 a = 0.712 nm; b =
0.645 nm; c = 0.949 nm; ScGdS 3 a = 0.704 nm; b = 0.639 nm; c =0.947 nm) and melting congruently.
Based on the ScLnS 3 phase , a two-sidedarea of homogeneity.In the Sc 2 S 3 system- Er 2 S
3complication of phase equilibrium is observed.Two complex sulfides are formed: 1) ScErS 3 (with e.u.
parameters: a = 0.697 nm;b = 0.633 nm; c = 0.942 nm) melting with decomposition; 2) ScEr 3 S 6 (with
e.a. parameters:a = 1.073 nm; b = 1.183 nm; c = 0.381 nm; γ = 108.2 °) melting congruently. Basedphase
Sc 2 S 3 there is an extended region of homogeneity up to 30 mol.% Er 2 S 3 .In the series of Sc 2 S 3 - Ln
2 S 3 (Ln = La - Lu) systems, the nature of phase equilibria dependson the ratio of the radii of scandium
and rare earth elements: Sc 3+ (r = 0.86 Å); La 3+(r = 1.19 Å); Lu 3+ (r = 1.00 Å) [1], a change in the nature
of the relationshipsSc 2 S 3and Ln 2 S 3 . For this reason, the phases formed at the beginning of the
series meltcongruently and do not form regions of homogeneity. Thermodynamic stability inseries
decreases, an increase in the area of the solid solution is observed and the complexityphase
equilibrium.1. M. Husain, Alka Batra, KS Srivastava // Polyhedron, 1989, v. 8, p. 1233-1237.98

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SYNTHESIS AND RESEARCH OF NEW HETEROBIMETALLICSETS BASED ON β- DIKETONATES

LUTETIUMSelivanov D.V.Moscow State University M.V. Lomonosov, Faculty of ChemistryRecently, more
and more practical and scientific interest is attractingcompounds combining metals of different nature
due to the possibletheir manifestation of unusual chemical and physical properties. To such
compoundsinclude heterobimetallic complexes based on rare earth elements and 3d metals,the
application of which extends from catalysis and molecularmagnets prior to their deposition of thin films
and coatings by the MOCVD method.To obtain 3d-4f heterobimetallic complexes, one can usevarious
synthetic approaches. One of the most applicable synthesis optionsis the strategy of using the 3d metal
complex as an additionala neutral ligand included in the coordination sphere of the REE ion.The
purposegivenworkwassynthesisandstudynewheterobimetallic complexes based on lanthanide with the
smallest sizeionicradius -lutetium, [Lu (pta) 3 M (SchiffBase)],where Hpta =pivaloyltrifluoroacetone, M =
Ni (II), Cu (II), H 2 (SchiffBase) = Schiff base,obtained by condensation of one mole of ethylenediamine
and two moles of salicylicaldehyde (H 2 (salen)) or acetylacetone (H 2 (acacen)). The resulting
compounds werecharacterized by IR-spectroscopic, elemental and PMR-analyzes(for copper-free
compounds). XRD data showed that the structure[Lu (pta) 3 Cu (salen)] consists of isolated bimetallic
molecules linkedwith each other into dimeric fragments through the interaction of copper witharomatic
fragment Cu (salen) of the neighboring molecule. Implementation of similarinteractions leads to a
significant distortion of the environment of the copper ion, whichin a free complex, Cu (salen) is flat-
square.The resulting complexes were studied by thermal analysis andisothermal vacuum sublimation. It
was found that complexes containingcopper, are able to sublimate without changing the composition,
while the complexes onbased on Ni-containing additional ligands sublimate with a
noticeabledecomposition into the original monometallic complexes.99

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SYNTHESIS, CRYSTAL STRUCTURE AND LUMINESCENTPROPERTIES OF NEW COMPLEXES OF

ACYLPYRAZOLONE WITH Tb AND EuSemyonov S.N., Drozdov A.A., Troyanov S.I., Zolin V.F.Moscow State
University M.V. Lomonosov, Faculty of ChemistryComplexes of 4-acylpyrazol-5-ones with terbium and
europium were successfulused to create emitting layers in electroluminescent cells(OLED). Such
complexes, in contrast to organic luminescent materials,provide narrow emission lines at high
intensities.From the analysis of the available data, it was concluded that in order to ensure
greaterluminescence intensity of the hydrocarbon radical must have a hardstructure [1]. To ensure
volatility, the radical must be bulky andsaturated.requirements meetwas the synthesis of the
corresponding ligand withadamantyl radical with acylgroup. The synthesis was carried out according to
the standardmethodology,acylation1-phenyl-3-methylpyrazole-one acid chloride Eu (III), Tb (III); L = Phen
(o-phenanthroline), Dipy(2,2'-dipyridyl), MeThisit is adamantyl. Therefore, the first stephe-5attoabout2
Dipy (4,4'-dimethyl-2,2'-dipyridyl). For ligand and complexesEuropium composition is also confirmed by
H 1 NMR spectroscopy. For ligand HQ adand a complex of the composition Tb (Q ad ) 3 (Me 2 Dipy), X-ray
diffraction analysis was performed.HQ ad crystallizes in monoclinic system with space group P2 1 / C.The
main structural elements of the HQ ad crystal are bilayers based onthe principle of the lipid bilayer. The
pyrazolone rings face the inside of the layer andinteract in the π - π type, and the adamantyl groups are
outside. CrystalTb (Q ad ) 3 (Me 2 Dipy) has a C 2 / C space group with unusually largeunit cell
parameters: a = 28.006 (6 ) Å, b = 9.671 (1) Å, c = 49.694 (10) Å,β = 96.66 (2). The main structural
element is molecular fragmentsTb (Q ad ) 3 (Me 2 Dipy). The photoluminescence spectra of all obtained
solidconnections.NNOO= HQ adone hundred

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SYNTHESIS AND RESEARCH OF NEW COMPLEX MANGANESE OXIDESRCaSnMnO 6 WITH DOUBLE

PEROVSKIT STRUCTURE(R = REE (III) OR Y)Seryakov S.A., Abakumov A.M., Rozova M.G., Antipov
E.V.Moscow State University M.V. Lomonosov, Faculty of ChemistryIn the presented work, the possibility
of obtaining complexmanganese oxides, with the ordering of MnO 6 octahedra into isolated layers (MnO
2 ) ∞ ,which is of interest for the study of electrical and magnetic propertieslow-dimensional systems.
The ability to layer-by-layer ordering of B ions (B = Ti 3+ ,Mn 3+ , Cu 2+ , Ni 3+ ) in double perovskite
АA'BB'O 6 was expressed by Anderson [1],who first described layered cuprate La 2 CuSnO 6 .The
synthesis of phases of the supposed composition RCaSnMnO 6 (R = REE (III) or Y) wascarried out on the
basis of oxides R 2 O 3 , CaO, SnO 2 , MnO 2 and Mn 2 O 3 by double annealingin a quartz evacuated
ampoule: 100 h at a temperature of 900 0 C followed byby grinding and holding for 150 h at 1100 0 C.
XRD of the obtained samples showedthat in the case R = La, Nd - Gd, Dy a new phase has formed. In case
R = Y, Ho-Tm wasonly a mixture of CaSnO 3 and RMnO 3 was found .X-ray diffraction patterns of the
obtained substances are indicated in rhombic system,systematic extinctions of reflexes correspond to the
space group Pnma ,Z = 2; a : b : с ≈ √2 • a per : 2 • a per : √2 • a per ( a per is the cell parameter of a
cubic perovskite),which indicates the realization of the structural type GdFeO 3 with disorderedthe
arrangement of the SnO 6 and MnO 6 octahedra . Parameters of unit cells obtainedsamples are
presented in the table:RLaNdSmEuGdDya , Ǻ5.6784 (6) 5.7103 (10) 5.7168 (6)5.7126 (13) 5.7130 (11)
5.6957 (5)b , Ǻ7.9105 (14) 7.851 (3) 7.7955 (14)7,815 (2)7.7949 (14) 7.7823 (12)c , Ǻ5.5657 (7) 5.5077
(13) 5.4763 (10) 5.4748 (12)5.4607 (8) 5.4364 (6)The unit cell metric and spatial symmetry
wereconfirmed by electron diffraction data for NdCaSnMnO 6 . For sampleSmCaSnMnO 6 structure was
refined by the Rietveld method (R I = 0.0390,R P= 0.0191), which confirmed that this compound belongs
tostructural type GdFeO 3 .1. MT Anderson et al // Prog. Solid State Chem., 1993, v. 22, p. 197.101

Page 102

SYNTHESIS AND STUDY OF SILICONS SUBSTITUTEDHYDROXYAPATITES Ca 10 (PO 4 ) 6-x (SiO 4 ) x (OH) 2-x
(x ≤ 1)Soin A.V. 1 , Veresov A.G. 1 , Putlyaev V.I. 21 Moscow State University M.V. Lomonosov, Faculty of
Materials Science,2 Moscow State University M.V. Lomonosov, Faculty of ChemistryMaterials based on
hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 (HA) are used forcreation of artificial substitutes for human bone
tissue. Chemicalmodification of hydroxyapatite is the main management methodbiological activity of the
material made on its basis. Bioactivity -complex characteristics of materials, taking into account, in
addition to biologicalprocesses of growth and differentiation of cells, also: the rate of dissolution of
material inslightly acidic environment created by certain groups of cells; settling ratehydroxylapatite
from interstitial body fluid on the surface of the material [1].Since we are talking about medical
materials, the choicemodifying additives are substantially limited. Currently largeOf interest is the
synthesis of thermally stable ceramic materials onbased on silicon-containing hydroxyapatite: it has been
shown that the presence of silanol(Si-OH) groups on the surface of the material facilitates the adhesion
of the implant withbone [2].This work consisted in obtaining HA powders modifiedsilicon, the study of
their thermal stability, obtaining a strong and porousceramics based on them and the study of the
behavior of ceramic materials in modelin vitro reactions.Si-HA powders were obtained by the solution
method according to the equation:10 Ca (NO 3 ) 2 + (6-x) NH 4 H 2 PO 4 + x Si (OC 2 H 5 ) 4 + (14 + x) NH
4 OH →→ Ca 10 (PO 4 ) 6-x (SiO 4 ) x (OH) 2-х + 20 NH 4 NO 3 + 4x C 2 H 5 OH + (12-2x) H 2 OReceived
powders, samples after heat treatment and ceramicmaterials were investigated by XRF, electron
microscopy, IR-spectroscopy, XFS and EDX. Bioactive properties of ceramic sampleswere investigated in a
model solution simulating the composition of interstitial fluid(SBF) at 37 o C.1. LL Hench // J. Am. Ceram.
Soc., 1998, v. 81, p. 1705.2. IR Gibson, SM Best, W. Bonfield // J. Biomed. Mater. Res., 1999, v. 44, p.
422.102

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ALKOXYSILANOLATES OF METALS.SYNTHESIS OF SIL-GEL SILICATES BY THE METHODE.V. SuslovaMoscow

State University M.V. Lomonosov, Faculty of ChemistryThe main number of publications on the
application of the sol-gel method for the synthesis of oxidematerials devoted to metal silicates using Si
(OEt) 4 (TEOS). Howeverless, data on ethoxysilanolates - M (OEt) n... mSi (OEt) 4or M [OSi (OEt) 3 ] n-
hypothetical precursors of silicates are practically absent in the literature.In this work, a study of the
interaction of alcoholates andmetal hydroxides with Si (OR) 4 , the conditions for the formation of
alkoxysilanolates were studied, andalso meta- and orthosilicates of barium and calcium (using sol-gel
technology).StudysystemsNaOEt-Si (OEt) 4 -EtOH,Ba (OEt) 2 -Si (OEt) 4 -EtOH,Al (OPr i ) 3 -Si (OPr i ) 4 - i
PrOH at 25 о С by methods of solubility and conductometryshowed that complexation does not occur in
them. Si-O-Al bond formationIt does not take place during the heat treatment and the mixture Al (OPr i )
3 -Si (OPr i ) 4 (7 hours at 200 to C) ormicrohydrolysis under the same conditions (confirmed by IR
spectroscopy).NaOSi (OEt) 3 was used as a starting material in the synthesis of ethoxysilanolates
,obtained by reaction:NaOH + Si (OEt) 4 → NaOSi (OEt) 3 + EtOHTo synthesize M [OSi (OEt) 3 ] nused the
exchange reaction of sodiumcomplex with metal chlorides. In this work, Ti [OSi (OEt) 3 ] 4 (up toonly
derivatives of Na, K, Al have been known recently). Ca (OH) 2 notreacts with Si (OEt) 4 .The use of the
sol-gel method for the preparation of silicates was studied using the examplesystems M II (OEt) 2 -Si
(OEt) 4 (M II = Ba, Ca). Micro- and macrohydrolysis of alcohol solutionswas carried out at the ratios [M]:
[Si]: [H 2 O] = n: 1: m, n = 1, 2, m = 1, 200. Productsinvestigated by methods of chemical analysis, IR, XRF,
DTA, TGA and electronicspectroscopy. At [Ba]: [Si] = 1: 1, BaH 2 SiO 4 crystallizes even at 80-90 о С (along
withwith amorphous BaSiO 3... nH 2 O), losing water <380 o С with crystallization of BaSiO 3 at850 o C.
M 2 SiO 4 crystallize, respectively, at> 700 o C (Ca) and ~ 1000 o C (Ba).The particle size after annealing is
1–2 μm.103

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NEW ACID COBALT AND NICKEL TRIFLUOROACETATESTokareva A.O., Tereshchenko D.S., Boltalin A.I.,
Troyanov S.I.Moscow State University M.V. Lomonosov, Faculty of ChemistryPreviously, the literature
describes the synthesis and structure of trifluoroacetate tetrahydratesnickel and cobalt (II). They can be
obtained by the interaction of metals orbasic carbonates with an aqueous solution of trifluoroacetic acid
[1].In this work, for the first time, we obtained and structurally studied anhydroustrifluoroacetic
complexes of cobalt and nickel. Weighed portions of M (CF 3 COO) 2 (H 2 O) 4 were dissolvedin
trifluoroacetic anhydride and kept over P 4 O 10 until the solvent was removed.By recrystallization of the
compounds obtained unstable in air from anhydroustrifluoroacetic acid, single crystal samples were
obtained. According tothe results of X-ray diffraction analysis (RSTA), these compounds representare
trinuclear linear complexes, each pair of metal atoms is connected betweenis three bidentate
trifluoroacetate groups. Composition of receivedcompounds corresponds to the formula [M 3 (CF 3 COO)
6 (CF 3 COOH) 6 ] CF 3 COOH, M = Co ( 1 )and Ni ( 2 ). Crystallographic data: 1, sp. Gr. Р 1, a = 13.199 (6)
Å, b = 14.649 (6) Å,c = 15.818 (6) Å, α = 90.04 (4) °, β = 114.32 (4) °, γ = 108.55 (4) °, V = 2611.3 (19) Å 3 ,
Z = 2,R 1 = 0.0480, wR 2 = 0.0972; 2 , ave. Gr. R 3 , a = 13.307 (2) Å, c = 53.13 (1) Å, V = 8148 (2) Å 3 ,Z = 6,
R 1 = 0.1112, wR 2 = 0.2949.To study the effect of synthesis conditions on the reaction products, a
sampleNi (CF 3 COO) 2 (H 2 O) 4 was dissolved in 99% trifluoroacetic acid. According to the dataРСтА
under these conditions the formation of partially hydrated acidicnickel trifluoroacetate [Ni 3 (CF 3 COO)
6 (CF 3 COOH) 2 (H 2 O) 4 ] (CF 3 COOH) 2( 3 ). Generalthe crystal structure motif is similar to that
described above. Crystallographicdata: gr. P 1, a = 9.121 (18) Å, b = 10.379 (2) Å, c = 12.109 (2) Å, α =
84.59 (3) °,β = 72.20 (3) °, γ = 82.80 (3) °, V = 1080.94 (40) Å 3 , Z = 1, R 1 = 0.0334, wR 2 = 0.0771.Thus,
partial replacement of bidentate-coordinated trifluoroacetate groups bythe water molecule does not
lead to the destruction of the trinuclear framework of the complex.1.S.A. Kasyanov // Materials of the
International Conference of Students andpostgraduate students in fundamental sciences "Lomonosov
2001".104

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FORMATION OF IMIDOYLAMIDINES AS A RESULTNi (II) -PROMOTED COUPLING OF ORGANONITRILS

ANDKETOXIMATronova E.A. 1 , Kopylovich M.N. 2 , Pombeiro A. Zh.L. 2 , Kukushkin V.Yu. 11 Saint
Petersburg State University,2 Technical University of Lisbon, PortugalRealization of reactions of
interaction of organic nitriles RCN (R = Me, Et,iso-Pr) with NiX 2 • 6H 2 O (X = Cl, NO 3 ) and 2-propanone
oxime (Me 2 C = NOH) followed bythe addition of [iso-Pr 4 N] (NO 3 ) leads to the formation of
amidinium nitrates -[RC (= NH 2 ) NH 2 ] (NO 3 ) [1]. When using NiX 2 • 2H 2 O, the reaction proceeds in
a differentdirection. As a result of the interaction RCN (R = Me, Et, iso-Pr, n-Pr, CH 2 Cl,CH 2 C 6 H 4 OMe-
p) with NiCl 2 • 2H 2 O and 2-propanone oxime imidoylamidinecomplexes Ni - [Ni {N (H) = C (R) NHC (R) =
NH} 2 ] 2+ [2]. In the case of a reaction of solidorganonitriles RCN (R = C 6 H 4 CN-p, C 6 H 4 CN-
m)fromsystemNi (CH 3 COO) 2 • 4H 2 O / MeEtC = NOHhappensformationneutralimidoylamidines - [Ni
{N (H) = C (R) NC (R) = NH} 2 ].Reactions proceed during reflux for a day with yields of 60–80%. Allthe
obtained compounds were characterized by elemental analysis, FAB massspectrometry, IR, 1 H NMR , 13
C { 1 H} spectroscopy and XRD (for somecomplexes).Imidoylamidine complexes can be used as synthons
forobtaining triazines, as precursors in the synthesis of sulfur and phosphorusnitrogenous
heterocycles.1. MN Kopylovich, V. Yu. Kukushkin, MFC Guedes da Silva, M. Haukka, JJRFraústo da Silva,
AJL Pombeiro // J. Chem. Soc., Perkin Trans. 1, 2001, p.1569-1573.2. MN Kopylovich, AJL Pombeiro, A.
Fischer, L. Kloo, V. Yu. Kukushkin, Inorg.Chem., 2003, v. 42, p. 7239-7248.105

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REFINING THE STRUCTURE AND SEARCHING FOR NEW COMPLEXHALOGENTELLURITES (SELENITES) OF

LEAD AND BISMUTHUlyanova E.A.Moscow State University M.V. Lomonosov, Faculty of ChemistryMany
of the known bismuth and lead halotellurites (selenites) exhibitnon-standard physical properties.
However, structurally, these compoundsinsufficiently characterized. To establish the relationship
between the composition andthe nature of the phase structure in the specified class of compounds, it is
necessary to clarify themstructures and expansion of this family.In this work, a search was undertaken
for phases of the BiEO 3 X type (E - Se, Te; X - Cl, Br), inwhich three-charged bismuth would be
completely or partially replaced bya combination of double and singly charged cations. As such cations,
we wereselected Pb 2+ and Na + (K + ), due to the proximity of their ionic radii. For implementationof
the formulated approach, samples of three series of compositions were prepared:PbO⋅EO 2 ⋅MX (I),
PbO⋅EO 2 ⋅BiOCl⋅MCl (II), PbO⋅TeO 2 ⋅6MX (III), where E - Te, Se, M - Na,K, X - Cl, Br. The initial mixtures
were annealed in sealed evacuated ampoules at400 ° C (I, II) or 800 ° C (III). According to the results of
XRF of final products, inthe described conditions, the formation of quaternary phases does not occur, the
interactionof these components leads to the formation of halogentellurites (selenites)lead or bismuth.
Obviously, the geometric factor is necessary, butinsufficient criterion for the implementation of
predicted compounds.It is concluded that sodium halides are suitable as a flux for obtainingsingle
crystals of halotellurites of the indicated metals. So, by annealing a mixture of compositionPbO⋅TeO 2
⋅6NaBr crystals Pb 3 TeO 4 Br 2 were obtained . The composition of the crystals is setbased on the results
of their EDX analysis (Pb: Te: Br = 3: 1: 2) and structuralX-ray diffraction experiment. The test substance
crystallizes intetragonal system with unit cell parameters a = 3.987 (4), c = 12.92 (3) Åand belongs to the
structural type of Silenus phases. Its structure is built of triplefluorite-like layers separated by layers of
bromide anions. Baseda powder neutron diffraction experiment, a model of the structureBiTe 2 O 5
Cl,interpretedasdistortedoption(spatialgroup R –3) structures of the Silene phase type.106

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SYNTHESIS AND STUDY OF NEW COMPLEX VANADIUM OXIDEK 2 SrV 3 O 9Tsirlin A.A.Moscow State
University M.V. Lomonosov, Faculty of ChemistryThe most important structural feature of vanadium
oxides is the varietycoordination environment of this atom, allowing the implementation of a variety
ofschemes of the mutual arrangement of polyhedra. In cases where the oxidation statevanadium atoms
are less than +5, d- electrons appear in the system and, accordingly,numerous variants of magnetic
structures arise. Especially interesting are thosevanadium oxides, which have a magnetically low-
dimensional structure, i.e.contain chains, ribbons or layers of magnetic cation polyhedra.In this work, a
new complex vanadium oxide K 2 SrV 3 O 9 was obtained .The crystal structure of this compound was
refined by the Rietveld method usingpowder X-ray data. Unit cell K 2 SrV 3 O 9It hasrhombic symmetry; a
= 10.1922 Å, b = 5.4171 Å, c = 16.1425 Å, Sp. Gr. Pnma, Z =4. In the K 2 SrV 3 O 9 structure , vanadium
atoms are coordinated in square pyramids withone short, vanadyl bond. Square pyramids linked in
isolatedchains through tetrahedrons V +5 O 4 ; potassium and strontium cations are orderedbetween the
chains. Thus, in its structure, K 2 SrV 3 O 9 is similar to Na 2 SrV 3 O 9 ,however, an increase in the size of
one of the cations leads to the "straightening" of the chains andincreasing the symmetry of the crystal
structure.K 2 SrV 3 O 9 exhibits magnetic properties typical of one-dimensional systems.The temperature
dependence of the magnetic susceptibility is well describedthe Bonner-Fischer relation [1] with the
exchange integral J ≈ 80 K. Meanwhile,there is no direct connection between the V + 4 O 5 polyhedra
through the oxygen atom in the structure.Thus, K 2 SrV 3 O 9 is another example of a complex vanadium
oxide, inwhere a significant superaxchange interaction is realized along a complex pathV +4 - (V +5 O 4 )
–V +4 , that is, with the participation of the polyhedron of the nonmagnetic cation.1. JC Bonner, ME
Fisher // Phys. Rev., 1964, v. 135, p. A640.107

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WITH THE SUPPORT OF THE YOUTH WORKING COMMISSIONSCIENTIFIC INTERDEPARTMENTAL

COUNCILRADIO CHEMISTRYDepartment "Radiochemistry"Jury:Fedoseev V.M.professor, doctor of
chemical sciences - chairmanBadun G.A.Associate Professor, Ph.D. - Deputy ChairmanKalmykov
S.N.Associate Professor, Ph.D. - secretaryA.A. Abramovprofessor, doctor of chemical sciencesAliev
R.A.Associate Professor, Ph.D. (SINP MSU)Beckman I.N.professor, doctor of chemical sciencesBerdonosov
S.S.Associate Professor, Doctor of Chemical SciencesA.P. NovikovArt. Doctor of Chemistry (GEOKHI
RAS)Presnyakov I.A.Art. Researcher, Ph.D.Tananaev I.G.Art. Doctor of Chemistry (GEOKHI RAS)108

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The sorption behavior of depleted uranium dioxideATTITUDE TO NEPTUNIUMBatuk O.N.Moscow State

University M.V. LomonosovObtaining nuclear fuel for the needs of the nuclear technological cycle has
ledto the accumulation of significant reserves of so-called depleted uranium (DU). INDU is currently
stored on the day surface as a highly toxicuranium hexafluoride (UF 6 ). Possible ways of OS utilization in
industrialscale are reduced to the production of mixed oxide fuels and the manufacturecontainers for
transportation of radioactive waste (RW). In this workthe possibility of using OC in the form of dioxide as
ageochemical barrier at the sites of radioactive waste disposal. The purpose of the work was to
studysorption properties of depleted uranium dioxide in relation to neptunium-237.Dioxide preparations
were selected as the objects of study.depleted uranium, obtained in industry at different annealing
temperatures ina reducing atmosphere. Methods were used to diagnose drugspotentiometric titration,
transmission and scanning electronicmicroscopy, nitrogen adsorption at 77 K and calculation by the BET
equation, distributionparticle size was obtained by dynamic light scattering. Forto establish the U / O
ratio in the bulk of the samples and on the surface, we usedmethods of X-ray phase analysis and X-ray
photoelectron spectroscopy.The sorption of Np (IV) and Np (V) was studied under different conditions.
Sorptionboth Np (IV) and Np (V) from deionized water depend on the concentration of U (VI) insurface
oxidized layer of drugs - it increases from less oxidizedsample to more oxidized. A significant difference in
the sorption of both Np (V) andNp (IV) from a solution simulating natural water of the proposed RW
storage facilityvarious drugs are not observed. Sorption of Np (V) is accompanied by partialreduction to
Np (IV). The ability of uranium oxide preparations to reduceactinides is an important property for the
creation of geochemical barriers, becausethe mobility of tetravalent actinides is significantly less than
that of pentavalent.This work was supported by ISTC grant 2694.109

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SORPTION OF Pu (V) ON LOW-TEMPERATURE HEMATITE ( α -Fe 2 O 3 ) INPRESENCE OF HUMIC

SUBSTANCESBlinova O.A.Institute of Physical Chemistry RASThe spread (migration) of radionuclides in
the environment is largelydeterminedgeochemicalconditionsgivenenvironment (oxidativerestorative
environment, mineral and organic composition) and as a result -a set of physicochemical forms (redox
states,organic and inorganic complexes, colloids), which this radionucliderepresented in a specific
ecosystem taken.Actinides pose a serious environmental hazard due to theirhigh toxicity and high
migration ability in the highest degreesoxidation. Humic substances (HS) play an important role in the
distribution of physicalchemical forms of actinides and their migration due to the ability to recover
andcomplexation of actinides, as well as the formation of colloidal forms and sorptionon minerals.This
work is devoted to the study of the behavior of plutonium on the mineral -natural water in the presence
of natural and synthetic humic substances.The kinetics of Pu (V) sorption on low-temperature hematite
(α-Fe 2 O 3 ) inpresence of synthetic humic acid (HA, Aldrich) at variousHA concentrations. It was shown
that under these conditions it is possible to restorePu (V) to Pu (IV), which caused its rapid sorption on
the hematite surface.It was shown that the rate of recovery increases with an increase in the
concentration of HA.The kinetics of Pu (V) reduction with humic and fulvic acids (FA),isolated from real
soils in the area of PA "Mayak". It has been shown that the speedrecovery increases with decreasing
molecular weight in the seriesHA <FA <low molecular weight organic acids.The data obtained will make it
possible to modify the GW in order torecovery and mobilization (binding) of actinides for the use of the
obtainedHS as geochemical barriers.110

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CONDITIONING OF WASTE BURNING SLAGSION EXCHANGE RESINSBortnikova M.S., Karlina O.K., Pavlova
G.Yu.GUP MosNPO "Radon"Currently, due to the increasing volumes of wasteion exchange resins at
nuclear enterprises, the problem of theirconditioning is highly relevant. The purpose of air conditioning
isreduction of the initial volume of resins, as well as their translation into a stable form,excluding the
transfer of radionuclides into the environment under conditionslong-term storage. To reduce the volume
of radioactive ion-exchangeresins are burned.SUE MosNPO "Radon" is developing a technology for
burning wasteion exchange resins using metallized powdered fuel. [1] INwithin the framework of this
work, the search for the optimal composition of the fuel usedfor burning radioactive ion exchange resins
in order to achieve the necessarycompleteness of combustion of ion-exchange resins and obtaining a
slag with properties,providingsustainabilityconditionedproduct.Forslag conditioning uses a magnesium-
phosphate composition of the mainthe structure-forming phase of which is magnesium-potassium-
phosphate hexa-hydrateMgKPO4 6H2O. The method of obtaining magnesium phosphate is also being
improved.composition with the study of its physical and chemical characteristics.In the experiment, we
used slag from the combustion of ion-exchange resin grade KU-2-8 with an initial specific activity of 3.5 *
104 Bq / kg. The resulting samples of the finalproduct magnesium phosphate ceramics contain up to 60%
of the mass. initial slag.The mechanical strength of the ceramic matrix is 6 MPa (admissible strengthfor
cement compounds ≥5 MPa). Leaching rate of 90Sr + 90Y from samples ~1 * 10-3 g / cm2 * day for 28
days, which meets the requirements of GOST. Speedleaching of the main matrix components (Mg2 +,
PO43-, SO42-, Na +) wason the 28th day no more than 1 * 10-4 g / cm2 * day.1. Development of thermal
technologies for the inclusion of radioactive waste in stable monolithicmatrices. Development of
technologies for radioactive waste processing using ceramicsand glass-like matrices: Research report
(interim) / MosNPO"Radon". Inventory No. 615 - Sergiev Posad - 2003. - 21 p.111

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PHOTON-ACTIVATION ANALYSIS OF COMPLEX OBJECTSCOMPOSITIONGainullina E.I.Moscow State

University M.V. LomonosovPhoton activation analysis (FAA) is based on the registration of
radioactiveradiation of products of nuclear reactions proceeding under the action of high-energy
photonsenergies. For the experiments we used a split microtroncreated at SINP MSU. The certified
samples of bottomsediments in which more than 21 elements were found and the limits were
calculateddetection for many of them. Optimal experimental conditions are proposed,such as: beam
energy and irradiation duration, holding time afterexposure, duration of measurement. The optimal
configuration of the target has been chosen. INthe average sensitivity for the determination of elements
that give long-lived productsactivation is slightly higher, since in this case a long-term accumulation
ofgamma spectrum. In addition, by the time of measurement, most of theshort-lived radionuclides,
which significantly reduces the continuous areaspectrum due to Compton scattering. Obtained
limitsdetection of many elements (Fig. 1) are comparable with the corresponding values,obtained by
other authors. The effects of nuclear interference were investigated. ForFor this, we carried out
experiments at different energies from 20-50 MeV. Studiedinterfering effect of uranium fission fragments
on the determination of other elements.0.11tenone hundred1000FeCaTiBaTi * MgZnSr Ti **
MnCrNiZrScCoRbAsLD, mcg35 MeV50 MeVFig. 1. Limits of detection of various elements in bottom
sediments112

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STUDY OF CRYSTALLIZATION PROCESSES IN HYDROGELPOLYMER MATRICESGopin A.V., Nikolaev A.L.,

Kulikov L.A., Perfiliev Yu.D.Moscow State University M.V. LomonosovCrystallization of various substances
in polymer hydrogels is widelycommon in nature and technological practice. Study of crystallization ingel
bodies allows you to identify a number of points that open the possibility of itsuse in medicine, in
particular in combination with ultrasoundimpact [1]. In this regard, it is of particular interest to
identifypatterns of influence of the nature of the polymer matrix and ultrasound on the
parametersphase formation process.In this work, precipitation of solid phases Fe 2 O 3 * nH 2 O in
polyacrylamidegel and in gelatin by the method of counter diffusion. By the Mössbauer
methodspectroscopy, the aging of sediments was traced, and the influence of ultrasound onthe
dynamics of changes in the ratio of various forms of iron hydroxide obtained inaqueous solution and
polyacrylamide gel. Analysis of the results shows thatthe nature of the polymer matrix affects the ratio
of the forms synthesized in itiron hydroxide. Especially strong influence on their ratio during synthesis as
inthe matrix and in the solution has an ultrasonic effect.Along with the method of Mössbauer
spectroscopy for studying phase formationthe method of scanning electron microscopy was used. For
this purpose speciallya method for the preparation of hydrogel samples was developed.
Throughscanning electron microscopy samples of hydroxideiron and calcium salt of an organic dye
precipitated in various gelsystems (polyacrylamide, gelatin, agarose). The effect of the nature of the
matrix onphase formation processes.A mathematical model of phase formation in a porous layer
atcounter flow of reagents. Using this model, calculations were madedescribing the behavior of such
systems at various kinetic parameters.1. Melikhov I.V., Nikolaev A.L., Andronova N.V., Treshchalina E.M.
Mechanismcrystallization in polymer gels in the aspect of sonodynamic therapyoncological diseases.
DAN, 2003, v. 390, no. 1, p. 53.113

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OBTAINING [ 3 H] -PANTOTENATE FOR STUDYING ITS CAPTUREAND BIOTRANSFORMATION BY

NEUROSTRUCTURESEvkovich I.N. 1 , Chernysheva M.G. 21 Institute of Biochemistry of the National
Academy of Sciences of Belarus,2 Moscow State University M.V. LomonosovIn recent years, the
pathogenetic role of pantothenic acid (PC) has been establishedand its coenzyme form - CoA in the
development of neurodegenerative pathology. Processcapture and biotransformation of PC in the
central nervous system is limited to highly specificmechanisms, the further study of which, as well as the
search for effectiveCoA precursors are possible only through the use of radionuclides.The use of tritium-
labeled compounds and their preparation seems promising.using the method of thermal activation of
tritium. In this work,study of the dependence of the yield of tritiated sodium D-pantothenate (PCNa)
onenergies of atoms incident on the target. The target was prepared by freeze-drying an aqueousPKNa
solution on the walls of the reaction vessel. Reaction with atomic tritiumcarried out at a gas pressure of
0.5 Pa, when the free passage of atoms fromatomizer to the target. The temperature of the tungsten
wire was varied within1740-1980 K. After the introduction of tritium, the analysis of labeled products
was carried out usingTLC and HPLC. It was found that the yield of 3 Н-PCNa from the temperature of the
atomizer hadextreme dependence with a maximum at 1900 K. 3 H-PCNa with specificradioactivity 0.1
TBq / g was used to study its capture andbiotransformations by neurostructures of the brain of white
Wistar rats atintraperitoneal injection. Extracts of brain and blood plasma
homogenateschromatographed (HPLC) and fractions were measured by scintillation counting.Against the
background of a decrease in the radioactivity circulating in the blood, an accumulation ofPC-containing
compounds in the brain: cerebellum> hippocampus> trunk>large hemispheres. It was found that the
intensity of phospho-PC formation inthe hippocampus is noticeably higher than in the large hemispheres
and is characterized by a rapidsaturation period. In general, the process of PC phosphorylation in the
cerebral hemispheresthe brain has a high intensity, but further biotransformationphospho-PC in CoA is
limited.This work was supported by grants RFBR No. 03-03-32410 and BRFFR No. B04-238.114

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BONDING A BLOCK COPOLYMER OF ETHYLENOXIDE ANDPROPYLENOXIDE WITH LIPID MEMBRANES AND

CELLSZhirnov A.E.Moscow State University M.V. Lomonosov, Faculty of Chemistry, jyrnoff@yandex.ruThe
resistance of cancer cells to drug therapy arising in the processtreatment of tumors is a serious problem
in oncology. It was recently shownthat the joint administration with the drug of block copolymers of
ethylene oxide andpropylene oxide (proxanols) helps to overcome the resistance of cancercells. At the
same time, proxanols practically do not affect the transport of drugs into cancercells sensitive to
chemotherapy. Reasons for selectivity of actionproxanols remain unknown to date. To investigate the
causesselective action of polymers on cells resistant to chemotherapy, inIn this work, we studied the
binding of proxanols with artificiallipid membranes and living cells.To study the binding of the polymer to
membranes, labeledtritium proxanols. Tritium was introduced into the preparations using the
thermalactivation. The target product was purified using gel permeation chromatography.The specific
radioactivity of the drug was 0.8 TBq / mmol, which iscorresponds to approximately one tritium atom
per polymer molecule.Partition coefficient of polymer between aqueous solution and phaseof
phosphatidylcholine membranes was found to be 76, which indicated a rather lowpolymer affinity for
membranes. In this case, the introduction of cholesterol into the membraneled to a decrease in the
distribution coefficient by several times.The binding of the polymer to cells was almost two orders of
magnitude higher than tolipid vesicles. At the same time, the cell affinity for the polymer increased
bynext row: normal lymphocytes <chemotherapy sensitivecells <resistant cells.Thus, the use of tritium-
labeled polymers made it possible to givequantitative assessment of the degree of interaction of
biologically active polymers withmodel membranes and cells.This work was supported by grants from
the Russian Foundation for Basic Research No. 03-03-32410, No. 03-03-32629.115

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SORPTION OF RADIONUCLIDES 90 Sr + 90 Y powder and vateriteCALCITE OBTAINED BY US-METHODI. V.

ZnamenskayaMoscow State University M.V. LomonosovFinely dispersed powders of inorganic substances
find a wideuse as carriers, fillers, catalysts and sorbents invarious fields of chemistry, chemical
technology and medicine. They are importanthave for the extraction of radionuclides from the aquatic
environment, especially such aslong-lived radionuclides of strontium, cerium and cesium. In this case, it
is desirable thatsorption of radionuclides proceeded irreversibly. As inorganic sorbentsradionuclides use
oxides, hydroxides, sulfates, carbonates, etc. Forensuring the irreversible nature of sorption, it is
necessary that the usedthe sorbent was recrystallized during sorption, and the radionuclide passed
fromsurfaces of sorbent particles into their internal volume. In this work, we investigatedsorption of
strontium-90 and daughter yttrium-90 on finely dispersed waterite,obtained using the ultrasound field.
Vaterite is a metastableunder normal conditions the phase of CaCO 3 , and its stable modification is
calcite. Forcomparison, the sorption of the indicated radionuclides and on highly dispersedcalcite
preparations.To obtain vaterite, solutions of Ca (NO 3 ) 2and Na 2 CO 3fromconcentration of 0.1 mol / l.
The deposition was carried out under the conditions of irradiation of the reactionenvironment by an
ultrasonic field (ultrasonic generator "Albedo", frequency 2.6 MHz, power 40 W) at20 ± 1 ° C. Calcite was
obtained by long-term recrystallization of vaterite in an aqueous mediumat the same temperature. The
synthesized preparations were characterized according to the dataX-ray phase analysis, scanning
electron microscopy and isothermsnitrogen sorption (BET).Sorption of strontium-90 and daughter
yttrium-90 was studied at a temperature of 20 ± 1 ° С fromsolutions without a carrier and from solutions
containing Sr (NO 3 ) 2 at a concentration of 10 -4 -10 -3mol / l. It has been established that the sorption
of radionuclides by vaterite proceeds in 2 stages. On thethe first stage (its duration is 15-20 min) is
adsorption capturesorbent surface. At the second stage (lasting several days)transition of radionuclides
into the volume of sediment particles is observed, which leads toirreversible capture of radionuclides by
calcium carbonate preparations.116

Page 117

ISOLATION OF TIN-117m FROM IRRADIATED PROTONSANTIMATE TARGETKim Dong KyuMoscow State

University M.V. LomonosovIn recent years, the use of radionuclides, not onlyin diagnostics, but also in
the treatment of various diseases, primarilyoncological. Currently, active research is underway in the
field ofobtaining radiopharmaceuticals based on 117m Sn, 166 Ho, 212 Bi, 225 Ac, 214 Po.Tin -117m is a
promising isotope for radionuclide therapy fromfor a relatively short half-life (13.6 days), low-
energyconversion electrons (130 and 159 KeV) and emitted γ-quanta 159 KeV. At presenttime started
research on the use of diethylenetriamine pentaacetate tin(Iv) for palliative treatment of cancer patients
with bone metastases.117m Sn is most promising to obtain by irradiating antimony with protons
onparticle accelerators, because this leads to the production of a radionuclide withoutcarrier. A target
made of metallic antimony was irradiated on a linear accelerator at INRRAS (Troitsk) at a proton energy
of 30-70 MeV. When irradiated, they form withvarious yields of more than 20 radionuclides of tellurium,
tin, antimony, indium, cadmiumand silver, with the yield of the target isotope ≈10%.Therefore, we were
faced with the following tasks: Dissolution of the target and retentionin a fairly compact aqueous
solution of large amounts of antimony (20-50 g). Resettarget materials, because in most of the studied
extraction systems, antimonyextracts either better than other radionuclides present or interferes with
themselective extraction. Selective isolation of tin isotopes in high yield.Proof of the radiochemical
purity of the obtained nuclide.Based on the literature and our own data, we proposedmethod of
processing antimony targets, which includes the following mainstages: 1. Dissolution of the target in HCl
with the addition of oxidizing agents (HNO 3 , Cl 2 ).2. Extraction of the matrix material (antimony) with
di-n-butyl ether. 3. Translationthe remaining mixture of nuclides into iodide solutions. 4. Extraction of tin
(IV) with benzene,purification of the extractant. 5. Re-extraction of tin with 0.1 M NaOH solution. 6.
Controlnuclide composition from γ-spectra at each stage. 7. Determination of radiochemicalpurity and
calculation of the yield of the target product.117

Page 118

DETERMINATION OF THE VALENCE OF NEPTUNIUM IN THE COMPLEXESON THE SURFACE OF LEAN-

URANIUM DIOXIDEMikhailina A.V., Batuk O.N.Moscow State University M.V. LomonosovAs a result of the
activities of nuclear enterprises in the worldsignificant reserves of depleted uranium (DU) have been
accumulated, produced in the processenrichment of natural uranium in the form of highly toxic fluoride.
Potentialthe possibility of using DU in the form of dioxide as an engineeringgeochemical barrier in
radioactive waste disposal sites requires an assessmentits sorption properties in relation to technogenic
radionuclides, establishingthe possibility of various redox reactions duringcontact with natural waters, its
chemical, radiation and heat resistance. OfThe reducing properties of tetravalent uranium are known in
the literature.in relation to neptunium in solution [1]. The purpose of the presented work wasstudy of
the potential reducibility of uranium dioxide, i.e.study of the valence of neptunium in the composition of
complexes on the surface of preparationsdepleted uranium dioxide.Uranium dioxide samples were
saturated with 237 Np (V) at various pH values, inrange 2-5. Neptunium was desorbed from the surface
of the preparations by deionizedwater and solutions of hydrochloric acid of various concentrations. No
desorptiondeionized water and the nature of the acid desorption curve indicatesthe formation of
complexes of actinide on the surface of the drug. Neptunium valencedesorbate was determined by
liquid extraction with 1- (theonyl) -3,3,3-trifluoroacetone(TTA)fromsubsequentliquid
scintillationspectrometry. The results of the desorption study indicate thatcomplexes of both Np (V) and
Np (IV) are formed on the surface, during sorptionpartial recovery of neptunium occurs. Same ratio: 30%
Np (V)and 70% Np (IV) was observed for all studied preparations of uranium dioxide.This work was
supported by ISTC grant 2694.1. Mikhailov VA, Analytical chemistry of elements: Neptunium, “Science”,
Moscow, 1971.118

Page 119

WEAKENING OF THE FLUX OF TRITIUM ATOMS BY ADSORPTIONLAYERS OF ALKYLTRIMETHYLAMMONIUM

BROMIDESMikhalina E.V. 1 , Chernysheva M.G. 2 , Tyasto Z.A. 21 Moscow State University M.V.
Lomonosov, Faculty of Materials Science,2 Moscow State University M.V. Lomonosov, Faculty of
ChemistryOne of the most important parameters that determine the capabilities of the methodthermal
activation of tritium in the study of the structure of biologicalmacromolecules, is the depth of
penetration of reactive tritium atoms deep intotarget. It has been experimentally found that amino acids
in proteins are labeledatomic tritium only in a thin surface layer not exceeding the sizeside chain of
amino acid residue [1]. At the same time, atomic tritium is capable ofto penetrate bilayer lipid
membranes, and weakening of the flux of atoms whenthe passage of such a membrane occurs only 15
times [2].In this work, we investigated how the flux of tritium atoms changes when itpassing through the
adsorption layers of alkyltrimethylammonium bromides (fromdodecyl to cetyl radical). As an indicator of
the flow of atomsused alanine, which has no surfactant properties.The experiment was carried out with
frozen solutions of alanine at a concentration0.1 M and a mixture of alanine of the same concentration
and surfactant at a concentration of 0.67 of its CMC.It is known that at such a surfactant concentration,
an adsorption layer withvertical orientation of molecules relative to the interface.After the introduction
of tritium and removal of the labile label by lyophilization of the solutionthe surfactant was separated
from alanine by TLC, and then alanine was isolated withusing ion exchange column chromatography.
Change in the flux of tritium atomswas evaluated by the change in the specific radioactivity of alanine,
normalized tothe initial radioactivity of the target. The dependence of the flow attenuation is
foundreaction tritium atoms by adsorbed surfactant layers on their lengthhydrocarbon tail and the
conditions of the experiment.This work was supported by the RFBR grant No. 03-03-32410.1. Baratova L.
A., Bogacheva E. N., Gol'dansky V. I. et al. Tritium planigraphybiological macromolecules. Moscow:
Nauka, 1999.175 p.2. Kordyukova LV, Ksenofontov AL, Badun GA, Baratova LA, Shishkov AV// Bioscience
Reports. 2001. V. 21. P. 711-718.119

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STUDIES OF PURIFICATION OF CONCRETE FROM 137 Cs AND 60 Co ISOTOPESELECTROKINETIC

METHODNikolaev A.N., Karlin Yu.V., Yurchenko A.Yu.GUP MosNPO "Radon"The aim of the work was to
study the possibility of cleaning concrete fromradionuclides by the electrochemical method and the
creation of a laboratory complex forresearch this method.The studies used model and really
contaminated concrete in the formcrumbs and solid block [1].The selection of the optimal agents for
decontamination of concrete from 137 Cs and 60 Co was carried outmethodleachinginstaticconditions
(withoutsuperimposingelectric field) [2].For the decontamination of crushed and monolithic concrete,
two laboratoryinstallations: for decontamination of crumb and whole block in an electrokineticmode
[3].1. It was shown that, under the conditions of static experiments, 137 Cs isotopes significantlyeasier to
leach out of concrete with various reagents than isotopes 60 Co.2. It has been shown experimentally
that the use of the electrokinetic methodallows to significantly accelerate the process of leaching from
concrete isotopes137 Cs and 60 Co.3. It has been shown experimentally that the electrokinetic method
allowsleach 137 Cs isotopes from really contaminated crushed concrete withspeed comparable to
samples of model-contaminated crushed concrete.This creates a prerequisite for the development of
appropriate technology.1. Simon A.D. Deactivation. - M .: Atomizdat, 1975.2. Vorbiev V.A., Komar A.G.
Construction Materials. Moscow: Stroyizdat, 1976.3. Akhverdov I.N. Fundamentals of Concrete Physics. -
M .: Stroyizdat, 1981.120

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CRYSTALLINE PHOSPHATES CONTAINING Cesium AND OTHERSALKALINE ELEMENTS: ENVIRONMENTAL

PROBLEMSRADIOCHEMICAL TECHNOLOGIESOrlova V.A.Nizhny Novgorod State University N.I.
LobachevskyThe complexity of the task when choosing a chemical form for curingradioactive waste with
a high content of alkaline elements consists inthe fact that their compounds are generally well soluble in
water and aqueous solutions. INthe present work as possible forms of detoxification of such
wasteMineral-like phosphates of the langbeinite modification are considered.Based on the performed
systemic crystal chemical analysisof known compounds with framework structures, we made a choice for
researchcompositions with the expected langbeinite structure. Phosphates of general formula
compositions:A 2 RZr (PO 4 ) 3 , A 2 Mg 0.5 Zr 1.5 (PO 4 ) 3 and ABR 2 (PO 4 ) 3 , where A = K, Rb, Cs; B =
Sr, Ba; R = Fe, Ga,REEs were synthesized and studied by XRF, neutron diffraction (incl.high-temperature
options), IR spectroscopy.This work shows the possibility of processing real compositionssalt alkaline-
chloride systems pyroelectrochemical regeneration technologynuclear fuel into crystalline materials,
including ceramics, with the expectedlangbeinite structure. Used as solvents halidemelts usually have a
mixed cationic composition: NaCl - KCl, NaCl - 2CsCl,as well as more complex compositions. Phosphates
of mixed compositions of langbeinitemodifications were obtained, including in the laboratories of the
Physico-technologicalDepartment of FSUE GNTs RF '' Research Institute of Atomic Reactors ''
(g.Dimitrovgrad) and investigated by XRF.Cesium-containing phosphates are also promising materials
formanufacturing of γ-radiation sources for medicine. Usingcrystal-chemical principle and based on
knowledge of the isomorphism of cations instructure of langbeinite, compositions of crystalline material
with highcontent of Cs for the manufacture of the active part of the cesium isotope source.Compounds
were synthesized, including at the "PO" Mayak "under conditionssimulating the technological mode of
obtaining sources of cesium-137. Studiedhydrothermal and thermal stability of phosphates, including
determinedproducts of thermal destruction during the synthesis of compounds at all stagestechnological
process.121

Page 122
CRYSTAL CHEMICAL PRINCIPLE IN DESIGNMINERAL-LIKE PHOSPHATE CERAMICS FORIMMOBILIZATION OF
RADIOACTIVE WASTEOrlova M.P.Nizhny Novgorod State University N.I. LobachevskyWe used knowledge
in the field of crystal chemistry of phosphates indesigning mineral-like ceramics for immobilizing
radioactivewaste. In the presence of a crystal-chemical base, it becomes possible to selectthe most
suitable structural form for curing waste of any composition anddifficulties.Results of own research and
research of other authorsused in this work to predict and form crystallinephosphates of complex
composition (close to real waste) with the expectedstructure of monazite. Crystalline modeling is based
on data onisomorphism and isostructurality of phosphates.Complex phosphates containing lanthanides
(III) and (IV), some 2- and 3-valence p- and d- elements, synthesized by coprecipitation and sol-
geltechnology.The formation of intermediate and final products was monitored usingXRF and SEM
methods. As a result of the synthesis, ceramics were obtained in whichthe dominant (under optimal
conditions) was the target phase, but there were alsoimpurity phases (orthophosphates of aluminum
and iron, metallic palladium).A comparative analysis of the results of crystallochemicalmodeling
phosphates with monazite structure and similar cationic compositionphosphates with other structures -
the minerals kosnarite and langbeinite obtainedour scientific group. The parameters for comparison
were as follows: type and quantityadded cations, crystallization temperature, thermal stability,the
number of impurity phases.122

Page 123

TECHNOLOGY OF THERMOCHEMICAL PROCESSING OF RADIOACTIVEWASTE. STRUCTURE AND

PROPERTIES OF THE FINAL PRODUCTOstashkina E.E., Karlina O.K., Varlakova G.A., Dmitriev S.A.GUP
MosNPO "Radon"A technology for conditioning radioactive waste (ashresidue, clinoptilolite, soil) using
the heat of chemical reactions [1]. Whenpreparation of the reaction mixture for conditioning radioactive
wasteare connected to the thermal base, between the components of which after initiationhigh-
temperature chemical reactions of an exothermic nature occur,proceeding in the form of layer-by-layer
condensed combustion.As a result of the passage of reactions and melting of radioactive wastethe final
product is formed, which is a glassymaterial with a density of 1.7 g / cm 3 to 2.9 g / cm 3 and mechanical
compressive strength9-20 MPa. The leaching rates of 137 Cs from the final products are inin the range of
6.3⋅10 -7 -2.5⋅10 -5 g / cm 2 day. Therefore, the final product providesreliable localization of
radionuclides [2].Comparison of the thermochemical method for processing radioactive waste
withwidespread cementation and vitrification shows thatthe above method has several advantages:
independence from sourcesheat supply, minimization of entrainment of radionuclides and components,
reliable fixationradionuclides, the possibility of implementing the process directly in the container
forsubsequent storage or disposal, reducing the volume of waste.1. Ostashkina E.E., Varlakova G.A.,
Karlina O.K. Thermochemical processingsoils contaminated with radionuclides. 3rd All-Russian Youth
Scientificconference on fundamental problems of radiochemistry and nuclearEnergy, Nizhny Novgorod,
2004, Abstracts, p. thirty.2. Karlina O.K., Varlakova G.A., Petrov A.G., Tivansky V.M., Ozhovan
M.I.,Dmitriev S.A. On the use of exothermic metallized mixtureswhen processing radioactive waste. VIII
Int. ecologicalsymposium "Nuclear Urals - Industrial Urals", Yekaterinburg, 2000,Abstracts, p. 116.123

Page 124
SPECIFIC BEHAVIOR OF TRITIUM-LABELED HUMICSUBSTANCES IN TWO-PHASE SYSTEMS WATER-
TOLUENE AND WATER-OCTANOLV.Yu. Pozdnyakova, M.G. ChernyshevaMoscow State University M.V.
Lomonosov, Faculty of ChemistryThe hydrophobicity of organic substances can be studied by measuring
their coefficientdistribution between organic and aqueous phase. As an accepted standardthe partition
coefficient between octanol and water is used. At the same timethe scintillating phase method is
developing, which makes it possible to determine usingtritium-labeled compounds not only the
distribution coefficient of the substance betweenwater and toluene phases, but also to measure the
thickening of the substance at the interface,that is, to obtain a characteristic of its surface activity.In this
work, using tritiated compounds, we investigatedkinetics of redistribution of humic substances in soils,
peat and coal between water andtoluene (scintillation phase method), and between water and octanol.
Afterof achieving equilibrium, the distribution coefficients of substances betweenaqueous and organic
phases. The effect of the pH of the aqueous phase on the coefficientdistribution and adsorption capacity
of humic substances. Carried outcomparison of results with data obtained for individual amino acidsand
cetyltrimethylammonium bromide. Found a correlation between the coefficientsdistribution of the
investigated substances in the water-toluene and water-octanol systems.Labeled preparations of humic
acids and fulvic acids of soils, peat and coal, andalso amino acids and cetyltrimethylammonium bromide
were obtained using the methodthermal activation of tritium.This work was supported by the RFBR grant
No. 03-03-32410.124

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SYNTHESIS OF [ 18 F] FLUMAZENIL: KINETIC ASPECTSAROMATIC NUCLEOPHILIC

RADIOFLUORINATIONRyzhikov N.N. 1,2 , Krasikova R.N. 11 Institute of the Human Brain, Russian
Academy of Sciences,2 Saint Petersburg State University[ 18 F] Flumazenil ( 18 F, T 1/2110 min) ([ 18 F]
FMZ) - a new promisingradioligand for the study of central benzodiazepine receptors by the
methodpositron emission tomography (PET). [ 18 F] FMZ is analogous to widelyused in PET diagnosis of
epilepsy [ 11 C] FMZ ( 11 C, T 1/220 minutes). INcomparative studies on monkeys, we have shown the
identity[ 18 F] FMZ and [ 11 C] FMZ as PET radioligands [Ryzhikov et al, 2005]. [ 18 F] FMZ
wassynthesized by the method of nucleophilic radiofluorination of FMZ ( I ) and Ro 15-2344
( II ):NNXNCOOEtONN18 FNCOOEtODMF, 160 0 C[ 18 F] KF / K222(I), RCY = 67 + -6% (n> 10)(II), RCY = 20-
80%X = F (I), NO 2 (II)To identify the reasons for the difference in the efficiency of radiofluorination of
thesesubstrates and low reproducibility of the radiochemical reaction yield (RCY) inIn the case of Ro 15-
2344, we carried out a detailed study of these reactions.The radiofluorination reaction ( I ) is a special
case of isotopicexchange 19 F / 18 F in the FMZ molecule. When studying the kinetics of this reaction, it
was shown thatthat its speed is described by the equation d [ 18 F-FMZ] / dt = k [FMZ] [ 18 F - ]. In
competitiveexperiments, the reactivity of ( I ) and ( II ) relative to 2-fluoro-5-nitrotoluene (a) and 1,4-
dinitrobenzene (b): k a / k ( I) - 123 ± 15; k b / k ( I) -102 ± 19; k a / k ( II)and k b / k ( II) > 500. Analysis of
the dependence of the radiochemical yield of [ 18 F] FMG on timereaction indicates a possible side
passivation process[ 18 F] fluoride with respect to nucleophilic substitution. As seen from the
comparisonrate constants of reactions, the contribution of this process can be significantly higher incase
Ro 15-2344. To confirm this hypothesis, furtherexperiments. The problem raised may have general
implications for nucleophilicradiofluorination of weakly activated substrates.125
Page 126

MECHANISMS OF SORPTION OF Np (V) AND U (VI) BY ROCKSSabodina M.N. 1 , Vlasova I.E. 21 Institute of
Physical Chemistry and Electrochemistry named after A.N. Frumkin, RAS,2 Moscow State University M.V.
Lomonosov, Faculty of ChemistryThe migration behavior of radionuclides in the environment is
largelydegree is determined by sorption on the host rocks. The purpose of this workwas the
establishment of the regularities of the sorption of 237Np and 238U by various mountainrocks - gneiss,
metadiabase and amphibolite. Sorption studieswas carried out with radionuclides in both a truly
dissolved form andas part of bentonite colloids.The sorption experiment was carried out with crushed
and groundsamples of rocks, at different values of pH and ionic strength. Sorptionthe properties of
crushed various rocks differ, which is probably due totheir different mineral composition. Sorption of
neptunium increases with increasing pH;with an increase in ionic strength (0.5 M NaClO 4 ), the
proportion of sorbed Np (V) does not exceed10% for all studied drugs.To determine the preferred
sorption of radionuclides by variousminerals of rocks used the methods of alpha-track
radiography,combined with scanning electron microscopy and energy-dispersivespectrometry. The
sorption experiment with polished sections was carried out at pH6.0 to 8.9; at zero ionic strength and in
a 0.5 M NaClO 4 solution .It was found that the distribution of Np (V) and U (VI) located indissolved state,
differs from the distribution of Np (V) and U (VI) included incomposition of bentonite colloids. So, in the
first case, the sorption of 237 Np and 238 U passesunevenly and depends on the mineral composition of
the polished section (observedpredominant sorption of Np (V) on Fe, Mn, Ti, Sn oxides). Sorption of
radionuclides,included in the composition of bentonite colloids does not depend on the mineral
phases,forming the rock, and occurs uniformly, only in a solution of strongelectrolyte (0.5 M NaClO 4 )
aggregation of bentonite colloids is observed and the samplecharacterized by an uneven distribution of
alpha tracks.Apparently, the mechanism of interaction of bentonite colloids containingNp (V) and U (VI),
with rocks is determined not by chemisorption, butelectrostatic effects of interaction of colloids with a
surface.supported by a grant from ISTC (2377).126

Page 127

SOLUBILITY OF URANIUM DIOXIDE IN MELTS OF THE SYSTEMLi 2 WO 4 - Li 2 W 2 O 7 UNDER AN INERT

ATMOSPHERESemenovykh V.V., Afonichkin V.K., Khrustova L.G., Moskalenko N.I., Molchanova
N.G.Institute of High-Temperature Electrochemistry, Ural Branch of the Russian Academy of
SciencesIsothermal saturation method using chemical andvoltammetric monitoring of the concentration
of dissolved uraniumthe effect of temperature and composition of the salt medium on the solubility of
UO 2 inmolten mixtures (1-x) Li 2 WO 4 - xLi 2 W 2 O 7 (x = 0 ... 0.5 ppm, step 0.05 ppm)
underatmosphere of purified helium at temperatures from the liquidus line to 940 o C instandard 3-
electrode cell. The container for the melt was a platinumcrucible, which also served as an auxiliary
electrode. Workingthe electrode was a gold plate with a surface area of 0.64 cm 2 . INa semi-submerged
in the melt was used as a reference electrodetungsten wire ∅ 2 mm. The melt samples were taken by
pulling it intoquartz tube ∅ 5 mm using an evacuated sluice device,which prevented air from entering
the cell. Oxidative -the recovery potential of the system under study was kept constant withusing a
tungsten wire placed on the bottom of a platinum crucible.The investigated electrolyte was prepared
immediately before the fusion experiment.thoroughly mixed weighed portions of tungsten trioxide and
lithium tungstate inplatinum crucible. Uranium was introduced into the melt in the form of a sample of
large-crystallineUO 2 , specially prepared by electrolysis of a tungstate melt, or in the formsintered
tablets UO 2 .It was found that with increasing temperature, the concentration of Li 2 W 2 O 7 in the
meltthe solubility of uranium increases. At a maximum temperature of 940 for Csolubility increases from
0.55 to 7.98 wt% with increasing concentrationLi 2 W 2 O 7 from 11.11 to 100 mol%. With an increase in
temperature from 770 to 940 о Сthe uranium solubility increases from 0.47 to 0.55 wt% at a
concentration of Li 2 W 2 O 7equal to 11.11 mol.%. In pure lithium divungstate, the solubility of
uraniumincreases from 5.60 to 7.98 mass% with an increase in temperature from 835 to 940 o C.A
conclusion was made about the chemical mechanism of dissolution of UO 2 in tungstate melts.The
results of the experiments performed form the basis of the thermodynamicmodels of the studied
system.127

Page 128

RESTORATION TECHNETIA (VII) WITH HYDRAZINE ANDHYDROXYLAMINE IN HYDROCHETIC

SOLUTIONSSemin V.A., Abramov A.A., Ermakov A.I., Kashirin I.A.Moscow State University M.V.
Lomonosov, Faculty of ChemistryControl of 99 Tc content in environmental objects around its
sourcesemissions is very important due to its increased migration capacity andaccumulation by aquatic
plants and organic part of soils and bottomdeposits. Development of methods for the extraction of
technetium from environmental sampleswill allow conducting research on the study of the patterns of
behavior of technetium inenvironment and use the results obtained to solveradioecological tasks. As the
basic operations used forconcentration of technetium from large volume water samples are
consideredreduction of technetium (VII) to technetium (IV), coprecipitation of the latter with
hydroxideiron and extraction chromatography using TEVA resin.In the present work, the method of LC
spectrometry was used to studykinetics of the reduction reaction of technetium (VII) to technetium (IV)
in an aqueous solution withusing hydrazine and hydroxylamine as reducing agents. Reactionswere
carried out in hydrochloric acid medium using trace amounts of Tc ininitial oxidation state +7. To
determine the change in the ratio of valenceforms during the reaction, we used the method of liquid
extraction (solution of TTS inchloroform 5 mmol / l) with preliminary stabilization of technetium forms in
solution 2M NaOH and the method of ZhS-spectrometry.Based on the experimental data, the kinetic
equations forreactions in hydrochloric acid solution.The kinetic curve data show that the reduction
reactiontechnetium (VII) hydroxylamine is characterized by a second-order equation inoxidizing agent
and is inhibited by the reaction product. Possible causes
consideredinhibition.Establishedwhatmechanismrecoverytechnetiumhydroxylamine includes two stages
with the formation asan intermediate product of the oxyhydrazine radical.128

Page 129

MIGRATION OF RADIONUCLIDES IN SOILS OF THE MIDDLE ZONESURFACE STORAGE OF GLAZED

RWSukhova Yu.V., Titaeva N.A. 1State Unitary Enterprise MosNPO "Radon",1 Moscow State University
M.V. LomonosovThe paper presents the results of studying the distribution of radionuclides and
theirmigration in the near-surface storage of vitrified radioactive waste of lowand the average level of
activity in the State Unitary Enterprise MosNPO "Radon".During the opening of the storage facility, about
60 soil samples were taken from various pointsnear the storage area. Radiometric and radiochemical
analysis performedsoil samples, determined the physical, chemical and mechanical characteristics of the
soil.The matrix for RW NSUA was borosilicate glass with highsodium content. Cesium isotopes accounted
for 97 - 98% of the total radioactivitywaste.Study of the spread of artificial radionuclides in the soil
aroundradioactive waste storage showed the presence of radioactive contaminationonly in the upper
part of the incision (up to a depth of 50 cm).Analysis of waters in contact with glass blocks throughout
the entire periodoperation of the storage facility (12 years) showed that the pH of the water increased
toslightly alkaline (from 7.5up to 8.2),increasedconcentrationionsNa +, K +, Mg 2+ , Cl-, NO 3 -.It was
found that the concentration of Fe ions in contact waters with timegradually decreased (over 12 years - 5
times). Studies have shown thatiron in the form of hydroxide is retained by the buffer filling at the
bottom of the storage. Whenthis, the stabilization of 137 Cs and 90 Sr radionuclides within the storage
facility is associated with theirco-precipitation with Fe hydroxides.In general, research results indicate
storage reliabilityvitrified waste NSUA in storage facilities of the near-surface type, whichcomposed of
loam.129

Page 130

STUDY OF MUTUAL TRANSFORMATIONS ACC AND MACCFOR ETHYLENE BIOSYNTHESIS IN APPLE

FRUITSUSING TRITIUM-LABELED COMPOUNDSToropkina A.S.Institute of Biochemistry. A.N. Bach RASIn
this work, we studied the role of ACC (1-aminocyclopropane-1-carboxylic acid) and its conjugate MACA
(1-malonyl-aminocyclopropane-1-carboxylic acid) in ethylene biosynthesis in apple ( Malus domestyka )
fruits independing on the way they are processed during storage. Ethylene biosynthesis in higherplants
occurs along the following path: methionine - › S-adenosyl-methionine - › ACK -› Ethylene. One of the
ways to regulate ethylene biosynthesis is the formationConjugate ACC - Matzke . At present, the question
remains open to the contrary.the transformation of MACC into ACC .To determine the ratio of ACC -
MACA in apple fruits, we usedtritiated compounds. The preparation of 3 H-ACC was carried out by the
method of thermalactivation of tritium. The preparation was purified using thin layer
chromatography.The conditions for obtaining 3 H-ACC with a specific radioactivity of 0.15 TBq / g were
found, andradiochemicalpurity 98%.3 H-MACA synthesizedof3 N-ACKandethylmalonyl chloride in the
presence of NaOH according to the scheme proposed in [1].The technique was adapted to trace amounts
of 3 H-ACC with control of the yield3 H-MACK using radiochromatography. Then microsynthesis of 3 H-
MACA was carried out , forwhich used 40 MBq 3 H-ACK.The obtained labeled preparations were used to
study the interconversionsACC and Matzke apples two varieties, differing ripening times:
Antonovkaordinary and Mantuan (Moldova). Results obtained on the effect of treatmentssolutions of
the antioxidant butyloxyanisole and a complex preparation 2-chloroethylphosphonic acid and metacide
per precursor ratiobiosynthesis of ethylene ACC and MACA in apple fruits.This work was supported by
the RFBR grant No. 03-03-32410.1. KM Kalantari, AR Smith, MA Hall // Plant Growth Regulation. 2000. V.
31.P. 183-193.130

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SORPTION OF Np (V) ON GOETHITA AND HEMATITIS IN THE PRESENCEHUMIC ACIDSKhasanova

A.B.Moscow State University M.V. LomonosovThe presence of organic matter, in particular humic (HA)
andfulvic acids (FA), significantly affects the interaction of actinides withsurface of minerals. The study of
this factor is an important parameter inmodeling the migration behavior of actinides in environmental
objects andto assess the safety of disposal of radioactive waste.Sorption of 237 Np (V) on synthesized
samples of goethite (α-FeOOH) and hematite(α-Fe 2 O 3 ) was investigated depending on the ionic
strength and pH of the solution in the presence ofvarious HA preparations (45 mg / l). The commercial
preparation HA was used( Humintech Ltd, Düsseldorf) and formaldehyde modified
samplecopolymerization of the parent drug and hydroquinone (HQ). Syntheticmineral colloids of
goethite and hematite were characterized by XRD methods,SEM, potentiometric titration, the free
specificsurface and porosity.During the experiments, an increase in the sorption of Np on goethite α-
FeOOH inthe presence of HA preparations in the region of low pH values, and in the case ofthe use of
the modified HQ preparation sorption of neptunium is essentialabove, in contrast to the commercial
sample of the Civil Code. It was determined that the balance ingoethite-Np-HA system is established in
less than 3 days.In the experiment on sorption of Np on hematite α-Fe 2 O 3in the presencemodified
preparation HQ, as well as in the experiment with goethite α-FeOOHan increase in the sorption of
neptunium in the region of low pH values was found, however, atthe use of an unmodified drug has no
significant effectwas observed.As in the case of the experiment with α-FeOOH, and with α-Fe 2 O 3, a
decrease inconcentration of modified and unmodified HA preparations in solutionwith a decrease in pH,
which indicates the formation of a ternary complex on the surface.This work was supported by a grant
from US DOE - CRDF (RUC2-20008 MO-04).131

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Curium alloys with ironT.A. ChernakovaFSUE GNTs RF "Research Institute of Atomic

Reactors"DimitrovgradExploredsamplesystems244 Cm – Fe,receivedwayhigh-temperature vacuum
condensation of vapors of metallic curium oniron substrate. Found intermetallic compounds: Cm 2 Fe
17fromhexagonal crystal lattice and CmFe 2with a cubic lattice.The absence of mutual solubility of the
system components at room temperature was established.temperature. The effect of high alpha
radioactivity of the nuclide 244 Cm oncrystal structure of the detected phases.132

Page 133

INTERACTION OF "HOT" (1600-2000 K) TRITIUM ATOMSWITH COLD (77 K) TARGETS OF AMINO

ACIDSAND ALKYLTRIMETHYLAMMONIUM BROMIDESChernysheva M.G., Tyasto Z.A., Pozdnyakova
V.Yu.Moscow State University M.V. Lomonosov, Faculty of ChemistryAs a result of reactions occurring
when "hot" (1600-2000 K) hitstritium atoms into cold (77 K) targets, labeled compounds are formed.
Substitutionprotium to tritium at the CH bond leads to the production of a labeled maternalcompounds,
while the interaction of tritium atoms with functional groupsmolecules can lead to modification of the
original target molecules. Ratiospeeds of the main (formation of the labeled parent compound) and
sidereactions depends on the energy of atoms, which can change due to non-reactivecollisions with
target molecules. To predict resultsinteractions of atomic tritium with targets of complex chemical
compositionit is necessary to study the basic laws of the system under study on simplemodel
substances.In this work, we study the interaction of tritium atoms,obtained during the dissociation of
tritium molecules on a tungsten wire in the rangetemperatures 1600-2000 K, with cold targets of amino
acids (homologous seriesalpha amino acids from glycine to norleucine, aspartic acid and lysine)
andalkyltrimethylammonium bromides (from dodecyl to cetyl radical).The experiment was carried out
under conditions of direct flight of tritium atoms from the atomizer totarget cooled with liquid nitrogen.
After removal of the labile label, the labeledamino acids were isolated using ion exchange column
chromatography, andalkyltrimethylammonium bromides - using thin layer chromatography.
Founddependence of the ratio of the rates of the main and side reactions on the energy of the
incidenton the target of tritium atoms and the length of the hydrocarbon radical of the investigated
substances.To interpret the results obtained, we used data on isotopicthe effects of the reaction of
atomic tritium with ordinary and deuterated glycine.This work was supported by the RFBR grant No. 03-
03-32410.133

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OXIDIZING AND REDUCING PROPERTIESOF MODIFIED HA RATIO TO Np (V) AND Pu (V)Shcherbina

N.S.Moscow State University M.V. LomonosovHumic acids (HA) are natural polyelectrolytes,
widelycommon in nature and capable of significantly influencing migrationradionuclides. Due to the
structural features, HA molecules can participate asin complexation reactions and in redox reactions
withmetal ions. The aim of the work was to find HA preparations capable ofreduce Np (V) and Pu (V) to
lower oxidation states. For this, HAs weremodified by the formaldehyde copolymerization reaction of the
original preparation(Powhumus) and a modifier (hydroquinone, pyrocatechol, benzoquinone,
naphthoquinone andanthroquinone) in various mass ratios. The drugs received werecharacterized by
potentiometric titration, 13 C-NMR, elementalanalysis and IR spectroscopy, the content of carboxyl
groups was determinedacetate method, as well as redox capacity.To determine the ability of these drugs
to reduce Np (V) and Pu (V),kinetic experiments were carried out, according to the results of which it
was found thatPu (V) is reduced by all HA preparations, including unmodified ones.The recovery of Np
(V) is rather slow and is observed only fordrugs modified with hydroquinone and pyrocatechol.
Moreover, the speedrecovery increases with an increase in the proportion of the modifier in the
preparation.To clarify the role of the modifier, an experiment was carried out onreduction of Np (V) and
Pu (V) with pyrocatechol and hydroquinone at their variousconcentrations. It was found that the
recovery of plutonium by unmodifiedwith the HA preparation completely proceeds in less than 10
minutes. The restorationPu (V) with pure catechol showed that up to 50% of plutonium is reducedin less
than 50 minutes. Recovery of neptunium with pyrocatechol at the sameconditions for 350 hours does
not exceed 10%. With increasing concentrationpyrocatechol, the recovery rate is significantly
increased.The work was carried out within the framework of the US DOE - CRDF project (RUC2-20006
MO-04).134

Page 135

Department of Physical ChemistryJury:Matveenko V.N.professor, doctor of chemical sciences -

chairmanDurov V.A.professor, doctor of chemical sciences - deputy chairmanKharlov A.E.n. researcher,
Ph.D. - secretaryVorobiev A.Kh.professor, doctor of chemical sciencesKasaikina O.T.professor, doctor of
chemical sciencesM. V. Korobovprofessor, doctor of chemical sciencesKuzmenko N.E.Professor, Doctor of
Physical and Mathematical SciencesPupyshev V.I.led. n. researcher, Ph.D.Roshchina T.M.Associate
Professor, Doctor of Chemical SciencesSafonov V.A.professor, doctor of chemical sciences135

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CHEMICAL SENSITIZATION PMK AgHalAbisheva A.B., Prosvirkina E.V.Kemerovo State

UniversityDevelopment of new generation photographic materials production methodswith an
adjustable level of light sensitivity is an urgent task.This work is devoted to the study of the effect of 1,1-
dimethyl-2-selenourea onsensitometric characteristics of flat AgBr microcrystals (PLC). With the aim
ofdetailed study of the effect of this sensitizer, carried out a chemicalsensitization of AgBr microcrystals
at various concentrations of seleniumsensitizer and the subsequent stage of photographic
processing.The object of the study was AgBr PMC (average d eq. = 2 μm,With v = 28%, St = 97%).
Chemical sensitization was carried out according to the generally acceptedmethodology. In the process
of chemical maturation, the following additives were used: 1.1 -dimethyl - 2 selenourea (C 3 H 8 N 2 Se),
hydrochloric acid (HAuCl 4 ).During the experiment, the concentration of the selenium sensitizer was
varied. Forthe comparison of the results of the study was carried out with a sulphurous-gold
sensitization(C [Na 2 S 2 O 3 ] = 1 * 10 -5 mol / mol Ag, C [HAuCl 4 ] = 1 * 10 -5 mol / mol Ag). resultsThe
studies performed are shown in Fig. 1.0ten20thirty4050600, E + 001, E-065, E-061, E-051, E-04С [C 3 H 8
N 2 Se], mol / mol AgS01234five67S0.85S0.2gD0γ , D 0Fig. 1. Dependence of photographic
characteristics of AgBr PMC depending onselenium sensitizer concentrationThe experiment showed that
chemical sensitization withthe use of 1,1 - dimethyl - 2 selenourea was found to be more effective;the
best results for the studied PMC were obtained at a concentration of a givensensitizer 1 * 10 -5 mol /
mol Ag.136

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CHEMILUMINESCENCE AT OXIDATION OF POLYVINYLALCOHOL UNDER THE ACTION OF HYDROGEN

PEROXIDEAgeeva A.F., Zimin Yu.S., Borisov I.M., Monakov Yu.B.Bashkir State UniversityIn this work,
chemiluminescence (CL) was detected in the visible regionspectrum during oxidation of polyvinyl alcohol
(PVA) under the action of peroxidehydrogen in the presence of iron (II) sulfate in aqueous solutions (90 °
C, [PVA] 0 =0.2 ÷ 7.0% wt., [Н 2 О 2 ] 0 = 0.02 ÷ 1.50 mol / L, [FeSO 4 ] 0 = (0.5 ÷ 7.0) ⋅10 –4 mol / L).
INmodel systems "PVA + H 2 O 2 + O 2 + H 2 O", "PVA + O 2 + FeSO 4 + H 2 O" and "H 2 O 2 +О 2 + FeSO 4
+ Н 2 О »chemiluminescence is not observed.The kinetic curve of the change in the CL intensity in the
reaction system "PVA+ Н 2 О 2 + О 2 + FeSO 4 + Н 2 О "passes through the maximum, which
characterizes the emitterluminescence as an intermediate product of liquid-phase oxidation of
polyvinylalcohol.The dependences of the maximum intensity of the CL signal (I max ) and the timeits
achievement (t max ) from the initial concentrations of polyvinyl alcohol, peroxidehydrogen and iron (II)
sulfate. At the same time, it was established:1. The maximum intensity of the CL signal increases with an
increase in the initialconcentration of polyvinyl alcohol. With [PVA] 0> 2% of the mass. observedslowing
down the growth of the glow intensity. Time to reach maximumthe CL signal intensity is practically
independent of the PVA concentration.2. The dependences of I max and t max on the initial
concentration of hydrogen peroxide haveextreme character. With increasing [Н 2 О 2 ] 0up to 0.2 mol / l
maximumthe intensity of the glow increases, and with a further increase in the concentration of Н 2 О 2-
falls. The time to reach I max also increases to the value [Н 2 О 2 ] 0 = 0.8 mol / L,and then decreases
slightly.3.With an increase in the initial concentration of iron (II) sulfate, the maximumthe CL signal
intensity increases linearly, and the time to reach I max - linearlyfalls.The obtained experimental results
are explained in terms of a radicalschemes of liquid-phase oxidation of PVA. Likely emitters of
chemiluminescenceare carbonyl-containing compounds formed in the elementary actdisproportionation
of peroxyl radicals.137

Page 138

REGULARITIES OF CHANGING THE ENERGY OF ADSORPTION OF SOMEANIONS AND MOLECULES ON THE

SURFACE OF GALENITEAzhigulova R.N., Ospanov Kh.K.Kazakh National University. al-FarabiThis paper
presents the results of modeling adsorption processesof some ions and molecules on the surface of a Pb
9 S 9 galena cluster carried out atusing quantum chemical calculations using the PM3 method, which is
included in the softwarecomplex MORAS 7.0. Calculated adsorption energies defined as the
differencethe total energy of the mineral - adsorbate system and the total energies of the mineral and
adsorbate inisolated state. The next series of changes in the adsorption energy was compiledanions and
molecules on the surface of the Pb 9 S 9 galena cluster :OH> SH> ECG> BCG> Un-> Cl> Br----> I-> HSO-4 >
O 2 > Cl 2 > H 2 OThe results of our calculations indicate that forOH is characterized by a higher
adsorption energy than other singly charged anions.It is known that OH---ion is formed on the surface of
sulfide minerals inas a result of their oxidation and hydrolysis during preparation (grinding) processes.For
halide ions, a regular decrease in Eads and ∆Q is observed in the seriesCl> Br-> I, corresponding to the
formation of a less strong covalent bond attransition from chloride to iodide ion. The issue of adsorption
requires separate considerationsulfur-containing compounds most commonly used in flotation
processes.We have calculated the adsorption characteristics of compounds such as SH---,ethyl xanthate C
2 H 5 OCSS (ECG), butyl xanthate C-4 H 9 OСSS (BKG), unitiolCH-2 (SH) CH (SH) CH 2 SO (Un). The
calculation results show that the maximumE-3-ads in this group of compounds is observed for the
sulfhydryl ion.The energy of adsorption of unitiol is slightly lower than that of xanthogenates,despite the
fact that it contains two sulfhydryl groups.It is known that in aqueous solutions, unitiol forms
stablecomplex compounds of the composition PbUn (pK = 17.42) and PbUn 2 (pK = 25.05). Shouldexpect
that, under certain conditions, unitiol can be successfullyused in the processing of lead ores.138

Page 139

PERTURBATION OF THE STATES OF THE RIDBERG ATOM A **NEUTRAL ATOM BAlyabyshev S.V.Moscow
State University M.V. LomonosovInvestigation of spectroscopy of Rydberg states of nanoclusters and
particles,adsorbed on the surface of a solid, it is convenient to carry out usingmultiple scattering theory,
which describes the motion of a weakly boundelectron in an effective force field created by a positively
chargedion and other fragments of the system, and operates with single-center operatorsscattering
[1].Within the framework of the generalized finite-radius potential (FCR) method, it is proposedthe
procedure for calculating the single-center scattering operator on isolated centers,which, unlike the
widely used method of the zero-radius potential(PNR) include in the theory P - scattering and higher
angular momenta La weakly bound electron of a Rydberg atom A ** on disturbing particles.The paper
also proposes a scheme for accounting for the influence of a long-rangeinteractions , which allows the
theory to be extended to intermediatecenter-to-center distances (of the order of the electron
wavelength), which representof greatest interest for describing nanoclusters, including their interaction
withsurface of a solid.Specific calculations and discussion of the results were performed for the
system...HeNa-**1. G.V. Golubkov, G.K. Ivanov. Rydberg states of atoms and molecules andElementary
Processes with Their Participation, URSS, Moscow (2001).139

Page 140

THERMODYNAMIC PROPERTIES OF O- SemiquinoneRODIA COMPLEXArapova A.V., Smirnova N.N.,

Abakumov G.A., Bubnov M.P., Kozhanov K.A.Institute of Organometallic Chemistry. G.A. Razuvaev RAS,
Nizhny NovgorodOf great interest is the study of the thermodynamic properties of the
complexdicarbonyl rhodium with 3,6-di- tert - butyl - o- semiquinone, whiskerswhich have the unique
property of bending reversibly under the action of light andheat [1,2]. In this work, the method of
adiabatic vacuum calorimetry was used to studytemperature dependence of the heat capacity = f (T) of
the dicarbonyl-rhodium complex with o -semiquinone in the range 6 - 355 K with an error of mostly
0.3%. In the range of 6 - 205 Kheat capacity increases smoothly with increasing temperature. In the
temperature range 205 -355 K, three anomalies are observed: the first in the range 205 - 234 K, which
resemblesthe H-type phase transition according to McCallough's classification [3], and two others inthe
shape of a “diffuse hump” in the ranges 266 - 315 K and 316 - 345 K, respectively.opCThe experimental
data on = f (T) were used to determine the enthalpies and entropiesphysical transitions, thermodynamic
functions are calculated:,,in the range from T → 0 K to T = 355 K.opC) 0 (H) (Hoo-Τ) (So Τ)(-) Τ(0ooHGThe
fractal dimension D is estimated - the most important parameter of the fractalvariant of the Debye heat
capacity theory. According to [4], D = 1 corresponds to a chainstructure, D = 2 - layered and D = 3 -
spatial. Found for the researchedcomplex, the value D = 1.2 means that it has a predominantly
chainstructure, which corresponds to its crystal structure [2].1. G.A. Abakumov, V.I. Nevodchikov. DAN
USSR. 1982. T. 266. No. 6. S. 1407-1410.2.CW Lange, M. Foldeaki, VI Nevodchikov, VK Cherkasov, GA
Abakumov,CG Pierpont, J. Amer. Chem. Soc., 1992, v. 114, No. 11, p. 4220.3. Phisics and Chemistry of the
Organic Solid State, Mir, Moscow, 1967, p. 76-78.4.T.S. Yakubov. DAN USSR. 1990. T. 310. S. 145-149.140

Page 141

PHYSICAL AND CHEMICAL REGULARITIES OF FUNCTIONINGMICROBIAL MEDIATOR REAGENTless

BIOSENSORBabkina E.E., Ponamoreva O.N., Alferov V.A.Tula State UniversityThe ability of mediators to
quickly transfer electrons to the electrode,generated by whole cells during the oxidation of substrates, is
used forcreation of amperometric biosensors and biofuel cells. Practicalpoint of view, it is more
convenient to use immobilized onelectrode surfaces of mediators, which allows you to create reagent-
free systemsanalysis. In the majority of works in the field of mediator enzyme biosensorsresearchers use
ferrocene and its derivatives, the possibilities of usingmediators of this type in combination with whole
cells are only being investigated. In
thismessagepresentedresultscomparativestudyingreactionselectrocatalytic oxidation of glucose by
bacteria Gluconobacter oxydans inpresenceinsolublemediatorsferrocenerow:ferrocene,1,1'-
dimethylferrocene, ferrocene carboxaldehyde and acetylferrocene.The system under study was a
graphite electrode with immobilizedmediator and cells of microorganisms and silver chloride reference
electrode. Establishedthat ferrocene and 1,1'-dimethylferrocene can be used as mediatorselectron
transport between membrane-localized dehydrogenases of bacteriaGluconobacter oxydans and an
electrode. Acetylferrocene and ferrocene carboxaldehyde inthe system under study did not show
mediator properties. So the introductionacceptor (carbonyl) substituents in the petadienyl ring
significantly impairsmediator properties of ferrocene derivatives. Determined concentration
intervalsglucose were 5-50 and 5-70 mM for biosensors modified1,1'-dimethylferrocene and ferrocene,
respectively. Kinetic dependences of speedelectrocatalytic oxidation of the substrate by bacteria on the
glucose concentrationinterpreted using the steady state equation in the frameworkmodified model of
the enzyme electrode for determining the limiting stagethe processes taking place in the receptor
element. It was found that for the studied microbialof mediator electrodes in a steady state, the limiting
stage isenzymatic reactions of glucose oxidation with the participation of a mediator, but not diffusion of
the substrateto the active centers of bacterial enzymes.141

Page 142

ENTHALPIC CHARACTERISTICS OF UREA INTERACTIONSAND ITS DERIVATIVES IN AQUEOUS SOLUTIONS AT

298.15 KBatov D.D., Ivanov E.V., Batov D.V., Korolev V.P.Ivanovo State University of Chemical
Technology,Institute of Solution Chemistry RAS, IvanovoUrea and its derivatives are promising
biologically activeconnections. The drug mebikar is widely used in medicine.(tetramethyl-bis-
urea,2,4,6,8-tetramethyl-2,4,6,8-tetrazabicyclo [3.3.0]octandion-3,7), which has a wide range of
medicinal properties. At the same time beforeto date, no unified generally accepted conclusions about
the structureaqueous solutions of urea and its alkyl derivatives, as well as changesthermodynamic
properties of such systems under the influence of their composition and external conditions.The above
has determined the necessity and content of this work.In order to determine in the framework of the
McMillan - Mayer formalism (equation 1)enthalpy coefficients of pair and triple interactions of
moleculesthe solute enthalpies were measured by the calorimetric method(∆ pd H o ) aqueous solutions
of urea (U), 1,3- dimethylurea (DMU), 1,1,3,3-tetramethylureas (TMU) and mebicar (MBU) at 298.15 K,
as well as enthalpydilutions of TMU and MBU solutions in D 2 O.∆ pd H ( m N → m K ) = h 22 ( m K - m N )
+ h 222 ( m K2 - m N2 )(1)Here m H and m K are the initial and final concentrations of amides.Analysis of
the results obtained showed that sequential methylationurea leads to an increase in the values of the
enthalpy coefficients of pairedinteractions. At the same time, it was found that h 22 mebikar in water
and heavy waterhave strongly negative values. It is noted that negative valuesisotopic effects δ ( h 22 ) =
h 22 (D 2 O) - h 22 (H 2 O) are characteristic of compounds withpositive enthalpies of dilution (U and
MBU) and, conversely, positivethe δ ( h 22 ) values are typical for compounds with negative
enthalpiesdilutions (DMU and TMU).The work was carried out with the financial support of the Russian
Foundation for Basic Research, project No. 04-03-32957.142

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DISSOCIATION OF NITRIC ACID MOLECULE:NON-EMPIRICAL DESCRIPTIONBezrukov D.S., Novakovskaya

Yu.V., Stepanov N.F.Moscow State University M.V. Lomonosov, Faculty of ChemistrySolvation processes
play an essential role in natural, includingatmospheric, phenomena. Recently, in connection with the
development of computingcapacities pay great attention to quantum mechanical modelingprocesses in
condensed phases. In particular, there are works devoted tothe study of solvation of acids by water
nanoclusters. In this work, empiricallythe dissociation of a nitric acid molecule surrounded by water
molecules has been studied.Considered as small clusters, with the number of water molecules from 1 to
8,and relatively large systems containing up to 100 molecules. Modelingsmall systems is performed in
the approximation of the limited Hartree-Fock method withtaking into account the second-order
corrections to the energy according to the Meller-Plesset perturbation theory withbasis 6-31 ++ G **.
When studying large systems, the method of effectivefragments, allowing you to correctly describe the
impact of the second and subsequentsolvation spheres, and the solvent continual model.The structures
of the individual zwitterion NO 3- … H 9 O 4+ andalso contact or separated ion pair NO 3- … (H 2 O) n … H
9 O 4+ , ratedthermodynamic characteristics of the process of its formation and subsequentstabilization.
The effect of the solvation shell on the stability of the contaction pair H 3 O + ... NO 3- . Experiments
performed with different numbers of moleculeswater allowed us to obtain the dependence of the
solvation energy of a pair of NO 3- and H 3 O + frommolecular size of the system and by extrapolating
this dependence toinfinite size to estimate the energy of hydration. The dependence of
"moleculardissociation constants "of nitric acid on the number of solvating molecules hasasymptotic
limiting value, which makes it possible to estimate the dissociation constant inliquid water. The data
obtained are in good agreement withexperimental estimates.This work was supported by the Russian
Fund for FundamentalResearch, the Foundation for the Promotion of Domestic Science and the Ministry
of EducationRF within the framework of the Leading Scientific Schools project NSh-1275.2003.3.143

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MODELING ELECTRON TRANSFER IN THE REACTION CENTERPHOTOSYNTHETIC PROTEIN SYSTEMSBelov

A.S., Yurkov I.I.Moscow State University M.V. LomonosovThe main function of photosynthetic protein
systems isconversion of light energy into the energy of chemical bonds. The key stagephotosynthesis in a
bacterial cell is the phototransfer of an electron from a reactionthe center of bacteriochlorophyll dimer
(P) to bacteriopheophytin (H) through the bridge -bacteriochlorophyll monomer (B). This process can be
represented as a diagram:PBH → P * BH → P + B - H → P + BH - , where * denotes an excited state. In
thisThis work has constructed a model that describes the dynamics of electron transfer from P to B ina
modified system in which access to the electron acceptor H is blocked [1].Calculation of full potential
energy surfaces and an accurate description of the quantumnuclei dynamics are impossible for proteins.
To analyze nuclear dynamics, one can usekinetic modeling, in which the motion of a wave packet along
an electronic termis represented as a chain of successive first-order reactions, and movement in the
regionconical intersections - as a set of parallel reactions [2]. The rate constants of suchreactions are
determined in terms of the travel times of the wave packet in electronic terms. On thebased on the
absorption spectra P + B - H and stimulated emission P * BH with femtosecondresolution [1] determined
the travel times of the wave packet in electronic termsand the probability of transition between terms.
This data was used to buildkinetic model of the process, on the basis of which the dependence of the
populationfinal state (P + B - ) versus time. The obtained result was compared with
experimentaldata.This work was supported by the Russian Foundation for Basic Research(grant 03-03-
32521).1. Yakovlev AG, Shkuropatov AY, Shuvalov VA Nuclear wavepacket motionproducing a reversible
charge separation in bacterial reaction centers // FEBS Lett. -2000. - V. 466. - P. 209-212.2. Eremin V.V.,
Pakhomova Yu.Yu., Kuzmenko N.Ye. Kinetic modelingfemtosecond dynamics of nuclei in systems with
quasi-crossingterms // J. Phys. chemistry. - 2004. - T. 78. No. 5. - S. 854-860.144

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DONNAN POTENTIAL AND LIMITING CURRENTS IN THE SYSTEMMEMBRANE MF-4SK - CHITOSAN

SOLUTIONBobylkina O.V., Kulintsov P.I., Bobreshova O.V.Voronezh State UniversityChitosan is a
biocompatible polymer that is used inmedical, food, pharmaceutical industry. Necessitystudies of the
properties of electromembrane systems with solutions containing chitosan,is determined by the
prospects of its electrodialysis purification from mineralimpurities, mainly sodium chloride.In this work,
the quasi-equilibrium potential difference(Donnan potential) at a separate boundary of the MF-4SK
membrane inindividual sodium chloride solution (0.01 mol / l) and with the addition of variousamounts
of chitosan chloride (0.01 and 0.05 mol-eq / l) using the original cell,proposed in [1]. It was shown that
with an increase in the amount of chitosan chloride insolution, the measured potential difference
decreases. Chitosan polycationis attracted to the negatively charged matrix of the membrane and blocks
partfixed ions, which leads to a decrease in the effective charge of the membrane andreducing the
potential difference between the membrane and the solution.On a plant with a rotating diaphragm disk,
differentialvolt-ampere characteristics of the MF-4SK membrane in the above solutions.It is shown that
the dependence of the limiting current on the square root of the angular velocitymembrane rotation in
systems with chitosan chloride is linear, but does not come outfrom the origin, which is typical for
systems with sodium chloride solution. Suchwe associate behavior with the presence near the
membrane-solution interfacereactions between hydroxyl ions of water and chitosan polycation.
Resistanceelectromembrane system with chitosan in the limiting state is higher than insodium chloride
solutions. This is due to the formation of a precipitate by the same reactionthe main form of chitosan,
which has no electrical conductivity.1. Bobreshova O. V., Kulintsov P. I., Novikova L. A. Interphase
differencepotentials in electromembrane systems with amino acid solutions //Sorption and
chromatographic processes. 2003. Vol.3. No. 3.P. 310 - 319.145

Page 146

CALCULATION OF PORPHYRIN PHOSPHORESCENCE BY THE METHODDENSITY FUNCTIONALVakulina A.V.,

Minaev B.F., Khomenko E.M., Yashchuk L.B.Cherkasy State Technological UniversityPorphyrins play a
central role in such important biological processes,like photosynthesis and respiration. In recent years,
porphyrins have been widely used inas active media for photodynamic therapy, for nonlinear optics,
fordevelopment of molecular electronics and photonics devices. Uniquephotochemical and
photophysical properties of porphyrins to a large extentdue to the specifics of their triplet states. It has
long been established that onlymetalloporphyrins give noticeable phosphorescence.Density functional
method B3LYP taking into account linear and quadraticresponse in the 3-21 G basis, the absorption and
phosphorescence spectra were calculatedporphine, as well as its complexes with internal atoms (Mg, Zn)
(table).Table. Calculated parameters of phosphorescence of porphyrinsMolecule E (S 0 )
completeSTE→∆)(0STM xz→)(0STM zx→xkzkPorfin08027.984-1.1105.1-five10 -×7105 -×4106.1 -×8105.2
-×Mg-Porf01075...1182-1.41five108.7 -×-610 -018.06102 -×Zn-Porf61564...2753-1.46five109.6 -×-4105.1
-×016.0074.0Note : the total energy of the molecule and the dipole moments of the transitions are given
inatomic units.STE→∆- energytransition (eV), is the rate constantradiation from01ST →xxkT spin sublevel
( sec ). For all molecules T1-1 state hassymmetry 3 B 2u .The low emissivity of porphin phosphorescence
is explained bymutual redemption of contributions to the transition dipole moment. In metal-
porphyrinsthe calculation predicts a blue shift of phosphorescence in comparison with porphin, whichis
in qualitative agreement with experiment. As follows from the table, the transitionТ 1 → S 0 is almost
completely polarized perpendicular to the porphin plane and is associated withradiation from the spin
sublevel T x in zero magnetic field. Transition T z1 → S 0 spolarization along the x axis has a negligible
rate constant.146

Page 147

STUDY OF RECEPTOR PROPERTIES OF TET- BUTYL DERIVATIVEKALIX [4] ARENA IN RELATIONSHIP TO

ORGANIC "GUESTS"Validova L.R., Ziganshin M.A., Stoikov I.I., Antipin I.S., Gorbachuk V.V.Chemical
Institute named after A.M. Butlerov KSUIn this work, the static method of vapor-phase gas
chromatographicanalysis process clathration derivative was studied tert -butylcalix [4] arene ( 1 ) and
vaporous benzene at 298 K.12Thermal stability and stoichiometry of saturated supramolecularcomplexes
of "host" 1 with organic "guests" were determined by the methodthermogravimetry. The data obtained
in this work on the receptor properties"Host" 1 were compared with the properties of tert- butylcalix [4]
arene ( 2 ) [1]. It wasit was found that the sorption isotherm of benzene vapors on "host" 1 has a
thresholdthermodynamic activity of the "guest" and the saturation area, indicatingthe formation of a
stable inclusion compound. Similar sorption isothermsvapors of organic "guests" were previously
obtained for calixarene 2 [1]. Shownthat the selectivity of clathrate formation and the dependence of
the stability parametersof calixarene 1 clathrates from the structural characteristics of the "guest"differs
from what was previously observed for calixarene 2 . It means thatcalixarene 1 can be used in artificial
odor recognition systemstogether with calixarene 2 .The work was carried out with the financial support
of the Fundamentalresearch and higher education ”with the participation of CRDF and the Ministry of
Education andscience of the Russian Federation (project REC007), the program "Universities of Russia"
(UR.05.01008).1. Gorbatchuk VV, Tsifarkin AG, Antipin IS, Solomonov BN, Konovalov AI,Seidel J., Baitalov
F. // J. Chem. Soc., Perkin Trans. 2, 2000, P.2287-2294.147

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PACKAGE OF MOLECULAR DYNAMICS DMOD:REPLIC EXCHANGE ALGORITHM, HARD FRAGMENTSV.V.

VanovskyMoscow State University M.V. LomonosovModeling the properties of molecular systems by the
molecular dynamics methodoften requires the calculation of long trajectories of movement, which faces
difficulties,caused by the prolonged presence of the molecule in areas of localminima of the PES
(potential energy surface), the exit of the trajectory from whichrequires a large number of modeling
steps. In the DMOD package developed inour laboratory, one of the modern methods of overcomingThis
problem is the use of the replica exchange algorithm (REMD). The mainapplications of this algorithm are
to create a representative sampleconfigurations and search for the global minimum PES.Recently, more
and more works devoted tomolecular dynamics with rigid fragments. In this case, the “fast”
degreesfreedoms (valence bonds, planar and dihedral angles) are frozen, which allowsincrease the time
step of integration, and thus increase the real lengthtrajectories. Hard fragments are also used in a
number of modifications of the methodQM / MM. The DMOD software package implements an
algorithm for working with hardfragments based on rigid body theory. Using this algorithmhas
advantages over previously used iterative schemesSHAKE / RATTLE due to a more adequate physical
model (preservationphase volume, time reversibility) which is especially important formodeling long
trajectories.The number of atoms in many objects of molecular dynamics researchcan amount to tens
and hundreds of thousands (proteins, nucleic acids).The number of integration steps for modeling, for
example, 1 ns trajectoryhas the order of a million. In this regard, the important question isperformance
of molecular dynamics software packages. One of the mostcommonly used ways to increase productivity
- usingparallel computing. The DMOD software package implements a two-levela parallelization scheme
combined with a dynamic distribution environmentOpenTS loads.148

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SYNTHESIS AND THERMODYNAMIC PROPERTIES OF MANGANITESRARE EARTH ELEMENTS Dy, Gd AND

NdVeryaeva E.S.Moscow State University M.V. LomonosovThe purpose of this work is to study the
thermodynamic properties of manganitesrare earth elements REMnO 3 and REMn 2 O 5 (RE = Dy, Gd
and Nd) by the EMF method withfluorine and oxygen ion electrolytes. To determine
thermodynamicproperties of these compounds were supposed to measure the EMF of the
electrochemicalcells:(-) O 2, Pt | RE 2 O 3 , REOF | CaF 2 | REMnO 3 , REMn 2 O 5 , REOF | Pt, O2(+) (I)An
obligatory step in setting up an experiment to determinethermodynamic properties of any complex
oxides, including REM manganites,the EMF method with fluorine-ion electrolyte is the proof of
equilibriumelectrodes. For this, preliminary annealing of the electrode mixtures was supplied.REOF -
REMnO 3 - REMn 2 O 5(RE = Dy, Gd, Nd). It was found that the DyOF mixture isDyMnO 3 - DyMn 2 O 5
under the conditions of an electrochemical experiment is heterogeneous,therefore, based on the results
of EMF measurements, the temperature dependence was calculatedGibbs energy of the reactionDy 2 O
3 + 2DyMn 2 O 5 => 4DyMnO 3 + 0.5O 2 ,(1)∆G 0 = -2FEIn the case of gadolinium, the interaction of
GdOF and GdMn 2 O 5fromformation of GdMnO 3 and RPF (RPF is the orthorhombic phase in the region
of richGdF 3 ). This fact does not allow to unambiguously correlate the measured values of the EMF
withthe Gibbs energy of a reaction similar to (1). To study thermodynamic propertiesorthorhombic
gadolinium oxyfluoride is planned to measure the emf of cell (II).(-) O 2, Pt | Gd 2 O 3 , GdOF | CaF 2 |
GdOF, RUF | Pt, O2(+)(Ii)The thermodynamic properties of phases in the Nd 2 O 3 -NdOF system are
significantlydiffer from the properties of oxyfluorides of other rare-earth metals, as a result of which
NdOFinteracts not only with NdMn 2 O 3 , but also with NdMn 2 O 5 to form NdMnO 3 .To determine the
temperature dependence of the Gibbs energy of the reactiondissociation of DyMn 2 O 5 and NdMn 2 O
5 :RMn 2 O 5 => RMnO 3 + 1 / 3Mn 3 O 4 + 1 / 3O 2 , ∆G 0 = -2.303RT logP O2the method of
electromotive force with О 2 - ionic electrolyte was used.149

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ANALYSIS OF THE CONFORMATION COMPOSITION OF MONO SUBSTITUTESETHYLINDANEVishnevskaya

E.E., Konovalov V.V., Pimerzin A.A.Samara State Technical UniversityIndan derivatives are valuable
technical raw materials. To optimizeprocesses for obtaining these compounds require thermodynamic
properties.The conformational composition of the compound is an important component inprediction of
thermodynamic properties. Conformational analysis 4-, 5-ethylindans were performed using ab initio
calculations (RHF / 3-21G * - constructionrotation barrier of a substituent in a molecule, RHF / 6-31G * -
determination of the optimalgeometry and relative energy of conformers) and the method of molecular
mechanics withAllinger force field (MMX). The table shows: φ 1 - dihedral anglerotation of ethyl relative
to the aromatic nucleus (the reference point is takenthe position when ethyl is in the plane of the
aromatic fragment and is turned toside of the limit cycle), φ 2 is the dihedral angle characterizing the
deviationlimit cycle from the plane of the aromatic nucleus, γ is the bond angle C ap C ethyl C ethyl ,
andalso the relative energy of the conformers.φ 1 , degreesφ 2 , degreesγ , degrees∆Е, kJ /
molConnectionseConformerD, LconformationsMMXRHF6-31G *(d, p)MMXRHF6-31G*(d, p)MMXRHF6-
31G*(d, p)MMXRHF6-31G*(d, p)1292.589.417.616.8110.7 111.1 0.000.0022196.7 182.617.616.2116.3
115.4 4.273.914-ethyl indan32267.1 270.017.616.9110.8 111.0 0.790.131286.389.217.517.06110.6
111.1 0.000.0022171.9-17.5-116.5-4.35-32270.6 270.817.417.02110.6 111.0 0.000.075-ethyl
indan42354.6-17.5-116.4-3.97-Allinger's force field reproduces the character of potential curvesrotations
of ethyl tops, calculated on the basis of HF / 3-21G * and HF / 6-31G *. MethodMMX indicates the
existence of two additional conformers in 5-ethylindane(conformers 2 and 4), with the ethyl fragment
located in the planearomatic kernel. This is consistent with the potential rotation function of
ethylsubstituent in ethylbenzene using the Allinger force field. The restthe methods presented show
good convergence in relative energy andconformer geometry.150

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STUDY OF THE PbS - PbSe - PbTe Quasi Ternary SystemVolykhov A.A.Moscow State University M.V.
Lomonosov, Faculty of Materials ScienceA number of practical problems require precise knowledge of
phasediagrams of multicomponent systems. To compare different setsexperimental data produced
thermodynamic modeling. Itis reduced to representing the excess Gibbs mixing function for each phase
informherdependenciesfromthermodynamicparametersfortunes(composition, temperature, etc.). The
coefficients of this equation are the parametersinteractions. They are most easily determined if the
dependence is knownthermodynamic properties of the phase on the composition. Using the phase
equilibrium condition,you can build a calculated phase diagram. Practically the same
parametersinteractions are selected to achieve the best descriptionexperimental data.In this work,
within the framework of the chosen model for describing phaseequilibria in the PbS-PbSe-PbTe system,
an expert assessment of the availableliterary data on the coordinates of solidus and liquidus in quasi-
binarycomponents of the system under study, as well as the region of solid solution decomposition. Of
thesedata and thermodynamic properties of the phases, the most adequate set
ofparametersinteraction,welldescribingmostreliableexperimental data.The analyzed dataset was
supplemented with missing data oncoordinates of solidus and liquidus of the PbS-PbSe-PbTe system,
which were determinedus expertly using differential thermal analysis.It was found that the coordinates
of the solidus and liquidus surfaces are satisfactoryconsistent with those predicted. Additionally, the
dependence of the parameterunit cell and microhardness of samples from composition in solid
solutionPb (S, Se, Te). The unit cell parameter of the solid solution according to the dataX-ray phase
analysis obeys Vegard's law.151

Page 152
DETERMINATION OF THE AMOUNT OF KSK-G GRAPPED ON SILICA GELPROTEIN BY ELEMENTAL ANALYSIS
AND POTENTIOMETRYGeyer A.V., Akzhigitov A.O.Moscow State University M.V. LomonosovIn the process
of modifying silica gels with proteins, it is very importantdetermination of the amount of grafted protein.
To do this, use the resultselemental analysis, in addition, in some works to determine the amountof the
grafted protein, titrimetric methods (potentiometric) are used.The work is devoted to comparing the
results of determining the amount of vaccinatedprotein obtained by elemental analysis and
potentiometric titration.We used samples of the following composition: silica gelsKSK-G, KSK-G with
grafted C 16 alkyl groups (KSK-G S16 ), KSK-G S16 withadsorbed protein, silica gel containing protein
linked by groups -H 2 C-HN-glutaraldehyde.In the first case, the amount of grafted protein was
determined based on the changecarbon content in the samples obtained by elemental analysis. In the
secondthe amount was determined by comparing potentiometric titration curvessamples containing
protein, with titration curves of the starting silica gels andconcentration curves of protein titration.Based
on the experiments, the values of the quantitygrafted protein and correlated the data obtained by the
elementalanalysis and using potentiometric titration.152

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FEATURES OF THE FORMATION OF ANODIC ALUMINUM OXIDE INSULFURIC ACID SOLUTIONSGolovataya

S.V., Rezvanova M.O.Belarusian State University of Informatics and RadioelectronicsAnodic aluminum
oxide (AOA) produced by electrochemicalanodizing, is widely used in various industries [1] and finds
newapplication [2]. Continuingworks [3, 4], in this experimentvolumetric growth K
pporousAOA,anodevoltage E aon a stationaryplot and other parametersanodic process in watersolutions
of sulfuric acid (SC), independing on the density of the anodecurrentj
aatvariousconcentrationselectrolyte(0.4, 1.0 and 2.0 M).OfcurvesdependenciesK p = f (j a ), shown in the
figure,it is seen that the increase in densitycurrent and decrease in concentrationelectrolytepromotean
increase in the volumetric growth of AOA.The presence of two sites of saturationcan be explained by the
fact that SCis strong and dual-base.1. Moriyama T., Tsuchida S.Recent Aluminum Alloys forNatural Color
Anodizing in Architectural Use // Sumitomo Light Metal TechnicalReports. - 1992. - V. 33. - Nr. 4. - P. 268 -
278.Current density j a mA cm -21.301.351.401.451.501.551.60Volumetric growth coefficient K p0.4
M1.0 M2.0 M8ten12fourteensixteen182022241234five678ninetenAnode voltageE a , BandbE a = 18.1 +
5.09 ln (j a -0.343)E a = 15.6 + 3.94 ln (j a -0.696)E a = 8.00 + 5.56 ln (j a -0.326)Fig. Dependence of the
coefficient of volumetric growth of AOAK p (a) and stationary voltage E a , V (b) fromcurrent density j a ,
mA cm -2 for 0.4, 1.0 and 2.0 M SC2. S. Shingubara. Fabrication of Nanomaterials Using Porous Alumina
Templates.Journal of Nanoparticle Research. - 2003. - V. 5. - Iss. 1-2. - P. 17 - 30.3. Surganov V.F., Mozalev
A.M., Mozaleva I.I. Volumetric growth of anodic oxideand the rate of electrochemical anodization in
oxalate electrolyte //Applied Chemistry Journal. - 1995. - T. 68. - Issue. 10. - S. 1638 - 1642.4. Surganov
V.F., Mozalev A.M., Mozaleva I.I. Electrochemical speedanodizing aluminum and volumetric growth of
anodic oxide in solutionsorthophosphoric acid // ZhPKh. - 1997. - T. 70. - Issue. 2. - S. 267 - 272.153

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PHYSICAL CHEMISTRY OF SODIUM URANYLMOLIBDATES,FORMED IN THE SYSTEM Na 2 O - UO 3 - MoO

3A.V. Golubev, E.V. SuleimanovNizhny Novgorod State University N.I. LobachevskySynthesized and
investigated by reaction calorimetrysodium uranomolybdates of the composition Na 2 U 3 Mo 9 O 37 ,
Na 4 U 3 Mo 2 O 17 , Na 2 U 3 Mo 4 O 22 ,Na 2 UMo 2 O 10 , Na 6 UMo 4 O 18 , Na 6 U 2 Mo 4 O 21 , Na
2 UMo 2 O 10 4H 2 O. Based on the obtainedthe results, the standard enthalpies of formation of the
obtained compounds were calculated.Samples for research were prepared by sintering NaNO 3 weighed
portions for 300 hours ,UO 3 , MoO 3 (reagent grade), taken in stoichiometric ratios.
Temperaturesynthesis was selected based on the state diagrams of the Na 2 O - UO 3 - MoO 3 system
,presented in [1]. Elemental composition and phase identity of compoundscontrolled using an SEM 515
electron microscope from PHILIPS withenergy dispersive analyzer EDAX 9900 (accuracy was 2-5 at.%)
androentgenometric. X-ray diffraction patterns of powdery samples were recorded usingdiffractometer
DRON-3.0 (radiation CuK α ). Compound Na 2 UMo 2 O 10 on contact withthe atmosphere transforms
into crystalline hydrate Na 2 UMo 2 O 10 4H 2 O. Thermal effects of chemicalreactions were determined
using a modernized calorimeter designed by S.M.Skuratov at T = 298K. The experiments were carried out
in a thin-walled Teflon ampoule,consisting of two vessels: an internal one, where a sample of the test
substance was placed, andexternal - with a solution of hydrofluoric acid (10M). Ratio (solid:acid) was
selected in such a way that dissolution occurred in 10-15 minutes,was at least 50 mg and the
temperature change during dissolution exceeded 0.1 0 СThus, during the study, the standard enthalpies
were determinedthe formation of compounds with the composition Na 2 U 3 Mo 9 O 37 , Na 4 U 3 Mo 2
O 17 , Na 2 U 3 Mo 4 O 22 , Na 2 UMo 2 O 10 ,Na 6 UMo 4 O 18 , Na 6 U 2 Mo 4 O 21 , Na 2 UMo 2 O 10
4H 2 O, the values of which turned out to be(kJ / mol): -11374 ± 5, -6612 ± 3, -7477 ± 4, -3500 ± 1, -6522
± 2, -7607 ± 3 and -4671 ± 1, respectively.For the Na 2 UMo 2 O 10 phase, the standard enthalpy of
hydration was determined to be 28.0 ± 0.6kJ / mol.1. Dion C., Noel A., Laureyns J. // Bull. Soс. Chim. Fr.
1977. No. 11-12. P. 1115-1120.154

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ELECTRICAL PROPERTIES OF APATITO-LIKE OXIDESLa x Ge 6 O 12 + 1.5x (x = 9.33 - 10.22 )Gorshkov M.Yu.,

Neuymin A.D., Polyakova O.N., Dunyushkina L.A.Institute of High-Temperature Electrochemistry, Ural
Branch of the Russian Academy of SciencesLanthanum germanate La 10 Ge 6 O 27 with an apatite-like
structure has a highconductivity and high transfer numbers of ions (p.p.) oxygen in a wide rangeрО 2 [1],
in connection with which this material is considered as an alternative to traditionalsolid oxide
electrolytes with a fluorite structure (for example, dopedzirconium and cerium oxides). It is known that
the electrical conductivity of oxides is sensitive tooxygen nonstoichiometry and, consequently, to a lack /
excess of cations. INIn this work, we studied the effect of La deficiency / excess in the La х Ge 6 O 12 +
1.5x (х =9.33-10.22) on structure and electrical properties.Samples were synthesized using ceramic
technology at an initialT obg. = 1300 ° C, 3 hours and final T compressed. = 1550 ° С, 3-6 hours. The
powder was ground in agatemortar. The density of the sintered samples was about 95% of the
theoretical.The results of X-ray phase analysis showed that all samples are single-phase andhave a
hexagonal structure. Cp.p., measured by the EMF method at 600-1000 ° C andpO 2= 10 5 -10 -16Pa,
close to unity. From temperature dependenceelectrical conductivity, the activation energy was
estimated, which was 0.6–0.8 eV.The dependence of the electrical conductivity on the composition of
the samples was extreme.The maximum values of the conductivity of the La x Ge 6 O 12 + 1.5x section
were observed at x = 10 andwere 1.70 × 10 -2 and 8.85 × 10 -2 S * cm -1 at 700 and 900 ° C,
respectively.According to [2], the structure of lanthanum germanate includes GeO 4 tetrahedra and
channels,formed by lanthanum and oxygen ions, with a large number of unoccupiedpositions. It is
assumed that ion transport occurs along oxygenchannels. The results obtained in this work are discussed
within the framework of this model.1. H. Arikawa, H. Nishiguchi, T. Ishihara, Y. Takita, Solid State Ionics,
136-137(2000) 31.2. L. Leon-Reina, ERLosilla, M. Martinez-Lara, S. Bruque, MAGAranda, J. Mater.Chem.,
14 (2004) 1142.155

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INFRARED AND PHOTOELECTRONIC SPECTRAVAN DER WAALS COMPLEX Cl-... H 2Grinev T.A.Moscow
State University M.V. Lomonosov, Faculty of ChemistryStudies of loosely bound complexes and clusters
formed by atomicand molecular ions are of great interest for understanding the processessolvation and
charge transfer. Recently, thanks to the improvementtechniques of supersonic beams and jets became
possible spectroscopicstudies of such systems with high resolution. In particular, activelycomplementary
methods of infrared (IR) and photoelectronic(FE) spectroscopy. This work is devoted to a comparative
analysis of the selection rulesand intensities of IR and PE spectra for the example of the complex Cl-... H
2 . In both casesexpressions for transition probabilities are obtained, adapted to strictvariational
calculations of nuclear wave functions. IR spectrum intensityobey standard selection rules and are
expressed in terms of matrix elementsoperator of the dipole moment. Simulation of the FE spectrum of
Cl-… H 2 + hν → Cl… H 2 +e-presents a significantly greater complexity due to the presence of
additionalangular momentum of a split-off electron. The expression for the intensities includesmatrix
elements of the transition to the continuous electronic spectrum, whichit is proposed to calculate by
expanding the total electron wave function inmultielectron functions of the fragments of the complex.
Results presentedcalculation of the IR spectrum of the Cl-... H 2 using non-empirical surfacepotential
energy and linear variational method. Calculated spectrumis in very good agreement with those
measured from the transition frequencies.Inconsistencies in the distribution of intensities are explained
by the deviation of the functiondistribution of the complex in a supersonic jet from equilibrium and
exchange reactionsortho- and para-forms of hydrogen.156

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EXTRAINING SOLID SOLUTIONS IN TELLURIDE SYSTEMSCadmium-Zinc Telluride, Mercury Telluride-Zinc

TellurideA.A. GroshevaMoscow State University M.V. LomonosovDetermination of the thermodynamic
stability of solid solutions in systemstype A II B VI are of particular interest because they are
promisingmaterials for electronic equipment. Experimental delamination in systemsCdTe-ZnTe, HgTe-
ZnTe has not been studied before.The purpose of this work is to study the possibility of delamination of
solidsolutions in the systems CdTe-ZnTe, HgTe-ZnTe.Forcheckslow
temperaturethermodynamicstabilitysynthesized solid solutions Cd 1-x Zn x Te (0.3≤x≤0.7) were kept at
100-370 ° C. Experiments, the conditions of which were selected on the basis of the results of work
[1],did not lead to delamination of the samples; XRF showed the samples to be single-phase.
Possibletwo reasons for this result: "weak" kinetics or erroneous valuesthe delamination temperature
recorded by the authors [1]. The annealing temperature wasreduced to 100-200 ° C in accordance with
the calculations of the region of the spinodal-binodaldecay performed in [2]. According to the results of
XRF and DTA(differential thermal analysis), sample aged under new conditionsremained single-phase,
therefore, to detect possible delaminationthe duration of annealing is increased. During the synthesis of
solid solutions,a two-phase sample of compositions Cd 0.67 Zn 0.33 Te and Cd 0.57 Zn 0.43 Te. When
heating thissample on the DTA curve, two peaks are recorded that are not reproduced atcooling. The
position of one of the peaks is consistent with the calculations [2] (105 ° C), the otherlies in the region of
higher temperatures (365-367 ° C).For solid solutions Hg 1-x Zn x Te (0.5≤x≤0.6), the conditions of low-
temperatureannealing was chosen on the basis of calculations [2], since experimentally the decay in it
does notstudied.1. A. Marbeuf, R. Druilhe, R. Triboulet, G. Patriarche, “Thermodynamic analysis of Zn-
Cd-Te, Zn-Hg-Te and Cd-Hg-Te: Phase separation in Zn x Cd 1-x Te and in Zn x Hg 1-x Te ”J. Cryst. Growth
117 10-15 (1992).2. G.F. Voronin, I. V. Pentin, “Decomposition of solid solutions of cadmium
tellurides,mercury and zinc ”Zh. Phys. Chemistry (2005), in press.157

Page 158

RESEARCH OF SORPTION PROPERTIES OF POROUS POLYMERPOROLAS-T BY GAS

CHROMATOGRAPHYGuskov V.Yu.Bashkir State UniversityPorous polymer sorbents represent a wide class
of sorbents.In this work, we studied a relatively poorly studied sorbent of this class -Porolas-T.The study
was carried out by gas chromatography with a detectorthermal conductivity. Organic compounds were
used as sorbatesdifferent classes. Based on experimental data using the Gluckauf methodthe isotherms
of adsorption are calculated at different temperatures. Specificretention volumes (V m ), thermodynamic
characteristics of adsorption, andthe values of A and B of Antoine's equation. It is shown that the values
of V m and thermodynamiccharacteristics depend on polarizability, boiling point and molecularmolecular
masses, but do not depend on the dipole moment. This characterizes Porolas-Tas a nonspecific sorbent
capable of interacting with the studiedadsorbates due to dispersion forces.adsorbatePorolas-T Porolas-
SG-2T Porolas-V-2T polysorb-1Propanol17.912.514.912.2Butanol42.428.223.814.1Ethyl
acetate26.1sixteen18.713.2Butyl
acetate134.373,782.615.6Hexane36.115.725.813.5Heptane82.933.151.914.9The table shows a
comparison of the V m values of Porolas-T with sorbents Porolas-SG-2T [1], Porolas-V-2T [2] and
polysorb-1 [3] at 200 ° C, based on which it is shownhigh efficiency of Porolas-T for concentrating trace
impuritiesorganic compounds from the atmosphere and water.1.I. A. Bardina, N. V. Kovaleva, Yu. S.
Nikitin, O. P. Polyakova, N. M.Shchepalina. Moscow State University Bulletin Ser. 2 Chemistry, 34, 248
(1993).2. I. A. Bardina, N. V. Kovaleva, Yu. S. Nikitin. Moscow State University Bulletin, ser. 2 Chemistry,
36, 19 (1995).3. I. A. Bardina, N. V. Kovaleva, Yu. S. Nikitin, I. S. Protonina. Journal. physicalChemistry, 67,
2005 (1993).158

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TRIFLUOROMETHYLATION OF C 60 AND C 70 FULLERENESDorozhkin E.I.Moscow State University M.V.

Lomonosov, Faculty of ChemistrySynthesis of fullerene derivatives with significant electron-
withdrawingproperties obtained by attaching fluorine atoms to the fullerene sphere,chlorine, bromine,
as well as CF 3 -groups, is one of the priority tasks in chemistryfullerenes in recent years.In 2001, a new
synthesis method was proposed in our laboratorytrifluoromethylated fullerenes C 60 and C 70 , which
consists in carrying out the reactionin the condensed phase between fullerene and trifluoroacetates of
transitionmetals in a dynamic vacuum [1]. Maximum degreethe trifluoromethylation that was achieved
was 22 CF 3 -groups as forfullerene C 60 and fullerene C 70 . The disadvantages of this technique areto
attribute low yields of fullerene trifluoromethylation products and smallefficient use of metal
trifluoroacetates due to high volatilitythe latter. Subsequently, this technique was changed, which made
it possible to significantlyto increase the yields of trifluoromethylated derivatives, as well as to
producechromatographic analysis of the resulting mixtures, isolate and partiallyto characterize a number
of trifluoromethyl derivatives of fullerene C 60 in an individualform [2].In this work, we studied in more
detail the interaction of fullerenes C 60and C 70 with silver trifluoroacetate. By varying the ratio of
reagents,time and temperature of synthesis, we were able to find the optimal conditions forobtaining
mixtures of trifluoromethylated fullerenes of a given composition. Methodhigh-temperature Knudsen
mass spectrometry (HTMS) measured the valueelectron affinity for a number of molecules C 60 (CF 3 ) n
and C 70 (CF 3 ) n , where n = 6-10. Throughhigh performance liquid chromatography, a number of
fractions were isolated,containing, according to MALDI mass spectrometry, compounds of the
composition C 70 (CF 3 ) n , wheren = 2-8.1. I.S. Uzkikh, E.I. Dorozhkin, O. V. Boltalin, A.I. Boltalin.
ReportsAcademy of Sciences, 2001, volume 379, no. 3, p. 344-347.2. A. Goryunkov, I. Kuvychko, I. Ioffe,
D. Dick, L. Sidorov, S. Strauss, O. Boltalina. J.Fluorine Chem., 2003, 124, p 61-64.159

Page 160

STUDY OF THE BINARY SYSTEM NONIONIC SURFACE WATERBY IR SPECTROSCOPYYelensky A.A.Moscow

State University M.V. LomonosovBinary mixtures of surfactants with water are characterized by various
typesself-organized structures. The phases that arise differ in properties, thereforein the practical use of
surfactants, it is important to control their structure.The sequence of the formation of phases usually
obeys the so-calledidealized Fontel sequence.If the viscosity changes abruptly with increasing surfactant
concentration,light scattering and other properties, this indicates a change in the typeself-organized
structures. LC structures are identified by methodsdiffraction of light, neutrons or X-rays; and NMR
spectroscopy.When studying the IR spectra of binary mixtures of nonionic surfactants (Tween-80) - water
at a wideby varying the concentration of Tween-80, changes were found in almost allabsorption
bands.The region 3600-3200 cm -1 reflects the interaction of amphiphilic molecules with water.The
maximum absorption of Tween-80 corresponds to 3475 cm -1 and shifts towards morelow frequencies
with increasing water content. Absorption region 3000-2800 cm -1characterizes stretching vibrations of
C-H bonds. Absorption band near 2850 cm -1sensitive to order in non-polar surfactant residues. This
absorption bandis especially pronounced at high concentrations of Tween-80 in the mixture, but it does
notcharacteristic of Tween-80 without water additives and disappears at a certain volume
fractionNonionic surfactants. Of particular interest is the absorption band in the region of 1090 cm -1
,since it reflects the stretching vibrations of ether groups of oxyethylenechains Twin-80.The absorption
band contours in the IR spectra of the studied systems are complex and fordetailed analysis of changes in
phase structures that occur when changingcomposition of the mixture, the stripes were decomposed
into components usingcomputer programs.This analysis made it possible to substantiate the possibility
of using IRspectroscopy to assess the phase state of surfactant - water mixtures. Dataconfirmed by
measuring the viscosity of the systems.This work was supported by the RFBR grant no. 04-03-32633.160

Page 161
THERMOCHEMICAL STUDIES OF SOLID SOLUTIONSSm 1 + x Ba 2-x Cu 3 O yEfremova M.M.Moscow State
University M.V. LomonosovStudy ofthermochemicalcharacteristicssuperconductorSm-123 (Sm 1 + x Ba 2-
x Cu 3 O y ) is necessary to build a thermodynamic model of thisphase. Difficulties encountered in
experimentalthe study of this substance consists in the fact that the phase has a regionhomogeneity
with respect to cations and non-stoichiometry with respect to oxygen.During the work, solid solutions
were synthesized by the ceramic methodSm 1 + x Ba 2-x Cu 3 O y compositions x = 0; 0.5; 0.7; 0.8. Phase
composition analysis and calculationunit cell parameters for each sample was carried out by the
methodX-ray phase analysis (XRF). According to the literature [1], the phaseSmBa 2 Cu 3 O y has an
orthorhombic-I structure, solid solution of composition x = 0.5is characterized by a tetragonal system,
and solutions with x = 0.7 and x = 0.8 haveorthorhombic-II structure.Oxygen nonstoichiometry in phase
123 is the result of partialoxidation of copper (II) to copper (III); quantitative determination of copper (III)
content inpreparations allows you to determine the deviation of the oxygen content fromstoichiometric.
The oxygen index in the samples was calculated from the dataobtained by iodometric titration. It was
shown that synthesizedthe samples have the following composition: SmBa 2 Cu 3 O 6.70 ± 0.02 , Sm 1.5
Ba 1.5 Cu 3 O 7.01 ± 0.02 ,Sm 1.7 Ba 1.3 Cu 3 O 7.05 ± 0.02 , Sm 1.8 Ba 1.2 Cu 3 O 7.01 ± 0.02 .Heat of
dissolution of the obtained substances in 1.07 N HCl at 298.15 Kwere determined in a sealed rocking
calorimeter with an isothermal shell. FROMusing the data obtained and the enthalpies of dissolution
published in the literaturefor samarium, barium and copper oxides, the standard enthalpies of formation
of phases were calculatedSmBa 2 Cu 3 O 6.70 ± 0.02 , Sm 1.5 Ba 1.5 Cu 3 O 7.01 ± 0.02 , Sm 1.7 Ba 1.3 Cu
3 O 7.05 ± 0.02 , Sm 1.8 Ba 1.2 Cu 3 O 7.01 ± 0.02 fromsimple oxides at 298.15 K.1. Sano M., Hayakawa
Y., Kumagawa M. // Supercond. Sci. Technol. 1996.V. 9 P. 478.161

Page 162

SYNTHESIS AND PROPERTIES OF NEW GLASSY MESOGEN -TETRA- ( p- TRIPHENYLMETHYLPHENOXY) ZINC

PHTHALOCYANINEZharnikova N.V., Usoltseva N.V., Bykova N.V.Ivanovo State UniversityOne of the most
intensively developing in recent years in the field of chemistrymacroheterocyclic compounds is the area
of synthesis and study of physicalchemical properties of phthalocyanine derivatives and its related
macrocyclicπ-delocalized molecules. These compounds are the most studied classfrom all organic
functional materials that are currentlyfind wide application in various branches of science and
technology. Hugethe interest of researchers is attracted to organic materials capable ofexhibit a
transition from a mesomorphic to a vitrified state. Low molecular weightcompounds with this property
are of great practical interest fordevelopmenteffectiveelectro-
opticaldevices,andexactlyelectroluminescent cells, photovoltaic cells, organicphotoconductors.
Therefore, the purpose of this work was to search for new mesomorphicvitrifying compounds and the
study of their properties. One way to getmaterials with such a property is the introduction of bulky
substituents indiscotic molecules. An important area of research is obtaining andstudy of new
compounds of phthalocyanine derivatives with bulky substituents,forming a columnar mesophase with a
transition from mesomorphic to vitrifiedstate. Continuing our previous work on the synthesis of
vitrifiedcompounds with bulky substituents, we synthesized tetra- ( p -triphenylmethylphenoxy) zinc
phthalocyanine [1, 2].It was found that the synthesized compound has mesomorphic properties,and
when cooled, it glazes; absorbs a wide range of visible spectral range withhigh molar redemption rate;
forms well-ordered thinfilms; has a high difference ∆ E HOMO / LUMO .This work was supported by the
RFBR grant (No. 04-03-32305) and the NNIO grant within the framework ofproject B4 under the section
"Sonderforschungsbereich 481".1. Zharnikova N.V. // Mater. IX int. scientific. conf. student, asp. and they
say. uch."Lomonosov". Moscow, Moscow State University, April 9 - 12, 2002.Vol. 2.P. 251.2. Zharnikova
N.V., Usoltseva N.V., Bykova V.V., Kudrik E.V., Telakkat M. //Jew. Christ. and their practice. use, Zhurn. int.
liquid crystal. Society"Commonwealth", 2004. Vol. 3 - 4 (9 - 10). S. 99 - 108.162

Page 163

STUDY OF THE Txy PHASE DIAGRAM OF THE SYSTEMSn - Ge - Te IN THE REGION OF COMPOSITIONS OF
SnTe - Te - GeTeZatolochnaya O.V.Moscow State University M.V. Lomonosov, Faculty of
ChemistryChalcogenides A IV B VI and solid solutions based on them are narrow-gapsemiconductors and
are used in optoelectronics in the infrared region of the spectrum. Manyphysical parameters such as
band gap, parametercrystal lattice, depend on the composition of the solid solution. Therefore it is
importantdetermine the conditions for the synthesis of materials of various compositions. T-x-y phase
diagramthree-component system contains all the necessary information for the selectionconditions for
growing crystals of a ternary solid solution of a given composition.The aim of this work was to determine
the compositions of equilibrium phases atset temperature.Crystals of solid solutions homogeneous in
composition were obtained fromsolutions in the tellurium melt, that is, not along the GeTe-SnTe section,
but from compositionsenriched with tellurium. To determine the compositions of equilibrium
phases,Samples Sn x Ge y Te z were prepared in the range of compositions: Te - from 55 to 70 wt. %, Ge -
from5 to 45 masses. %, Sn - from 5 to 45 wt. %. Three series of anneals were carried out attemperatures
of 1025 K, 980 K, 800 K. Then, for all samples, the compositions were determinedsolid and liquid phase.
To select sample compositions and annealing temperaturesthe data on the liquidus surface Txy of the Sn-
Ge-Te phase diagram were used,previously determined by differential thermal analysis. Studyof the
obtained samples was carried out by X-ray phase analysis by the powder method andlocal X-ray spectral
analysis on polished surfaces. ThroughX-ray phase analysis proved the monophase of crystals and
calculated the parameterscrystal lattices. Based on the results of local X-ray spectral analysisthe
compositions of the solid phases are determined.Thus, as a result of the work, the compositions of the
equilibrium phases were determined,liquidus temperatures, connodal lines are plotted on the Txy phase
diagram.163

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METAL EXCHANGE REACTIONS OF CADMIUM COMPLEXESPROTOPORPHYRINS WITH COBALT CHLORIDE

IN ACETONITRILEZvezdina S.V., Berezin M.B., Berezin B.D.Institute of Solution Chemistry RAS,
IvanovoSpectrophotometricmethodstudiedreactionmetal exchangecadmium mesoporphyrin (CdMP),
cadmium protoporphyrin (CdPP), deuteroporphyrincadmium (CdDP) with cobalt chloride in acetonitrile
(AN).NNNNRH 3 CCH 3RCH 3CH 2H 3 CCH 2COOCH 3CH 2CH 2COOCH 3CdСdРР: R = CH = CH 2CdMP: R =
CH 2 -CH 3CDDP: R = HThe order of the reaction with respect to salt is determined as the tangent of the
slope of the lineardependencies lgk eff. = f (logC CoCl2 ). The metal exchange rate is described by the
equationthe first order in the concentration of the complex, as evidenced by the rectilineardependence
of log (s 0 / s) on the reaction time τ. It has been established that in allcases, the reaction proceeds
according to an associative mechanism , at the first stage of whichan intermediate is formed:CdP + [M
(solv) 4 Cl 2 ] ⇔ [Cd-PM (solv) 2 ] 2 +… 2Cl - ,(1)where M = Co 2+ + ; solv = AN.In the second stage, the
intermediate slowly disintegrates:[Cd-PM (solv) 2 ] 2 +… 2Cl → MP + [CdCl 2 (solv) 2 ](2)A comparative
analysis of the data on the reaction of metal exchange CdMP, CdPP,CdDP with cobalt chloride in
acetonitrile. The dependence of the speedmetal exchange from the nature of porphyrin.164

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MOLECULAR MODELING OF COMPLEX FORMATIONΒ-CYCLODEXTRIN MOLECULE AND VITAMIN K 3

MOLECULESKazachinskaya E.P. 1 , Baskin I.I. 1 , Mamonov P.A. 21 Moscow State University M.V.
Lomonosov, Faculty of Chemistry,2 Moscow State University M.V. Lomonosov, Faculty of
BiologyCyclodextrins (CD) are polymers with a commonformula (C 6 H 10 O 5 ) n . CD is characterized by
the formation of inclusion complexes withinorganic and hydrophobic organic compounds. Usingfat-
soluble vitamins in industry and pharmacology is highly complicatedthe fact that they do not dissolve in
water and have extremely low resistance tothe impact on them of the environment [1]. Complexation of
vitamins with CDallows you to eliminate these problems, therefore, fundamental research in thisareas
are of great applied and theoretical importance [2], [3].We used β-CD as the object of research.
Moleculardynamics, we studied the interaction of a β-CD molecule with a different number of
moleculeswater. It was found that with an increase in the number of water molecules up to
205inclusively, the interaction energy between the CD molecule andwater molecules and the number of
hydrogen bonds between them. Hence the solvatethe shell of one β-CD molecule is approximately 205
water molecules. Besides,the formation of β-CD dimers surrounded by water molecules and the
formation ofcomplex with a molecule of fat-soluble vitamin K 3 . It is determined that the
complexinclusion of two molecules of β-CD and vitamin K 3 is possible only in one of the threepossible
orientations of CD molecules relative to each other.1. Szejtli J. // Cyclodextrins and their Inclusion
Complexes. Budapest, AkademiaiKiado. 1982.296 pp.2. Szejtli J., Szente L., Kulosar G., Kernoczy LZ //
Cosmet. Toiletries. 1986.101.No. 10. pp. 74-79.3. Hedges AR // Chem. Rev. 1998.98 pp. 2035-2044.165

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PRODUCTION OF HIGH PURITY LEAD IN CASCADEELECTROLYSER FROM THE MELT OF ITS

CHLORIDEKalashnikova N.A.Institute of High-Temperature Electrochemistry, Ural Branch of the Russian
Academy of Sciences, YekaterinburgThe purpose of this work is to propose a new technology for
producing leadcoolant for a new generation nuclear reactor. Your attentionthe results of laboratory
studies performed in a cascadeelectrolysis cell by electrolysis of molten lead chloride. Lead refiningwas
carried out in a laboratory apparatus, which is a multifunctionalcascade electrolyzer, which was made of
quartz glass. In it firstmetal lead was produced by primary electrolysis, and after fillingeach cell
(cascade), the electrolyzer began to work as a multiplerefining. The design of the electrolyzer made it
possible to use the principlebipolar electrode. In air, the apparatus was loaded with crushed lead
chloride,pre-purified by zone melting, purged with argon and carefullyheated. The primary electrolysis
was started. Lead level on the left side and salt level inthe right one was controlled visually through the
viewing windows. As you spendlead chloride periodically carried out additional loading of salt.
Afteraccumulation of lead in the left side to the level of 40 mm began electrolyticrefining. After filling all
the cells of the electrolyzer with lead metalthe process entered a stationary regime. Metal samples were
taken periodically andsalt, as well as products (refined lead) using quartzThe parameters of the primary
electrolysis: current - 10 A, voltage - 5-10 V.Refining parameters: current varied from 5 to 25 A. Voltage -
25-32 V.work (680 hours) by electrolytic refining in a cascade electrolyzer withlead chloride of
qualification "h", purified by zone melting7010 products. Samples were analyzed at FSUE NIKIET
(Moscow) atspark mass spectrometer JMS 01BM-2 “Jeol” (Japan). According to the receivedthe results
show that the purification is in progress, and the purest lead onplates 5-8, its purity is 99.999 in the sum
of impurities and 11 basicelements (out of 17).Lead after electrolytic refining in a cascade electrolyzer
withlead chloride of qualification "h", purified by zone melting, satisfiestechnical requirements for the
coolant of the BREST-OD-300 nuclear reactor.166

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STUDY OF SOLUBILITY IN A SYSTEMEt 2 NH 2 Cl - KHCO 3 - NH 4 HCO 3 - H 2 O AT 10 ° CKalinenko E.V.,

Kosolapov A.S., Kistanova N.S.Perm State UniversityThe priority area for the development of science is
currentlydevelopment of waste-free and low-waste technologies for obtaining importantthe national
economy of substances, including mineral fertilizers.The purpose of this work is to identify the possibility
of obtaining potash from potassium chloride,carbon dioxide using diethylamine and ammonia. Physico-
chemicalthe basis of this method of obtaining potash is solubility in the quintuple mutualsystem K + , NH
4+ , Et 2 NH 2+ // HCO 3- , Cl - - H 2 O (1). This work is devoted tothe study of solubility in the system Et 2
NH 2 Cl - KHCO 3 - NH 4 HCO 3 - H 2 O (2),which is a section of system (1) for a stable triplet of salts.The
solubility isotherm of system (2) was plotted according to the data of solubility incontouring systems:
KHCO 3 - Et 2 NH 2 Cl - H 2 O (3), KHCO 3 - NH 4 HCO 3 - H 2 O (4),Et 2 NH 2 Cl - NH 4 HCO 3 - H 2 O (5).
System (3) is a cut of the quadruple mutualsystems K + , Et 2 NH 2+ // HCO 3- , Cl - - H 2 O (4) on a stable
pair of salts. System (4) is nothas a stable diagonal. Systems (2) and (3) are of simple eutonic type. Study
ofcrystallization surface of potassium bicarbonate in the system Et 2 NH 2 Cl - KHCO 3 -NH 4 HCO 3 - H 2
O at 10 ° C was investigated by studying the solubility in two sections,outgoing from the top KHCO 3 to
the side Et 2 NH 2 Cl - NH 4 HCO 3 : KHCO 3 - S 1 (78.0%wt. Et 2 NH 2 Cl, 22.0% wt. NH 4 HCO 3 ) - H 2 O
and KHCO 3 - S 2 (90.4% wt. Et 2 NH 2 Cl, 9.6%wt. NH 4 HCO 3 ) - H 2 O.In the compositions of saturated
solutions of system (2), the presence ofcarbonate ions. The compositions of two triple peritoneal
solutions were determined: the firstsaturated with respect to KCl, KHCO 3 and NH 4 HCO 3 , the second -
with respect to NH 4 HCO 3 ,Et 2 NH 2 Cl and KCl. On the diagram of the solubility of system (1) except
for surfacescrystallization of the salts that make up the system, a crystallization surfacepotassium
chloride, which arose as a result of an incongruentphase reaction. A significant area of the salt part of
the composition diagram iscrystallization surface of ammonium bicarbonate, the least developed
fieldcrystallization of diethylammonium chloride.Solubility data in the system Et 2 NH 2 Cl - KHCO 3 - NH
4 HCO 3 - H 2 O at10 ° C are used for technological calculations.167

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THERMODYNAMIC PROPERTIES OF A SERIES OF LINEARALIPHATIC POLYURETHANESKandeev K.V.,

Smirnova N.N.GOU VPO "Nizhny Novgorod State University named after N.I. Lobachevsky "Due to a
complex of unique physical and chemical properties, polyurethanes(PU), at present, occupy one of the
leading places among industrialpolymeric materials. In this work, the methods of adiabatic
vacuumcalorimetry in the range of 6-350 K with an error of mainly ± 0.2% and dynamiccalorimetry in the
range 320-500 K with an error of ± 1.5%, the temperaturedependence of heat capacity = f (T) of four
samples of linear aliphatic PUcomposition [-O- (CHopC2 ) m —OC (O) —NH- (CH 2 ) r —NH — C (O) -] n
(m, r = 4, 6).In the indicated temperature range, the samples existed in partcrystalline and liquid states.
According to experimental data onthe thermodynamic characteristics of their physical transformations
were determined,numerical values of zero entropy, calculated thermodynamic functions:(T),,,; the
nature of theheterodynamicity of their structure.opCopC) 0 (H) (Hoo-Τ) (So Τ)(-) Τ(0ooHGIn a calorimeter
with an isothermal shell and a static bomb, theircombustion energy and calculated standard
thermodynamic characteristicsformation in the crystalline and highly elastic states at 298.15 K.The
thermodynamic characteristics of PU synthesis (∆ poloH , ∆ poloS , ∆ poloG ) inareas from T → 0 K to 360
K.A linear dependence of the thermodynamic functions of the investigatedPU on the number of
methylene groups in their composition. It was found that the transfer of twomethylene groups from the
isocyanate to the diol part of the monomeric unit of the isomericPU (m = 4, r = 6 and m = 6, r = 4) has a
noticeable effect on the characteristics of theirphysical transformations, while the numerical
valuesdifferinsignificantly.opC168

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STUDY OF PHYSICO-CHEMICAL CHARACTERISTICS OF TRIACETATECELLULOSE SUBJECTED TO β

-RADIOLYSISKasimova V.Yu.Saint Petersburg State University of Film and TelevisionThe main result of
irradiation of cellulose acetates is their destruction, leading todecrease in molecular weight,
accumulation due to oxidative processescarboxyl and carbonyl groups, lowering the degree of
substitution and viscositysolutions. In addition, conformational and configurational changes
occur.glucopyranose cycles up to their opening and, as a consequence, themacromolecules, which
noticeably changes the structure of the irradiated polymer as a whole.The work investigated the effect of
β-radiolysis on completely substituted and partiallysaponified cellulose triacetates (TAC).The values of
the characteristicviscosities for TAC samples subjected to various radiation doses. Outputthe destruction
of G for the completely substituted TAC turned out to be rather high andaveraged 2.4 breaks per 100 eV.
It is noticed that for partially saponifiedTAC the value of G is slightly reduced. For both samples with
increasing doseradiation, a sharp increase in solubility was observed in thermodynamically worsein
comparison with chlorine-substituted alkanes solvents.IR spectra showed that the most noticeable
changes in intensitythe absorptions in the samples subjected to training are observed in the
followingfrequency ranges: 2600–3800 and 600–900 cm -1 . In the first area, redistributionintensities of
bands of primary and secondary OH-groups indicates the formationadditional secondary hydroxyls,
which mainly result frombreaking the glycosidic bond. Redistribution of intensities of bands 900 and 600
cm -1can be explained by an increase in the number of conformations of acetate groups caused byby
turns around the C – O bonds [1].This study was the first step in the work on the modificationfilm-
forming solution of TAC by the products of its radiolysis to obtainfilm material with increased strength
parameters.1. Panov V.P., Zhbankov R.G. Sugar conformations (physical methodsresearch). Minsk, 1975,
p. 216.169

Page 170
STUDYING THE COMPLEXITY OF KAZKAIN Sβ- CYCLODEXTRIN IR SPECTROSCOPYKemelbekov U.S., Beketov
K.M., Praliev K.D.Institute of Chemical Sciences named after A.B. Bekturova MES RKOf particular interest
for practical medicine, including military fieldmedicine and disaster medicine, represents a highly
effective localanestheticandantiarrhythmicKAZKAIN(1- (2-ethoxyethyl) -4-ethynyl-4-benzoyloxypiperidine
hydrochloride) [1], created jointly by scientists andspecialists of the Institute of Chemical Sciences,
Kazakh State MedicaluniversityandNovokuznetskresearchchemical-pharmaceutical institute. On its basis,
various medicinalforms: 0.25, 1 and 5% solutions for injection. Currently under developmenttableted
and prolonged dosage forms based onwater-soluble polymers. Of no small interest is the creation of a
newdosage form based on inclusion complexes with β-cyclodextrin (β-CD),since β-CD is widely used to
improve biopharmaceutical propertiesbiologically active substances.The complexation of β-CD with
cascaine was studied by IRspectroscopy. The figure shows IR spectra: (a) β-CD, (b) kazcaine, (c)complex of
cascain with β-CDprecipitated from solution and (d)equimolarphysicalmixtures of cascaine with β-
CD.Ofexperimentaldata revealed thatbond absorption bands -С = О (1722 cm -1 ), –С≡С (2118cm -1 )
and C 6 H 5(1600 cm -1 )observable for purecascaine and physical mixture,shift to 1729, 2113 and1642
cm -1 in the case of a complex.In addition, the intensity and shape of these three bands vary for the
complexinclusions in comparison with the absorption bands of pure cascaine and the physical
mixture.This allowed us to assume that the cascaine molecule is incorporated into the internalthe cavity
of the β-CD molecule with its aromatic part.g .in.b.and.Fri Feb 18 10:38:50 2005 Kemelbekov
FC1.16080% TTue Feb 15 16:00:04 2005 Kemelbekov 1-180859095% TTue Feb 15 16:10:53 2005
Kemelbekov KAZHCLone hundred105110% TTue Feb 22 15:42:21 2005 CD406080one hundred%
T500100015002000250030003500Wavenumbers (cm-1)1.PatentRK.3137Hydrochloride1- (2-
ethoxyethyl) -4-ethynyl-4-benzoylpiperidine, which has local anesthetic activity(KAZKAIN) // Praliev K. D.,
Isin Zh. I., Yu V. K., Tarakov S. A., Bosyakov Yu.G., Utepbergenova R.K., Shin S.N., Kadyrova D.M., Publ.
01.06.90.170

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PECULIARITIES OF THE KINETICS OF DISSOCIATIONMANGANESE (III) OCTAETHYLPORPHINES DEPENDING

ON NATUREPROTOLYTIC SOLVENTKiseleva E.N., Klyueva M.E., Lomova T.N.Institute of Solution Chemistry
RAS, IvanovoIt is known that most metalloporphyrins dissociate under the action ofstrong acids, and the
best medium for quantitative measurements are mixedprotolytic solvents. It was shown earlier [1] that
upon dissociationmanganese (III) octaethylporphyrins (X) MnOEP (where X = Cl - , AcO - ) in
concentratedsulfuric acid, an extreme character of the dependence of the rate constantdissociation from
acid concentration. The reason for the appearance of an extremum isthe change in the reactive particle
promoting the coordinated ligand whendissociation of the complex. Therefore, it is of interest to study
the influence of natureand the composition of the medium acting as a solvent and reagent, on the
regularities of the reactiondissociation.In this work, a comparative study of the dissociation of (X)
MnOEP underthe action of sulfuric acid in an aqueous and acetic acid medium. For
determiningmechanism of dissociation reactions obtained quantitative kineticcharacteristics of the
processes, as well as the effect of macrocycle modification on kinetics.Dissociation of manganese (III)
porphyrins in a mixed solvent H 2 SO 4 - AcOHwas studied using the example of manganese (III)
octaethylporphyrins with graduallyincreasing phenyl substitution at the meso- positions of the porphyrin
ligand.It was found that the stability of the complexes depends on the electronic naturesubstituents, as
well as from violation of the aromaticity of the molecule due to deviationfrom coplanarity in complexes
with exhaustive meso- substitution.According to the results of studies of the kinetic stability of
substitutedcomplexes, recommendations were given on the search for effective
catalystsdisproportionation of hydrogen peroxide.Completed with the support of the Foundation for the
Promotion of Russian Science.1. Kiseleva E.N., Klyueva M.E., Lomova T.N. "Reactivitymanganese (III)
octaethylporphyrins in sulfuric acid ”. J. "Izvestiya VUZv.Chemistry and Chemical Technology ", 2004, V.
47, no. 5, pp. 76 - 79.171

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MODELING OF THE SOLUBILITY ISOTHERM OF FIVE WATERSALT SYSTEM OF SIMPLE EUTONIC

TYPEKistanova N.S., Dvinyaninova N.B., Kosolapov A.S., Kalinenko E.V.Perm State UniversityInformation
on solubility in multicomponent water-salt systems isphysicochemical basis for the production of many
inorganic salts. Mathematicalthe model of solubility isotherms of these systems makes it possible to
intensify the process of theirresearch, to determine the sufficiency of experimental material for
reliablecalculating the compositions of equilibrium phases of a given composition of the initial reaction
mixture(SIRS) F, apply solubility data to calculate technologicalparameters of obtaining mineral salts in
equilibrium conditions.The proposed algorithm is an extension of the method of mathematicalmodeling
of solubility isotherms of quaternary water-salt systems,developed at the Department of Inorganic
Chemistry of the Perm Stateuniversity. On the solubility isotherm of the quintuple system, fivegroups of
phase areas (one five-phase, four four-phase, six three-phase,four two-phase and one single-
phase).Belonging of point F of a given composition to one of the phase regionsis determined by
sequentially excluding those areas in whichpoint F falls, starting with five-phase and ending with single-
phase. To excludegroups of domains in which the point F does not explicitly fall, a preliminaryanalysis.
When determining points on surfaces and hypersurfaces along whichprivate areas are constructed, the
simplex method is used.The proposed model adequately reflects the physicochemical naturesystem,
allows you to fully describe all phase equilibria, gives an unambiguoussolution and allows
implementation on a PC. A program in the languageC ++ programming, which is tested on the model
solubility isotherma fivefold system of a simple eutonic type with points on all lines,surfaces and
hypersurfaces of crystallization. The program is used forstudy of the crystallization hypersurface NaHCO
3in the NaCl – KCl– systemEt 2 NH 2 Cl – NaHCO 3 –H 2 O.172

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OXIDATION OF MAGNESIUM WITH BIPHENYL ANTIMONY CHLORIDE ANDDIPHENYLBISMUTH IN THE

SYSTEM DIMETHYLFORMAMIDE - p-XYLOLKlementyeva S.V., Losev Ya.V., Malysheva E.V.GOU VPO "Nizhny
Novgorod State University named after N.I. Lobachevsky "Interaction of magnesium with
diphenylantimony and diphenylbismuth chloridesleads to the formation at the first stage of the green-
like reagents Ph 2 EMgCl (E =Sb, Bi)Ph 2 ECl + Mg → Ph 2 EMgClwith the subsequent establishment of
Schlenk equilibrium in the reaction mixture:2Ph 2 EMgCl ↔ (Ph 2 E) 2 Mg + MgCl 2The intermediate
product then reacts with the original oxidizing agentaccording to the equation:Ph 2 EMgCl + Ph 2 ECl →
Ph 2 E – EPh 2 + MgCl 2 ,forming unstable dimers containing the E – E bond, which rapidly
decomposescheme:Ph 2 E – EPh 2 → Ph 3 E + (PhE) n + E + Ph 2Curves of dependences of the rate of
magnesium oxidation on concentrationorganoelement chlorides and donor solvent in the DMF - p-
xylene system,obtained using the resistometric method, pass through the maximum. itindicates that
surface reactions are described by the Langmuir scheme -Hinshelwood, assuming the adsorption of the
components of the oxidizing mixture onidentical active centers of the metal surface. Regression analysis
methodkinetic equations, the effective equilibrium constants of adsorption are determinedreagents and
rate constants of the initial stage of magnesium incorporation at the E– bondCl. From the temperature
dependences of the obtained values, the effectiveenthalpy and entropy of adsorption of DMF and the
corresponding oxidants on the metal, andalso the activation energies of the processes.It was found that
the enthalpy of adsorption of Ph 2 BiCl on the magnesium surface is almostan order of magnitude lower
than the corresponding value for Ph 2 SbCl. This is probably due tohigh energy costs required for
deformation of the Bi – Cl bondcompared with the Sb – Cl bond.173

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THERMODYNAMIC CHARACTERISTICS OF DISSOLUTIONFULLERENE C 60 IN MIXED SOLVENTSKozlov A.V. 1

, Islamova N.I. 21 Ivanovo State University of Chemical Technology, IO VKhK RAS,2 Institute of Chemistry
of Solutions RASThis work is devoted to the study of the solubility of the C 60 fullerene inindividual and
mixed organic solvents for varioustemperatures and analysis of the data obtained.A correlation equation
was proposed linking the thermodynamicdissolution characteristics of C 60 with molar volume,
refractive index anddielectric constant of the solvent:40005000εσµσ013312012123122210121)
(VRTAVRTAnnAAxRTLn+++-+=-(1),where x is the mole fraction of fullerene.The solubility of С 60 in the
systems carbon tetrachloride – toluene andcarbon tetrachloride – o-dichlorobenzene in the entire range
of compositions of mixedsolvent in the temperature range 25–65 0 С. An equation describingsolubility of
C 60 fullerene on temperature and composition of the mixed solvent:40005000SSpcpcXTTKXKRSRTHLnX)
15.298(15,29800-∂∂++∆+∆-=(2),It is noted in the literature [1, 2] that the nonmonotonic temperature
dependencesolubility is associated with the tendency of fullerenes to form crystal solvates.To obtain
more complete information on the forms of existence of C 60 in solution andpossible phase
transformations depending on temperature, we wereDSCs of fullerene crystal solvates were
performed.1. Korobov MV, Mirakyan AL, Avramenko NV, Oloffsson G., Smith AL, RuoffRS “Calorimetric
Studies of Solvates of C 60 and C 70 with Aromatic Solvents” // J.Phys. Chem. B, 1999, V. 103, P. 1339-
1346.2. Doome RJ, Dermaut S., Fonseca A., Hammida M., and Nagy JB “New evidencesfor anomalous
temperature-dependent solubility of C 60 and C 70 fullerenes in varioussolvent ”// Fullerene Science and
technology, 1997, V. 5, No. 7, P. 1593-1606.174

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CAPILLARY CHROMATOGRAPHY OF ADAMANTANE C DERIVATIVESUSING MODIFIED FIXED

PHASESKonstantinova K.K., Kurbatova S.V.Samara State UniversityIn recent years, capillary
chromatography has developed most intensively,but the problem of choosing suitable sorbents is still
relevant,allowing you to solve such complex tasks as the separation of complex mixturesorganic
compounds and medicines. This paper examinespossibilityusemodifiedmotionlessphases(adamantyl
silicones) to solve similar problems. Adamantane derivativeshave a wide range of pharmacological
action: antiviral,psychostimulating, antispasmodic, etc. In this regard, an interestingthe study of
adamantane and its derivatives as sorbates, andsorbents of various structural modifications.We
investigated the characteristics of the chromatographic retention of the seriesadamantane derivatives of
the composition Ad-X (where X is -CH3, -COOH; -COCH3; -OH; = O; -Cl;-Br; phenyl-; tolil-, tenil-, etc.)
using different polaritiesstationary phases and adamantyl silicone.To characterize the properties of
adamantyl silicone,chromatographic behavior of organic compounds within homologousseries of the
main classes of organic compounds.Based on the experimental data, sorption,thermodynamic,
chromatographic characteristics of the compounds under study.Correlation relationships between
chromatographicretention, differential free molar energy of sorption andsome structural and topological
characteristics of derivativesadamantane (molecular volume, polarizability, molecular refraction,Randich
and Wiener indices), which are of independent scientific interest,and serving as a basis for building
predictive models "structure -property. What is especially important when simulating drugs withgiven
properties based on adamantane derivatives and stepwise controlsynthesis of such high-boiling difficult-
to-chromatographic compounds.175

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INTERACTION OF C-NUCLEOPHILES WITH CHLORINATEDSYNTHETIC DIAMOND SURFACEV.V.

KorolkovMoscow State University M.V. Lomonosov, Faculty of ChemistryChemical modification of
diamond powders leads to the creation of a newclass of promising materials, since they combine unique
propertiesdiamond and the specific properties of the grafted chemical compound.We used DALAN
synthetic diamond in the work, it representsis a polydisperse powder (particle size from 0.005 to 10 μm)
with a specificsurface 22 m 2 / g (BET). Pretreatment in a stream of hydrogen at 800 Cfor 5 h leads to
monofunctionalization of the surface. As a result of thisa layer of hydride groups formed on the surface
of the diamond powder(cf. IR spectra a and b).Fig. Fourier transform IR spectra of the initial diamond
powder (a), treatedhydrogen (b) and bottled (c)To create electrophilic centers on a hydrogenated
surfacediamond powder, we proposed a method of sequential chlorination withusing SOCl 2and SO 2 Cl
2 , which makes it possible to obtain extremely chlorinatedthe surface of the diamond. After thorough
vacuuming of the reaction mixturethe chlorinated diamond was treated with n- BuLi in hexane. This
allowed us to introducen- butyl groups on the diamond surface, which is confirmed by IR
dataspectroscopy (spectrum c). By treating chlorinated diamond with PhLi or NaCN onphenyl and nitrile
groups were introduced on its surface. Hydrolysis eitheralcoholysis of the latter allowed the formation of
a layer on the surface of the diamondcarboxyl or ester groups.Thus, the paper proposes methods for
creating a diamondpowder of an essentially hydrolytically resistant grafted organic layersubstances. The
developed methods will make it possible to create new promisingchromatographic materials based on
diamond.176

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HYDROPHOBIC EFFECTS IN BIOLOGICAL SOLUTIONSACTIVE SUBSTANCESA.V. Kustov 1 , Krestyaninov M.A.

1 , Bekeneva A.V. 2 , Syshchenko A.F. 3 , Emelyanov A.A. 3 ,V.P. Korolev 1,21 Institute of Chemistry of
Solutions RAS, Ivanovo,2 Ivanovo State University of Chemical Technology,3 Belarusian Interuniversity
Center, MinskHydrophobic effects play a fundamental role in shaping propertiessolutions of non-polar
particles, determine the behavior of macromolecules in aqueoussolution. We have measured the heat
effects of dissolution of L-phenylalanine and L-histidine in aqueous solutions of dimethylformamide
(DMF) and urea (Mp) intemperature range 25-40 0 C. The measurements were carried out on
establishedThermochemical laboratory of the Institute of Chemical Chemistry of the Russian Academy of
Sciences calorimetric installationsensitivity of the order of ~ 10 -5 0 С and accuracy of temperature
maintenance inthermostat above ± 0.001 0 С. Measurement of resistance of the temperature sensor
-thermistormeasuredThe referencemetertemperature (ITE),designed by the Belarusian Interuniversity
Center. One ITE entrancedesigned to measure thermistor with resistance from 0 to 20 kOhm
(resolution0.001 Ohm), the second input is used to measure temperature with a platinum
thermometerresistance (resolution 0.0001 0 С) and can be used both for measuringheat capacity and
temperature control in the thermostat. Received dataaccepted and processed by a computer. The
enthalpies andthe heat capacity of dissolution in water at 25 0 С is in good agreement with the
availableliterary data. The parameters of pair and triple interactions are determinedbiologically active
substances with amide molecules. Found thatinteraction with DMF in all cases is enthalpically
repulsive,moreover, the repulsion is induced by the influence of hydrophobic groups in the
moleculesinteracting particles. In the case of Mch, the interaction is attractive. Shownthat the enthalpy
parameters of the interaction of the zwitterionic group of amino acids withDMF is close to zero, while its
interaction with urea is accompanied bystrongly negative change in enthalpy. It was discovered for the
first time that the enthalpyinteraction parameters are not linear functions of temperature, butpass
through weakly expressed extrema at T ~ 33 0 С, where there is a changethe sign of the interaction
heat.This work was supported by a grant from the Ministry of Education and Science of the Russian
FederationA 03-2.11-184 and RFBR project 05-03-96401-reg.177

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NEW POLYIMIDE MATERIALS FOR MEMBRANESYNTHESIS GAS SEPARATIONSLazareva Yu.N., Vidyakin

M.N.Institute of Petrochemical Synthesis. A.V. Topchiev RASOne of the topical areas of modern hydrogen
energy isobtaining pure hydrogen from traditional sources of hydrogen-containing
mixtures,inparticularsynthesis gas.Mosteconomicalwaycleaningthe hydrogen-containing raw material is
membrane technology. However, its application incurrently constrained by the lack of membranes and
polymermembrane materials allowing to achieve a high degree of purification of mixturesH 2 / CO in one
stage. Thus, the search for new highly effective polymermaterials for the separation of synthesis gas is an
urgent issue of modernscience and technology. Dependence of the transport properties of polymers on
their chemicalstructure serves as the basis for targeted search and synthesis of new polymersmembrane
purpose. Analysis of the TIHS RAS Database [1] showed thatthe necessary elements of the chemical
design of such polymers can be foundamong low-permeability and highly selective polyimides.Several
objects of study were selected in this work.groups of new structurally related polyimides having a
common dianhydrideor a diamine fragment, including copolyimides of regular structure,membrane
properties of which have not yet been studied. For each researchedpolyimide for a number of gases (Н
2 , СО, СО 2 , СН 4 ) were experimentallythe coefficients of permeability, diffusion, solubility and
selectivity are determinedgas separation at room temperature. Obtained experimental dataconfirmed
the assumptions about the influence of individual fragments of the structure of polyimideson their
transport properties. Based on the analysis of the Database [1] andexperimental results, chemical design
elements were selectedstructures of polyimides, promising for further improvement of
selectiveproperties of polymer membranes.1. Database "Gas separation parameters of glassy
polymers".Informregistr RF. 1998. No. 3585.178

Page 179

CHANGING THE PROPERTIES OF 2D FULLERENE C 60 FILMSFORMED ON A WATER SUBSTRATE WITH

VARIOUSCONCENTRATION OF ELECTROLYTESLevacheva I.S.Moscow State University M.V. LomonosovOne
of the directions of using fullerene is the creation on its basisa variety of sensor systems and adsorbents.
The basis of most of these systemsis a thin film of modified fullerene deposited on one or
anothersubstrate. Difficulties in obtaining thin films are associated with chemical propertiesfullerene,
which determine its propensity for association. Cation adsorptiondifferent metals on the surface of the C
60 globule can lead toforces of electrostatic repulsion between individual molecules.The work studied
the effect of electrolytes dissolved in a water substrate, onwhich were formed 2D fullerene films. The
properties of these films werestudied by the Langmuir method.It was found that the parameters of the
two-dimensional pressure isotherms of 2D fullerene filmsdepend on the amount of the initially applied
substance. When applied 8.3 · 10 -8 M,probably more aggregates are formed in the gaseous film than in
the caseof application 5.6 · 10 -8 M. This is possible due to the difference in evaporation timesolvent
from the surface of the aqueous subphase during spreading of the applied 1.4 · 10 -3 Mfullerene
solution.During the adsorption of cations on the surface of fullerene globules,probably, their
hydrophilization, which explains the decrease in the value of π max . Magnificationthe diphilicity of a
fullerene molecule caused by the adsorption of cations on its surface,leads to a decrease in the
aggregation of molecules in a gaseous film andincreasing its effective two-dimensional surface activity
and effectivemodulus of elasticity of the film. Change in the amount of applied fullerene from 5.6 · 10 -8
to8.3 · 10 -8 M leads to an increase in the A 0 value from 54.5 Å 2 / mol to 59.1 Å 2 / mol for systemsin
the absence of electrolyte. Increasing the value A 0happens for systemscontaining MnSO 4 . For cases of
introduction of ZnSO 4 and (NH 4 ) 2 SO 4 into the subphase ,more complex dependencies, but the
general pattern of increasing the value of A 0saved in all systems.This work was carried out with the
financial support of the RFBR grant No. 04-03-32633179

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STUDY OF PHOTOCHEMICAL TRANSFORMATIONSPARA- AND META-NITROSONITROBENZENESA.A.

Logunov, S.V. ZelentsovNizhny Novgorod State University N.I. Lobachevsky,zelentsov@chem.unn.ruWe
have studied the reactions occurring during the photochemical decompositionisomeric nitrosonitro- and
dinitrobenzenes in the presence of molecular oxygenin non-polar environments. In the spectra of steam
- and meta- nitrosonitrobenzenes anddinitrobenzenes irradiated with different doses of UV radiation,
twoisobestic points appearing at different time intervals. Last thingspeaks of the pseudo-two-component
nature of the studied reaction systems in thesetime intervals and the course of two successive
photochemicalreactions. It has been proven that molecular oxygen photochemically oxidizesnitroso
groups to nitro groups, and the rate of this process is about 70 timesexceeds the rate of
photodegradation of nitro groups.Two possible mechanisms for the photooxidation of
nitrosonitrobenzenes have been proposed.The first is associated with the intermediate formation of
NO.ROONORO + NO 2RNORROO+ O 2NO+hνNO-,(1)+RNO 2RNO 2...(2)The key stage of the second
mechanism is the transfer of a hydrogen atom frommolecules of the medium to triplet
nitrosoperoxide.3RNORNO1RNO* ischν+3O 2 1RN (O) OO* isc 3RN (O) OO, (3)PH ++ OH.RNO 23RN (O)
OOP-RN (O) OOH(4)Both schemes assume an active role for the reaction medium. Definedyields of
benzene hydroxylation products during photolysis of nitrosonitro- anddinitrobenzenes in benzene, in the
presence of oxygen. Phenol yields increase withincrease in exposure time and for nitrosonitrobenzenes
is lower than forthe corresponding dinitrobenzenes.The authors are grateful to the "Universities of
Russia" program and RFBR for financialsupport.180

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ANODE PROCESSES IN AQUEOUS SOLUTIONS OF SODIUM SUCCINATEMagamedbekov R.M., Khibiev

Kh.S., Khidirov Sh.Sh.Dagestan State University, MakhachkalaBy the method of stationary potentiostatic
polarization curves onplatinum anode, the processes of electrochemical oxidation of anionsdicarboxylic
acids and oxygen evolution in aqueous solutions of succinic saltsacid. The polarization curves show
clearly pronounced three delayscurrent at potentials: 1.2; 1.4; 1.7V due to adsorption processes of
variousforms of chemisorbed oxygen, and a current delay at a potential of 1.9 V, associatedwith
decarboxylation of succinate anions.A qualitative comparison of stationary polarization curvesobtained
in aqueous solutions of sodium succinate with those in acetate solutionssodium under the same
conditions. In sodium succinate solutions, the processdecarboxylation begins much earlier (1.9 V) than in
acetate solutionssodium (2.1-2.2V). At the same time, the oxidation currents in sodium succinate
solutions throughoutthe ranges of the studied potentials are an order of magnitude higher than in
sodium acetate solutions.The effect of the thiocyanate additive inhibiting the oxygen reaction was
studied.ammonium on the character of stationary potentiostatic polarization curves onplatinum anode
in sodium succinate solutions. As in salt solutionsmonocarboxylic acids, ammonium thiocyanate shifts
the potential of the oxygen reaction tothe anode side and reduces currents associated with adsorption
and evolution of oxygen anddecarboxylation.Experimental data on the effect of the concentration of
amber saltacids, additives of ammonium thiocyanate for the processes of adsorption and evolution of
oxygen anddischarge of succinate anions. Based on these data, a significant difference is shownanodic
processes occurring in solutions of salts of dicarboxylic acids, according tocompared with
monocarboxylic.181

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STUDY OF PROCESSES WITH THE PARTICIPATION OF SULFUR-CONTAININGELECTRODE IN ACCURRENT

POLARIZATIONMamyrbekova A.K., Baeshova S.A., Baeshov A.International Kazakh-Turkish University. HA.
Yasawi,The Republic of KazakhstanSulfur and its compounds are raw materials for the chemical and many
other industriesindustry. The study of the physical and chemical properties of sulfur will explainsulfur
behavior in the development of new technological processes. Despitegreat theoretical and practical
interest, research of electrochemicalprocesses with the participation of sulfur are still in the
development stage.The electrochemical behavior of sulfur with AC polarization is practicallynot
investigated.The purpose of our research is to study the processes occurring duringpolarization of sulfur-
containing electrode with alternating current in hydroxide solutionpotassium. The influence of the main
parameters of electrolysis was studied: current density onsulfur-containing and titanium electrodes,
electrolyte concentration and temperature,duration of electrolysis and frequency of current for
electrooxidation-reductionsulfur.Based on the experiments performed, it was found that sulfur dissolves
inmainly with the formation of sulfite and sulfide ions by the following reactions:in the anodic half-cycle:
S o + 6 OH - -4e → SO 32- + 3H 2 OE о = -0.657 Bin the cathode half-period: S o + 2e → S 2-E about =
-0.48 BIt was shown that with an increase in the electrolyte concentration over 3 mol / L and
temperatureabove 60 0 С, the composition of the formed electrolysis products changes significantly
withthe formation of polysulfide and thiosulfate ions. Probably the ratio of speedsreactions in the
cathodic and anodic half-periods change and mainly proceednext reaction:2nS o + 6OH - → 2S n-12- + S 2
O 32- + 3H 2 OThus, we have studied for the first time the electrochemical behavior of sulfur
atpolarization with alternating current in an alkaline medium. The results of ourresearch helps to expand
knowledge in the field of non-stationary electrolysiscurrent.182

Page 183

THERMODYNAMICS OF CALCIUM URANYL BORATEMarochkina M.N., Smirnova N.N.Research Institute of

Chemistry GOU VPO NNSU them. N.I. LobachevskyUranyl borates belong to a wide class of inorganic
uranium compounds withgeneral formula A k [UO 2 An] k ⋅nH 2 O, where A k - one-, two-, trivalent
metals, An -BO 33- , SiO 3 OH 3- , GeO 3 OH 3- , PO 43- , VO 43- , AsO 43- , NbO 43- having a great
scientific andpractical interest. In this regard, in this work, the enthalpy was determined for the first
timeformation and studied the heat capacity of crystalline calcium uranyl
borate.Experimentalthermochemicalmaterialgotfromhelpmodernized calorimeter designed by S.M.
Skuratov and used forcalculating the standard enthalpy of formation of calcium uranyl borate:∆ f H 0
(298, Ca (BUO 5 ) 2 , k) = - 4491.0 ± 8.0 kJ / mol.The heat capacity was studied in the BKT-3 adiabatic
vacuum calorimetercompounds in the range 7 - 304 K, which monotonically increases throughout the
studiedtemperature interval without showing visible anomalies. Numerical integrationdependences C p
= f (T) and C p = f (lnT), the enthalpies of heating and the absoluteentropy of the studied substance.
Gibbs heating functions for each temperaturecalculated by the Gibbs-Helmholtz equation. Required for
these calculationsdata on the heat capacity of a substance in the region below 7 K were obtainedby
extrapolating the experimental dependence of the heat capacity according to the Debye equation.The
absolute entropies of calcium uranyl borate and the corresponding simplesubstances calculated the
standard entropy of formation at 298.15K of the studiedconnections:∆ f S 0 (298, Ca (BUO 5 ) 2 , k) = -
887.1 ± 2.1 J / (mol⋅K).This value and the standard enthalpy of formation were used to calculate the
standardGibbs function of formation at 298.15 K of calcium uranyl borate:∆ f G 0 (298, Ca (BUO 5 ) 2 , k)
= - 4226.5 ± 8.5 kJ / mol.This work was supported by the Russian Foundation.fundamental research
(projects No. 01-03-32061, 02-03-32162) andMinistry of Industry and Science of the Russian
Federation.183

Page 184

COORDINATE REPRESENTATION OF Q- DEFORMEDHARMONIC OSCILLATORA.A. Mel'dianov, V.V.

EreminMoscow State University M.V. Lomonosov, Faculty of ChemistryIn recent years, a new
construction has been applied in theoretical chemistry- quantum groups, with the help of which, for
example, describe vibrationalrotational spectra of di- and polyatomic molecules [1]. Many
applicationsquantum groups are associated with deformation of standard commutation relations.The
most popular model in q -deformed quantum mechanics isharmonic oscillator, which is defined by
means of the creation anddestruction that satisfy the generalized commutation relation:aa + - qa + a =
1,where q ∈ (0, 1) is the deformation parameter. Algebraic properties have been studied in the
literature.given model, but the explicit coordinate representation for the operators a and a +found by us
for the first time. Using this representation for the HamiltonianH = Ѕω ( aa + + a + a )found the wave
function of the ground (vacuum) state, the probability densitywhich for any q has a Gaussian form and
coincides with the probability densityconventional harmonic oscillator. Sequential application of
operatorscreation to a vacuum state, expressions are obtained for all energy levels andwave functions of
a q -deformed oscillator. Energy dependence onquantum number is nonlinear:E n = ω ([ n ] + q n /
2),where [ n ] = 1 + q +… + q n –1 . This is the basis for the application of the model in the theory of
molecularspectra.This work was supported by the Russian Foundation for Fundamentalresearch (grant
03-03-32521).1. Xie M., Hou X.-W., Ma Z.-Q. q -Deformed harmonic oscillators applied to thevibrational
spectrum of methane // Chem. Phys. Lett. - 1996. - V. 262. - P. 1-7.2. Macfarlane AJ On q -analogues of
the quantum harmonic oscillator and the quantumgroup SU (2) q // J. Phys. A: Math. Gen. - 1989. - V. 22.
- P. 4581-4588.184

Page 185

STUDY OF PHOTOLYTIC DECOMPOSITION OF CARBONYLCHROMIUM COMPLEXES IN HYDROCARBON

SOLUTIONSMishchenko O.G.Nizhny Novgorod State University N.I. LobachevskyPhotolytic decomposition
of metal carbonyl complexes has been studied in detailon the example of homoligand derivatives of
elements of groups VI-VIII. Special interestrepresent organometallic compounds, in the coordination
sphere of whichthere is a ligand with an accessible multiple bond, since on their basis it is
possibleobtaining polymers and copolymers with unique characteristics.Photolysis of StCr (CO) 3 , CbCr
(CO) 3 and DFBCr (CO) 3 (St - styrene, Cb - stilbene, DFB -diphenylbutadiene) in hydrocarbon solutions
upon irradiation with monochromaticlight with λ = 313 (366, 405, 435) nm is accompanied by the
formation of CO.The dependences of the quantum yield of CO accumulation (φ CO ) on the
lengthwavelength, radiation intensity, temperature and initial
concentrationinvestigatedorganometallicconnections,identifiedsomeintermediate and final reaction
products. Based on the receivedexperimental data, a probable scheme for the photolysis of
carbonylcomplexes of chromium, including the decay ofexcited molecule of the carbonyl complex with
the abstraction of the CO ligand, and assecondary - the reaction of the formed coordination unsaturated
fragment withthe original molecule of the organometallic compound.1. Introduction to the
photochemistry of organic compounds. Ed. prof. G.O. Beckerand prof. A. V. Eltsova. Per. with him. L.,
"Chemistry", 1976.2. J. Barltrop, J. Coyle, Excited States in Organic Chemistry. Undered. Dr. chem. M.G.
Kuzmina. Per. from English M., publishing house "Mir", 1978.3. J. Calvert, J. Pitts, Photochemistry. Ed. Dr.
Phys.-Math. R.F.Vasilyeva. Per. from English M., publishing house "Mir", 1968.185

Page 186
RESEARCH OF CADMIUM OXIDATION IN ALKALINE SOLUTIONS WITHAPPLICATION OF T ONCOLAYER
CELLMoskvichev A.A., Kozina O.L.Nizhny Novgorod State Technical UniversityCadmium electrodes are
widely used in alkaline Ni - Cd batteries.To improve the electrical characteristics of porous electrodes,
knowledge is requiredmechanism of processes occurring in a limited volume of electrolyte. In thatcase,
diffusion processes are hampered, leading to significantchanges in the concentration at the surface of
the particles of the active substance.To simulate such conditions, we have developed a specialthin layer
cell. Limited electrolyte volume and diffusion difficultieswere created using a highly porous separator
and a cellulose hydrate film.The concentration and diffusion coefficient were determined from the
dependence of the transitiontime from the inverse current density [1].Table. Concentration of cadmium
hydroxo complexes in NaOH solutionsWith NaOH, mol / l248ten15С · 10 3 , mol / l0.420.810.871,21The
calculated diffusion coefficient was D = (0.6 ÷ 0.8) · 10 -6 cm 2 / sec and is characteristicfor cadmate ions
[2]. The obtained concentration values turned out to be 6-7 times higherequilibrium, which can be
explained by the formation of a supersaturated cadmiumsolution. Further decomposition of this solution
leads to the formation of hydroxidecadmium on the electrode surface, followed by passivation of its
surface.Stoichiometric coefficient OH -participating in the education of cadmatcomplex was 4.1. Galyus
Z. Theoretical foundations of electrochemical analysis. M., 1974, p. 551.2. Obedkov Yu.I. Study of the
cathodic process in the Cd / Cd (OH) 2 / KOH system. -Abstract dissertation. Cand. tech. Science - Saratov,
1976, p. 24.186

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CALCULATION OF VAPOR PRESSURE DISPERSION AND FORMATION ENTHALPYCOMPONENTS IN THE

SYSTEM Si (crys.) - SiCl 4Nepopalova I.V., Rusin A.D., Kuzmenko N.E.Moscow State University M.V.
LomonosovMeasuring steam pressure versus temperature provides valuable informationabout the
thermodynamic properties of steam, especially in systems at high temperatures,when there are complex
equilibria between the constituent parts of the steam andcondensed phase (Si (crystal) - SiCl 4 ). One of
the processing methodsexperimental data of the dependence P (T) ( P exp ) is the calculation of the
vapor pressure( P calc ) at each temperature point ( i ) and pressure variance based on the
vectorenthalpies of formation [1]iniicalcPPs)(1exp2∑==-=...The aim of the work was to determine the
two-dimensional sections of the surface s 2 anddependence of the vapor composition in the Si (crystal) -
SiCl 4 system on the enthalpy of its formationcomponents, study the degree of change in the
composition of the steam when varyingenthalpies of formation of vapor components ( SiCl, SiCl 2 , SiCl
3 ).Two-dimensional section of the surface s 2is a function with twoasymptotes as ∆ f H → ± ∞. A
minimum is possible between these asymptotes. Calculationcomposition of the steam showed that with
an increase in the enthalpy of formation of each product,its concentration in vapor tends to zero. In this
case, the value of the design pressure is alldepends less on ∆ f H, and s 2 also to a certain limit. When
decreasingenthalpy of formation, the concentration of the corresponding product increases
andapproaching a certain limit.There is some difference between the calculated enthalpiesformation of
SiCl, SiCl 3 from reference data and the results of previous ones, whichrequire a separate detailed
analysis.1. Rusin A.D., Yakovlev O.P. Moscow University Bulletin, serieschemical, 1973, vol. 14, no. 5, p.
541.2. Schafer H., Nickl JZ anorg. allg. Chemie. 1953, Bd. 274, p. 250.187

Page 188
THERMODYNAMIC PROPERTIES OF POLYKETONES LOWMOLECULAR MASSNikischenkova L.V., Smirnova
N.N., Bykova. T.A., Kulagina T.G.Research Institute of Chemistry GOU VPO NNSU them. LobachevskyStudy
of the thermodynamic properties of polyketones, relatively new andpromising from the point of view of
practical application of monoxide copolymerscarbon with unsaturated hydrocarbons, is currently an
importanttask. Earlier [1,2] high molecular weight copolymers of monoxidecarbon with ethylene and
propylene. In this work, in order to identifypatterns of influence of the molecular weight of copolymers
on their thermodynamicproperties for the first time by methods of adiabatic vacuum and dynamic
calorimetrythe temperature dependences of the heat capacity = f (T) of low-molecularcopolymers of
carbon monoxide with ethylene in the range of 10 - 530 K and propylene inareas 6 - 350 K, identified and
characterized physical transformationsinvestigated copolymers occurring in the specified temperature
range.opCBased on experimental valuesnumericalvalues of zero entropy of copolymers and
thermodynamic functions(T),,,; combustion energy measured and calculatedstandard thermodynamic
characteristics of the reaction of formation of copolymersat 298.15 K, and the thermodynamic
characteristics of the processessynthesis (∆opCopC) 0 (H) (Hoo-Τ) (So Τ)(-) Τ(0ooHGcopoH , ∆ copoS , ∆
copoG ) low molecular weight monoxide copolymerscarbon with ethylene and propylene at p = 101.325
kPa.The data obtained indicate a discrepancy between the heat capacity curvescopolymers of carbon
monoxide with ethylene and propylene having differentmolecular weight, and the presence of a
noticeable effect of molecular weight onthermodynamic properties of polyketones.This work was carried
out with financial support from KCFE (project code A04-2.11-1166).1. Lebedev B.V., Zhogova K.B.,
Denisova Ya.V., Belov G.P., Golodkov O.N.Izv. Academy of Sciences. Ser. chem. 1998. No. 2. 284.2.
Lebedev B.V., Tsvetkova L.Ya., Smirnova N.N., Belov G.P., Golodkov O.V.Kurskiy Yu.A. Izv. Academy of
Sciences. Ser. chem. 1999. No. 8. 1527.188

Page 189

SYNTHESIS OF HIGH PRESSURE PHASES BASED ONHEXAGONAL MODIFICATION OF FULLERITE C 60Nikulin

M.M. 1 , Skokan E.V. 1 , Davydov V.A. 2 , Arkhangelsky I.V. 1 ,Senyavin V.M. 1 , Rachmanina A.V. 2 , Human
N.V. 1 , Agafonov V.N. 31 Moscow State University M.V. Lomonosov, Faculty of Chemistry,2 Institute for
High Pressure Physics, L.F. Vereshchagin RAS, Troitsk,3 University named after F. Rabelais, Tours, FranceTo
date, the formation of polymer phases by the action of highpressures and temperatures on samples of
the fcc phase of fullerite C 60 has been studied in sufficient detail.The structure, properties and
conditions for the formation of polymer modifications have been determined. Synthesishigh pressure
phases was carried out using as an initial statemetastable hexagonal (hcp) modification of fullerite C 60 .
Other usemolecular packing of the initial phase suggests a change in the mechanismpolymerization to
obtain other types of polymer phases. The polymer phases wereobtained in high-pressure chambers of
the "toroid" type under conditions of quasi-hydrostatic andhydrostatic compression in a wide range of
pressures (1.2-5.5 GPa) and temperatures (100-600C). The samples were characterized by XRD, IR
spectroscopy, and DSC.It is shown that the composition of the formed fullerite phases is different from
the polymer phases,obtained by thermobaric treatment of a stable fcc phase at the same valuespressure
and temperature.XRF data revealed a difference in the samples obtained under the conditionsquasi-
hydrostatic and hydrostatic compression. It was shown that in the casequasi-hydrostatic compression,
the polymerization process is preceded by a phase transitionGPU in the fcc phase. Therefore, the
samples of the hcp phase were subjected only to hydrostaticimpact. Petroleum ether was chosen as the
transmission medium.The sample obtained at 170C did not change its hcp structure, but its
parametersdecreased and amounted to: a = 0.9894 nm and c = 1.6147 nm versus 1.002 nm and 1.638
nm forthe initial hcp phase, respectively. The IR spectrum of this sample turned out to be close to the
spectrumdimeric phase, obtained by thermobaric treatment of the fcc phase of fullerite.The DSC method
revealed the presence of a depolymerization process with a maximumat a temperature of 190C. These
results make it possible to speak unambiguously about education.dimeric phase with hcp structure.It
was found that the depolymerization of the obtained high-pressure phasesis a kinetically inhibited
process, and at a heating rate of 10K / min the depolymerization process does not proceed completely
up to 550C. Productdepolymerization contains the initial hcp phase.189

Page 190

STUDY OF ELECTROCHEMICAL Dissolution of Cu-Zn-ALLOYS IN ACCURRENT POLARIZATIONNurdillaeva

R.N.International Kazakh-Turkish University. HA. Yasawi,The Republic of KazakhstanCurrently, AC
electrolysis has attractedthe attention of a wide range of researchers in the field of theoretical and
appliedelectrochemistry, in connection with the search for conditions that provide
intensificationelectrochemical processes.Known literature data [1] indicate that Cu-Zn alloysare
passivated with direct current polarization in neutral andalkaline environments. In aqueous solutions of
sodium and ammonium chlorides, the ionization of brasscomplicated by the formation of surface oxides,
since the presence of oxygensuppresses the processes of selective and uniform dissolution due to
passivation.In this regard, it is of certain interest to study the dissolution processCu-Zn alloy (brass) with
alternating current polarization.We have studied the process of dissolution of brass during polarization
with alternating currentfrequency of 50 Hz in sodium chloride solution. The influence of the current
density,electrolyte concentration, solution temperature, electrolysis duration,frequency of alternating
current to the current output (VT) dissolution of the investigated electrode.The experimental results
showed that under optimal conditions with polarizationbrass with alternating current in a sodium
chloride solution is observed quiteits intensive dissolution with the formation of copper (I) and zinc (II)
ions with a yield ofcurrent 96.9%.It was found that with alternating current polarization, the
processpassivation of the brass electrode, and the dissolution rate increases significantly, whichdue to
increased activation of the alloy surface as a result of fracturesurface oxide layer occurring periodically in
the cathodehalf-cycle of alternating current.1. M.V. Rylkina, Yu.G. Selezneva, S.M. Reshetnikov. Anodic
behavior of Cu-Zn-alloys in perchlorate media. // Protection of metals, 2000, Vol.36, No. 5, P.494-
500.190

Page 191

CATHODIC REDUCTION OF TELLURATE IONS IN AQUATICSOLUTIONSNurshimov A.K., Rakhymzhanova P.,

Beibitova A., Baeshov A.International Kazakh-Turkish University. HA. Yasawi,Kentau Institute, Republic of
KazakhstanThe main representatives of chalcogenes - selenium and tellurium - find a wideapplication in
semiconductor technology, therefore, the study of their electrochemicalbehavior in order to obtain pure
elements, represents a theoretical andpractical interest.We have investigated the effect of the electrode
material on the cathodic behavior of tellurateion in sulfuric acid solutions. The experimental results
showed that the wavehexavalent tellurium is observed only at the lead electrode. On thepolarization
curve recorded two waves, the first of which is present and onthe background polarization curve, and
corresponds to the reduction of lead sulfate,formed at the time of immersion of the lead electrode in a
sulfuric acid solution.The second wave appears in the potential range of -0.6 ÷ -0.7 V and, according to
our datacorresponds to the processes associated with the reduction of hexavalent tellurium.The fact that
the reduction of tellurate ions occurs only on leadelectrode, apparently, is explained as follows. After the
first highcurrent at potentials -0.4 -0.6 V, the electrode surface iselemental freshly formed lead. In this
case, the electrode surface is chargedpositively, since the potential of zero charge is in the range of -0.6
-0.7 V. Thusthus, favorable conditions are created for the adsorption of the tellurate ion onpositively
charged cathode surface and the flow of chemicalreduction of hexavalent tellurium with elemental lead
to formlead chalcogenides, which further undergoes cathodic
decomposition:÷÷ThoseHPBeHePB2022+→++Τ+...Comparison of the obtained data with the
electrochemical behavior of leadan electrode covered with a film of lead tellurides in a sulfuric acid
solution,confirms the mechanism proposed by us for the reduction of tellurium (VІ).191

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RESEARCH OF THE ELECTRIC DISSOLUTION PROCESSSULFUR-ELECTRODE IN AQUEOUS

SOLUTIONSOmarova A.K., Baeshova S.A., Baeshov A.International Kazakh-Turkish University. HA.
YasawiSulfur is a diamagnetic element, a typical non-metal, a very poor current conductor.However, a
review of literature data and analysis of the results of the study of electrodeprocesses involving sulfur
and its compounds showed that in a powder state, andthey have electrochemical activity [1].Previously,
the electrochemical behavior of powdered sulfur was studied atcathodic and anodic polarization on solid
electrodes only with directcontact with the surface of the collector.The aim of this work is to study the
electrochemical behaviorelemental sulfur using specially developed by us underthe leadership of Doctor
of Chemical Sciences, Professor A. Baeshov, which has no analoguesconductive sulfur electrode.The
features of the electrochemical behavior of the sulfur electrode anddependence of the current efficiency
of electrolysis products on various factors: densitycurrent, electrolyte concentration, solution
temperature and durationelectrolysis with DC polarization in alkaline, acidic and neutralsolutions.The
experiments were carried out in a glass electrolyzer with separationelectrode spaces with MK-40 cation
exchange membrane in aqueous solutions. INSulfur electrode of special composition is used as a working
electrode,a graphite rod served as an auxiliary electrode. After electrolysisthe qualitative and
quantitative composition of the test solution was determined.Thus, we have studied for the first time the
electrochemical behaviorelemental sulfur in aqueous solutions using compact non-metallicsulfur -
electrode and it was found that sulfur has a good electrochemicalactivity and dissolves with high current
yields of product formationelectrolysis.1. Baeshov A., Zhdanov S. et al. Electrochemistry of sulfur and its
compounds. Almaty, 1977,p. 160.192

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ADSORPTION OF ZINC IONS ON THE SURFACE OF TEFLON ANDFACTORS AFFECTING ITPautova I.N.Altai
State University, BarnaulWhen determining low concentrations of components in solution,
significantbecomes the magnitude of their adsorption on the walls of the dishes used in the analysis.
Fordetermination of the content of ions in the sample at the level of 10 -7 mol / l and less widelyuse the
method of stripping voltammetry (IVA). It is for this methodchange in the concentration of the
determined elements due to adsorptiondesorption processes is a significant value.The aim of this work
was to study the adsorption of zinc ions on the surfacepolytetrafluoroethylene (Teflon), which is
recommended in a number of monographs inas the material of the cell in IVA. The choice of zinc ions is
due to their highadsorption capacity on the Teflon surface. The adsorbent was used inthe form of
smooth rings with an area of 0.95 cm 2 each to simulate a surfaceelectrochemical cell.It was shown that
the equilibrium value of the adsorption of zinc ions on the surfaceTeflon is set within half an hour, while
the analytical signaldecreases by almost half. Increase in background electrolyte concentrationleads to a
decrease in the amount of adsorption of zinc ions. Usingbackground electrolytes with a different nature
of the cation, it was found thatthe adsorption of the ions to be determined had a minimum value in the
NaCl solution andmaximum in the KCI solution, which does not agree with the theoretical laws.In the
course of the work, the pH ranges were determined in which the adsorption of zinc was reduced
tominimum and maximum. Thus, by varying the composition of the solution, one cansignificantly change
the adsorption characteristics of zinc ions on the surfaceteflon. The results of this work can find practical
application when choosingstorage conditions and analysis of objects of various nature for
maintenancetrace zinc impurities when using Teflon cookware.193

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CATHODIC BEHAVIOR OF SILICIDES OF METALS OF THE IRON GROUP BACID ELECTROLYTES OF VARIOUS
COMPOSITIONPovroznik V.S., Shein A.B.Perm State UniversityIntermetallic and metal-like compounds of
various compositionsturn out to be promising in the search for new electrode materials withhigh
corrosion resistance and low hydrogen overvoltage. However,there are almost no systematic data in the
literature onbehavior of silicides in acid solutions.The purpose of this work is to study the process of
cathodic hydrogen evolution atsilicides of metals of the iron subgroup and their constituent components
in sulfuric acidelectrolyte and the influence of a number of halide ions of various concentrations on this
process.The investigated materials were metal silicides of the iron subgroup (FeSi,CoSi, NiSi) and their
constituent components (Fe, Co, Ni, Si with a purity of 99.99 wt%).Electrochemical studies of the
hydrogen evolution reaction (r.v.) werewere carried out on a PI-50-1 potentiostat using the method of
polarizationcurves.The results obtained indicate that in the case of silicides, practicallyalways, according
to the degree of inhibition of the cathodic process, halide ions form a series: CI - <Br - <I - . However, on
silicides, they do not cause such a sharp deceleration of the r.v.v. How onpure metals, which is associated
with the influence of halogen ions mainly on atomsmetal in the silicide sublattice. It was shown that the
presence of halide ions causesdisplacement of the Ψ 'potential in the negative direction, increasing the
speed of the stagedischarge and enhanced control of the cathodic reaction at the stage of
recombination.It was found that the hydrogen evolution reaction on metal atoms in the
compoundlighter in comparison with atoms of the same metal in its own phase, whichconfirmed by a
decrease in the orders of the cathodic reaction for monosilicidesmetals of the iron subgroup compared
with values for pure metals.194

Page 195
CALCULATION OF BINARY ADSORPTION ISOTHERMES ON ZEOLITES ONBASIS OF THE THEORY OF IDEAL
ADSORPTION SOLUTIONS(ON THE EXAMPLE OF THE SYSTEM "N 2 - O 2 - ZEOLITE NAX")Predtechenskaya
D.M.Moscow State University M.V. LomonosovIn the mathematical modeling of the separation processes
of binary gasmixtures, the problem arises of calculating joint adsorption isotherms in suchgas systems.
At the moment, the calculation of binary isotherms of adsorption based onbasic provisions of
thermodynamics is impossible. Binary isotherms of gasesare obtained in time-consuming and complex
experiments. The main advantagetheory of ideal solutions is that data on binary isotherms can beobtain
directly from the data of the individual gas adsorption isotherms.Based on the theory of ideal adsorption
solutions (IAS), an analysis was carried outexperimental data on joint adsorption of nitrogen-oxygen gas
mixtureon zeolite NaX. Experimental data on equilibrium binary adsorption of nitrogenoxygen mixture
on NaX zeolite, obtained by the authors of [1] were grouped inthree massifs referred to the
corresponding temperatures of 253.2K, 272.8K and 303K. Whenat each temperature, the authors of [1]
measured the adsorption isotherms of pure components inpressure range 0-6.3 MPa.In this paper, we
compare the values calculated by the IAR methodadsorption under conditions similar to those of
measurements of work [1]. Shown, thatapplication of the IAR theory to the description of microporous
systems in individual casesquite acceptable. Moreover, by combining the IAR theory and isotherms
derived inwithin the framework of the theory of stoichiometric adsorption, one can obtain a
convenientcomputational method for modeling multicomponent adsorption based onon experimental
isotherms of individual adsorptives [2].1. Gorbunov M.B., Arkharov A.M., Gorbunova N.A., Kalinnikova
I.A., SerpinskyV.V. Dep. VINITI, M., 1984, No. 1600 - 84.2. Kheifets LI, Predtechenskaya DM, ZhFKh, 2005,
in press.195

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INFLUENCE OF THE CEMENTITIC PHASE OF IRON CARBON ALLOYSON THEIR ANODE BEHAVIOR IN AN
Oxalic Acid EnvironmentPutilina M.S., Bespalova I.V.Lipetsk State Technical UniversityOxalic acid is used
as an etching reagent in metallography andcorrosion studies and as a tank cleaning agentstorage of
radioactive waste. However, the mechanism of this processanodic dissolution, which is accompanied by
passivation of alloys, is not completelystudied. Previously published results do not take into account the
effect of carbonaceousphase of cementite and its shape on the electrochemical behavior of alloys
inoxalic acid medium, the study of which is the purpose of this work.The studies were carried out in a
three-electrode cell in a solution of oxalicacid and potassium oxalate composition 0.1 M H 2 C 2 O 4 + 0.1
MK 2 C 2 O 4 (pH 3.5) with platinumcounter electrode and silver chloride reference electrode using
methodsvoltamper, chronoamper, chronopotentiometry and quantitative metallography.The objects of
study were: armco iron with a pure ferritic structure,carbon steels U8 (pearlite structure) and U12
(hypereutectoid ferritecementite structure).It was found that the voltammetric curves (2 mV / s) contain
a maximum of the anodiccurrent (I max1 ) at a potential E max1 = -0.3 V, observed on all alloys.
Moreover, oncurves of steels U8 and U12 there is a second maximum current observed atpotentials E
max2 = -0.03 ÷ 0.07 V. It is shown that the nature of the first maximumis the same for all studied alloys.
It was revealed that with the addition of Fe 2+ ions tosolution I max1 decreases with increasing
concentration of Fe 2+ ions . It can be assumed that one ofstages of anodic dissolution of the ferrite
phase is: FeOH ads + 0.5HC 2 O -4 + H +=0.5FeHC 2 O 4ads + 0.5Fe 2+ + H 2 O + e, as a result of which the
product isalong with the passivating layer Fe 2+ ions. It was suggested that the processthe oxidation of
the cementite phase is expressed by the equation: Fe 3 C-6e = 3Fe 2+ + C.It can be concluded that the
passivation of iron-carbon alloys inoxalic acid medium proceeds in two stages: at potentials lower than E
max2 ,ferrite is passivated, and at potentials more positive than E max2 ,the cementite component of
the metallographic structure is oxidized.196

Page 197

ADSORPTION MODEL OF FINITE LENGTH CHAIN MOLECULESRome A.V.Moscow State Academy of Fine
Chemical Technologynamed after M.V. LomonosovThe most famous theories of polymer adsorption on
solid surfacesrefer to the adsorption of infinitely long chain molecules. However, oligomershave their
own specific features that distinguish them from polymers. Therefore thesethe models are not very
suitable for studying the adsorption of oligomers because of the equal reactionthe ability of sites along
the chain length, the conformation of the Gaussian coil, excludedthe volume of the chains.Thus, the
proposed model of adsorption of chain molecules differs fromthe models described in the literature as
follows: 1) the sequenceprocesses ("proper" adsorption, reaction on the surface); 2) numberunreacted
surface centers does not correspond to the number of reactioncapable centers; 3) the inequality of the
places of oligomeric chain was usedmolecules.During adsorption, surface centers are divided into two
types: 1) active, that iscapable of further adsorption; 2) inactive, that is, not capable of adsorption.This
division of the active centers of the surface is carried out as in the case of adsorptionlow-molecular
compounds, and during the adsorption of chain molecules.To describe the equilibrium adsorption of low
molecular weight compounds, the mostthe Langmuir adsorption isotherm equation is used [1,2], which
impliesobligatory fulfillment of two conditions: 1) on one active center of the surfaceone molecule is
adsorbed; 2) all unreacted surface centers are activein reaction. During the adsorption of chain
molecules, both of these conditions are violated: 1) chainthe molecule is a multicenter system and can
be adsorbed by manycenters; 2) there are unreacted centers inaccessible for adsorptionsurface.
Therefore, the use of the Langmuir adsorption isotherm can hardly givedescription of the observed
experimental dependences on the adsorption of chainmolecules, which is known in the literature.
During the adsorption of chain molecules, inactivecenters are divided into several types: 1) centers that
have reacted with molecules; 2)unreacted centers, and inaccessible for the adsorption of other
molecules; 3) centers,located between the adsorbed molecules; their number is less than the
minimumnecessary to hold the molecule on the surface.197

Page 198

ELECTRIC REDUCTION OF BINUCLEAR MACROCYCLICCOMPLEXES OF COPPER (II) AND NICKEL (II) ([M 2 L]
Cl 2 ) IN WATERAND WATER-ORGANIC MEDIARoznyatovskaya N.V.Moscow State University M.V.
LomonosovIn this work, by the method of classical polarography on a mercury electrodethe effects of
electrocatalysis of the reduction of hydrogen peroxide in aqueousmedium (pH 6.0) in the presence of the
[Ni 2 L] Cl 2 complex and inhibition in the presence of[Cu 2 L] Cl 2 . To explain these effects, we studied
electroreduction[Cu 2 L] Cl 2 and [Ni 2 L] Cl 2 on a mercury electrode in an acetate buffer solution
(pH6.0). It was found that the reduction of [Cu 2 L] Cl 2is diffusion-controlled pH-dependent process with
transfer of four electrons,which corresponds to one polarographic wave. Reduction of [Ni 2 L] Cl
2complicated by strong adsorption of the reagent on the electrode surface. Previouslyelectroreduction
of [Cu 2 L] Cl 2 was studied only in organic solvents, inwhich are realized successive one-electron
reactions. The reasons for suchessentialinfluencesolventon thedifferenceredox potentialssuccessive
transitions are of independent interest. In order todetection, we carried out experiments on the
reduction of [Cu 2 L] Cl 2inmixed media (water-acetonitrile) on a platinum electrode (CVA method)
andmercury electrode (classical polarography). The findings indicateon the dependence of the number
of electrons transferred in the region of the first recovery wave[Cu 2 L] Cl 2on the water content. They
allow you to formulate the statementsubsequent model study of the molecular nature of the unusual
effect.This work was supported by the Russian Foundation for Basic Research, project No. 05-03-3238 / a
and the CouncilPresident of the Russian Federation on grants for leading scientific schools, grant NSh-
2089.2003.3198

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NON-EMPIRICAL CALCULATIONS OF EXCITEDVIBRATORY-ROTATIONAL STATES OF THE O 2

MOLECULERumnenko N.D., Adamson S.O.Moscow State University M.V. LomonosovCarried
outnumericalmodelingexcitednon-stationary(resonant) vibrational-rotational states arising in a system of
threethe lower 3 Π u electronic states of the O 2 molecule . Required for calculationpotential curves and
matrix elements of non-adiabatic binding werecalculated by the KV NIK method [1]. The received data is
in goodaccording to the results of previous calculations [2,3]. Calculation of non-stationaryvibrational-
rotational states was carried out by the method of external complexscaling.It is shown that in the
studied molecular system nonstationary electronvibrational-
rotationalfortuneslocalizednearareaspseudo-intersections of potential curves (~ 85000 cm -1 , 10.5 eV).
Good markproperties of these states can be obtained in the adiabatic approximation without taking into
accountnon-adiabatic interaction between electronic states. Accounting for similarof interactions only in
some cases leads to a sharp change in the widthresonant states. It was found that the widths of the
studied resonance statesweakly depend on the amplitude of the non-adiabatic binding functions.The
authors thank the Russian Foundation for Basic Research (RFBR)for support of the work (project No. 03-
03-3285а).1. MOLPRO a package of ab initio programs designed by H.-J. Werner andPJKnowles, version
2000.5.2. RJBuenker, SDPeyerimhoff. // Chem. Phys. Lett. 1975. V. 34. P. 225.3. BRLewis, ST Gibson and
JPEngland. // J. Chem. Phys. 2002. V. 116. P. 3286.199

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DIMENSIONAL REDUCTION IN THE QUANTUM DYNAMIC PROBLEMRyabinkin I.G., Novakovskaya Yu.V.,

Stepanov N.FMoscow State University M.V. LomonosovThe solution to the problem of the evolution of a
quantum system in time runs intoinsurmountable difficulties due to the very rapid
increasecomputational costs with an increase in the number of degrees of freedom of the system. In the
same timethe concept of the reaction path, actively used by chemists, emphasizes thatthe fact that the
trajectories of most of the systems of the statistical ensemble describingreaction, take place within a
relatively small area of the configurationspace, i.e. in a neighborhood of a manifold of low dimension.The
Hamiltonian of the reaction path was first introduced by Miller, Handy andAdams, who obtained the
expression of the corresponding classical functionHamilton. Later, a number of authors constructed
quantum Hamiltonians,corresponding to different reaction pathways, within the framework of different
modelideas about reactions.We have constructed an effective one-dimensional Hamiltonian for
studyingphotodissociation of a triatomic ozone molecule in excited electronstates. At the same time,
assumptions were made about the smallness of the distortion of the reaction path inexcited state
compared to the path in the ground state and aboutharmonic character of the potential energy surface
along the directions,perpendicular to the reaction path.Features of the behavior of the ozone molecule
in excited electronstates during photodissociation required a transition to diabaticrepresentation of
solutions to a molecular problem. For research itselfthe quantum dynamic problem was used the
method of wave packets.The overall reliability of the approach was monitored by
comparingexperimental branching ratio for singlet and triplet channelsdissociation with calculated
theoretical values.This work was supported by the Russian Fund for FundamentalResearch, the
Foundation for the Promotion of Domestic Science and the Ministry of EducationRF within the
framework of the Leading Scientific Schools project NSh-1275.2003.3.200

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PARTIAL MOL VOLUMES OF TETRAALKYLAMMONIUM IONSIn N, N-DIMETHYLFORMAMIDESvettsova E.V.

1 , Safonova L.P. 21 Ivanovo State University of Chemical Technology,2 Institute of Chemistry of Solutions
RASThis work is devoted to the study of volumetric effects upon solvationtetraalkylammonium ions in N,
N-dimethylformamide.Partial molar volume of an ion at infinite dilution 0V maybean indicator of the
manifestation of steric effects created by peripheralion groups. As objects of research, we usedsolutions
of salts of tetraalkylammonium bromides R 4 NBr (Et, Pr, Bu, Hex, Hep, Oct) in N, N-
dimethylformamide.The density of the investigated solutions (concentration from 0.05 to 0.4 mol / kg)
wasdetermined on a vibration densitometer "A.Paar" at 25ºC.Analysis of various extrapolation methods
in order to find standardthermodynamic quantities showed that a more accurate expression for
describingconcentration dependence of V φ using the Debye-Hückel theory..five232102qmbmmAVVV++
+=φ(1)where V φ is the apparent molar volume of R 4 NBr, b and q are empirical constants, A
Vtheoretical limiting slope for partial molar volume arising fromDebye-Hückel theory. Based on this
equation, the partialmolar volumes of electrolytes at infinite dilution.The values of V io
tetraalkylammonium ions were calculated using the valueV io (Br - ) = 15.492 cm 3 / mol.The analysis of
various contributions to the limiting partial molar volumelarge tetraalkylammonium ions. Conclusion of
partial penetrationsolvent molecules into free space inside large ionstetraalkylammonium.This work was
supported by the Ministry of the Russian Federation.(Grant No. Е-02-5.0-309).201

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NUMERICAL SIMULATION OF OZONE SYNTHESIS IN THE BARRIERDISCHARGESemyonov S.N., Tkachenko

I.S.Moscow State University M.V. Lomonosov, Faculty of ChemistryThe dynamics of the development of a
surface barrier discharge ingas. In modern literature, such a discharge is assumed to be an electric
dischargeat high (from 0.1 to several atmospheres) pressure, which occurs inconditions when the gas is
above the surface of the dielectric layer withlocated on it with a metal electrode. On the other side of
the dielectricthere is a wide electrode in the form of a metal plate. Attached betweenelectrodes, a
voltage of several kilovolts leads to breakdown andthe occurrence of physicochemical processes in the
low-temperature plasma of thisdischarge.To solve this problem, a 2.5-dimensional approximation of the
timeand the spatial development of the discharge in a self-consistent field. Dynamicssurface barrier
discharge was described by the differential systemcontinuity equations taking into account the emission
of electrons from the cathode surface,photoionization and ionization of gas molecules, electron
multiplication, kineticspositive and negative ions. Electric field configuration forthe discharge region and
for the dielectric was determined by the Poisson equation. Forthe method of fictitious charges was used
to determine the boundary conditions.The dynamics of modeling was given in the approximation of local
equilibrium.The simulation results are as follows:The spatial and temporal distribution of charged
particles indischarge region, the distribution of the electric field strength nearconductive electrode and
dielectric surface. It is concluded thatthe breakdown of the discharge gap is controlled by
photoprocesses. With increasing densitypositive ions, photoprocesses are replaced by ionic emission.
Ionic emissionleads to the formation of a cathode layer. The appearance of the cathode layer
abruptlyincreases current, supports the development and propagation of the conducting channel.The
accumulation of charge on the surface of the dielectric stops the discharge. Energy calculationprocess
and the amount of oxygen formed gives an idea ofproductivity of this ozonizer, which is about 10 W / g,
whichagrees well with experiment.202

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SORPTION OF RADIOACTIVE AND HEAVY METALSTWO-CALCIUM SILICATE FROM AQUEOUS

SOLUTIONSSemenova I.A., Nevraeva K.I., Pashkeev I.Yu., Mikhailov G.G.South Ural State UniversityThe
authors conducted studies of the sorption properties of dichloromethanesilicate, which is the main
mineral constituent of ferrochrome slag, withthe purpose of determining the possibility of using it as a
sorbent of radioactive andheavy metals from aqueous solutions. Sorption of cerium (IV), strontium(II),
copper (II) and iron (III) from aqueous solutions of salts of cerium (IV) nitrate, chloridestrontium (II),
copper (II) nitrate and iron (III) chloride.As a result of the research, the following sorptioncharacteristics
of dicalcium silicate:1. The distribution coefficient of cerium, copper and iron between the sorbent and
the watersolution of cerium (IV) nitrate, strontium (II) chloride, copper (II) nitrate and chlorideiron (III).2.
The degree of extraction of cerium, strontium, copper and iron from aqueous solutionscerium (IV)
nitrate, strontium (II) chloride, copper (II) nitrate and iron (III) chloride.3. Full exchange capacity of the
sorbent for Ce 4+ , Cu 2+ , Fe 3+ ions .4. The degree of extraction of cerium (IV), copper (II), iron (III) from
waste insolutions of cerium (IV) nitrate, copper (II) nitrate, iron (III) chloride of sorbent samples.5. The
minimum height of loading the material under study insorption column, in which the degree of
extraction of cerium (IV) from an aqueous solutioncerium (IV) nitrate was maximal.The study concluded
that it is possible to usedicalcium silicate as a sorbent for radioactive and heavy metals fromaqueous
solutions, which is important for any industrial enterprise. BesidesMoreover, research has expanded
knowledge of the properties of silicates, in particular, abouttheir sorption capacity.203

Page 204

TRANSITION STATES OF RADICAL SEPARATION REACTIONS:COMPARATIVE ANALYSIS OF QUANTUM-

CHEMICAL METHODS ANDMODELS OF CROSSING PARABOLES E.T. DENISOVSemesko D.G., Khursan
S.L.Bashkir State University, UfaA comparison of ab initio (quantum-chemical calculations) andempirical
(E.T.Denisov's model of intersecting parabolas - MPP) resultsdescriptions of the kinetics of reactions of
abstraction of H-atoms by free radicals, includingsulfate radical anion (SAR) from organic compounds of
various classes.The rate constants of the last reaction in water were determined in the laboratory of
chemicalkinetics of the Institute of Organic Chemistry, Ufa Scientific Center, RAS.By comparison with
reliable experimental data, the optimalcalculation method (B3LYP / or B3PW91 / 6-311 + G (d, p)) that
correctly reproducesgas-phase activation energies in reactions of abstraction of H-atoms by radicals H,
HO, Me,MeO, MeOO, NH 2 . Satisfactory correlation of geometricparameters of the reaction center and
activation energy found usingempirical and theoretical methods.The transient states of SAR reactions
with aliphatichydrocarbons С 1 - C 4 , chloromethanes Сl 1 - Cl 3 , methanol, dimethyl ether,acetone,
acetonitrile, nitromethane and dimethylsulfone; determined energiesactivation of the reaction of
abstraction of H-atoms in the gas phase.The effect of the solvent on the kinetics of radical SAR reactions
is shown. Influencesolvation for the activation energy was taken into account by two independent
methods: usingcontinuous model CPCM (COSMO), as well as using the MPP(the missing parameters for
calculating the energy of solvation are calculated quantumchemically). The results of calculating ∆E solv
by both methods correlate well with each other.friend (r = 0.97).The result of the work was the creation
of a model system usingexperimental data and results of empirical and quantum-chemicalcalculations.
An integrated approach allows one to quantitatively explain the kineticregularities and effect of the
medium for radical reactions of H-atom abstraction.204

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EFFECT OF MULTIPLE MODIFICATIONS ONADSORPTION PROPERTIES OF ACTIVE CARBONGladkova O.S.,

Solovieva Yu.V. 1Institute of Coal and Coal Chemistry SB RAS,1 Kemerovo Technological Institute of Food
IndustryActive carbons (AC) are used to extract a wide variety of substancesfrom a gaseous environment
and solutions. The adsorption capacity of these materialsdetermined by the structure and chemical
features of the surface. Changesurface parameters allows you to control the adsorption properties, so
theirmodification is currently receiving much attention.In this work, a comparative study of the
adsorption properties ofcarbon adsorbents: industrial AU brand AG-OV-1 (JSC "Sorbent") andsamples of
experimental activated carbon (EAU), as well as EAU coal,modified with ε-caprolactam.Natural coal
grade D was used as a matrix for the EAU(highway Gramoteinskaya) of the Kuznetsk coal basin, which
was carbonized, andthen activated. Thus, mono (EAU-1M), twice (EAU-2M)and three times (EAU-3M)
modified samples. Porous structure parametersThe obtained adsorbents were determined by nitrogen
adsorption at 77 K (350 0 C).Sorption properties for all samples were investigated using expressmethods
for determining the sorption capacity for benzene and iodine.Studies have shown that this modification
methodis a promising method for improving the adsorption properties of active carbons.Modification of
the carbon surface increased the total surface areaand the total pore volume, the volume of micropores
and the specific surface of the mesopores. Sorptionactivity, both for benzene and iodine of the obtained
modified samples forlevel and even higher than industrial coal grade AG-OV-1, which has highadsorption
characteristics. An increase in the multiplicity of modification leads toan increase in the adsorption
properties and all parameters of the porous structure.205

Page 206
NONADIABATIC TRANSITIONS BETWEEN ION-PAIREDCONDITIONS IN COLLISION OF IODINE
MOLECULESSuleimanov Yu.V.Moscow State University M.V. LomonosovTheoretical studies of non-
adiabatic transitions atcollision of an iodine molecule excited into an ion-pair (IP) state E0 g+ , withiodine
molecule in the ground state. To study the dynamics of collisionsthe well-known semiclassical version of
the perturbation theory of the firstorder. Relative motion of colliding molecules and their
rotationconsidered as classical degrees of freedom, oscillations and electronicmovement in molecules is
like quantum. Potential energy surfaces (PES) andmatrix interaction elements (MEDV) required for
modelingcollision dynamics, constructed using a simplified version of the theoryfirst-order perturbations
based on the approximation of diatomic fragments
inmolecule,moreoverintermoleculardisturbancemodeledthroughinteraction of anion and iodine cation
with Xe atoms. To account for multiparticleeffects in the formulas for the PES and MEDV corrections for
the long-rangeinteraction. It is shown that the dipole moment of the transition between closely spacedIP
states E0 g+ and D0 u+ makes the same contribution to the interaction potential atlarge distances, as
well as a constant dipole moment of the same magnitude and introducesdirect contribution to the
matrix element of interaction of states. Theoretical modelcorrectly reproduces the resonant distribution
of products over vibrationallevels obtained in the experiment, but the absolute values of the cross
sections are overestimatedcompared with experimental. It was found that a sharp increase in cross
sections atdecrease in the energy difference between the initial and final vibrationalby the levels E and D
of the state, respectively, occurs mainly due tolong-range interaction.206

Page 207

ELECTROCATALYTIC OXIDATION OF THIOPHENE IN IONICLIQUIDSTerekhov A.A.Moscow State University

M.V. LomonosovTo create molecular conductors, it is promising to usestarting materials of conductive
polymers based on thiophene, pyrrole, benzene,aniline, which have physicochemical properties that also
allowuse them in chemical sensors, fuel cells, ion-selectiveelectrodes and in electrocatalysis [1]. Such
polymers are characterized by widedegree of polymerisation, irregular structure and
unpredictableproperties. Electrochemical method of synthesis in an ionic liquid [2] aselectrolyte allows
you to control the stereoregularity of polymers, theirmolecular weight characteristics and other
important properties.Cyclic voltammetry and coulometry were used to
studyelectrochemicaloxidationthiopheneinionicliquids⎯1-methyl-3-
butylimidazoliumtetrafluoroborate.Measurementswere heldinthree-electrode cell, as a working,
auxiliary and reference electrodeused Pt.The range of electrochemical stability of the ionic liquid is
determined(-2.0 - 2.5 V) and the potential for the onset of substrate oxidation (1.1 V). Determined
thatelectrochemical oxidation of thiophene is a complex multistage process,including oxidation of the
substrate with the formation of the corresponding radical cation.The linear character of the dependence
of the current density of the formation of cationof the monomer radical of the square root of the
potential sweep rate, which isserves as evidence of the reversible nature [3] of the initial stage of
oxidation .The products of thiophene oxidation in the potential cycling mode were obtained, andalso at
potentials 1.4 V, 1.7 V and 2.0 V. The total number ofelectrons participating in the oxidation of one
monomer unit. The proposed schememechanism of electrocatalytic polymerization of thiophene in an
ionic liquid.1. MacDiarmid AG, Synth. Met., 1997, Vol. 44, p. 27-34.2. Ionic Liquids in Synthesis, Ed. by
Wasserscheid P., Welton T., 2002 Wiley-VCHVerlag GmbH & Co. KGaA, Weinheim, Germany.3. Baizer
MM, Lund H., Organic electrochemistry, Moscow: Chemistry, 1988, p. 99.207

Page 208

STUDY OF TEMPERATURE DEPENDENCE OF HEAT CAPACITYBISULPHATE GRAPHITETimokhova O.A.,

Leshin V.S., Arkhangelsky I.V.Moscow State University M.V. Lomonosov, Faculty of ChemistrySome of the
most promising compounds from a practical point of view andinteresting - with the fundamental are
graphite interstitial compounds (IVG),interest in which is primarily due to the structural features of the
SVG - regularlayered structure, high anisotropy of properties, as well as an unusual characterconnection
of embedded substances with a graphite matrix.In this work, we investigated the temperature
dependence of the specific heatgraphite bisulfate (BG) with different content of embedded sulfuric
acid.BG samples are synthesized by electrochemical method with anodic polarizationhighly oriented
graphite in conc. sulfuric acid ( I = 100 μA). Phasethe composition of the obtained samples was
controlled by the XRD method. Heat capacity of bisulfategraphite was determined by differential
scanning calorimetry intemperature range from -70 to 20 of S. These limitations are caused by
onecapabilities of the device, and on the other hand, stability and reactionability of connections. As a
standard for calculating heat capacitya sample of high-purity crystalline sapphire was used. Experiment
andheat capacity calculations were performed according to ASTM E 1269.In our work, it is shown that
the heat capacity of graphite bisulfate in the region of lowtemperatures above the additive heat capacity
of the corresponding amounts of graphite andsolid sulfuric acid, and at temperatures above the melting
point of sulfuricacid (~ 10 о С), on the contrary, its heat capacity is lower than the additive heat
capacityappropriate amounts of graphite and liquid sulfuric acid. Receivedthe results indicate a special
state of sulfuric acid in the graphite matrix,which has a greater degree of freedom than sulfuric acid in
crystallinecondition, but less than in liquid.Differential scanning calorimetry was used to detectlow-
temperature phase transitions of the first order, the magnitude and temperature of whichdepends on
the amount of incorporated sulfuric acid.208

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COMPLEX FORMATION OF TWIN-80 WITH BOVINE WHEYALBUMIN AND STABILIZATION OF THIN FOAM
FILMSFilatova L.Yu.Moscow State University M.V. LomonosovInteraction of proteins with nonionic P.A.V.
very little has been studied despitewidespread use of their mixtures in the food, pharmaceutical
industries and inmedicine.The work is devoted to the study of the interaction of nonionic P.A.V. Twina -80
with bovine serum albumin using a complex of methods(tensiometry, study of the conditions for the
formation of stable foam films, I.K., U.F. -spectroscopy). Three series of solutions with a constant protein
concentration of 6 * 10 -6 , 1 * 10 -5 , 1 * 10 -4 and variable concentration of Tween-80.The critical
concentration of the association was determined by tensiometric method(K.K.A.) - the minimum
concentration of P.A.V., at which in the aqueous phase beginsassociation of modified protein molecules.
Introduced the concept of a complexmaximum saturation (M.K.K.), its composition was determined (per
one B.S.A.there are 10 PAV molecules). Maximum concentration of M.K.K. (S.m.c.k.) inthe aqueous phase
corresponds to the concentration of the protein in the binary mixture.By the method of W.F. -
spectroscopy found that after K.K.A. observedthe appearance of a new phase in the three-component
system water - P.A.V. -protein.By the method of I.K. - spectroscopy showed that the complex is formed
due tohydrogen bonds between the amino groups of the side chains of amino acids locatedon the
surface of the protein, and the carbonyl oxygen atom of the ether group of Tween - 80and that there is
no change in the secondary structure of B.S.A.A mechanism for the stabilization of foam films by binary
mixtures is proposed.Twin -80 / B.S.A.This work was carried out with the financial support of R.F.F.I.
project No. 04 - 03 - 32633209

Page 210

SCHEME OF ELECTROCHEMICAL DISSOLUTION OF ARMCO-IRON INLEMONIC ACIDFilatova Ya.B.Lipetsk

State Technical UniversityWidespread use of citric acid in various industriesleads to the need to create
effective means of protecting technologicaliron-based alloys used in the process of storage,
transportation,recycling and disposal, for which the latter is an aggressive environment.The theoretical
prerequisite for this is the study of the mechanismelectrochemical dissolution of iron-carbon alloys in
citric acidsolutions, carried out using the voltammetric method of analysis.The studies were carried out
on Armco iron in citric acid solutions (5.5 <pH <8) with the addition of sodium citrate and a constant
ionic strength of 0.48. Electrodekept at a potential of -0.8 V relative to saturated silver chlorideelectrode
for 5 min, and then subjected to potentiodynamic anodicpolarization. It was found that from the
thermodynamic point of view, the smallestthe oxidation reaction of metallic iron to Fe (II) - ions withthe
formation of a citrate complex FeC 6 H 6 O 7 upon interaction with the environment. Together withSo, of
the four possible forms of existence of citric acid in solutionthe most likely participants in the anodic
process are hydrocitrate ionsC 6 H 6 O 72 - because the value of the logarithm of the anode current in
the Tafel region is lineardepends on the logarithm of the concentration of a given ion for different pH
valuessolution, while the order of the reaction for hydrocitrate ions is close to 1, and for H + -ions - to 0.
The values of the slope of the Tafel straight line and the transfer coefficient,found from semilogarithmic
dependences were 0.063 and 0.47respectively.On thebasisof thiscanoffernextfour-stage scheme of the
anodic process of iron dissolution:1. Fe 0 + H 2 O ↔ Fe (OH) -ads + H + - fast;2. Fe (OH) -ads + C 6 H 6 O
72- + H + ↔ FeC 6 H 6 O 7- + H 2 O + e -limiting;3. FeC 6 H 6 O 7- ↔ FeC 6 H 6 O 7 + e - fast;4. FeC 6 H 6 O
7 ↔ FeC 6 H 5 O 7- + H + - fast.Electrochemical parameters calculated taking into account the proposed
scheme(reaction order, Tafel slope and transfer coefficient) are in goodagreement with those found
experimentally.210

Page 211

STRUCTURE OF ANTHRAQUINONE AND FLUORENONE COMPLEXES WITH LCCALUMINUM OXIDE

SURFACESFokina I.V., Lyashkov V.M., Fionov A.V.Moscow State University M.V. Lomonosov, Faculty of
ChemistryOne of the most widely used methods for studying acid-basesurface properties of catalysts
based on metal oxides is the EPR methodparamagnetic complexes of probe molecules with Lewis acid
sites(LCC) oxide surfaces. In this regard, the study ofmechanism of adsorption of molecules on the
surface of oxide catalysts withthe subsequent formation of paramagnetic complexes.In this work, a
quantum chemical calculation of geometric andmagnetic resonance parameters of complexes of 9-
fluorenone and 9,10-anthraquinone withalkali metals and protons in solutions by DFT method. Good
receivedcorrespondence with the literature data, thereby showing that the chosen methodcan be used
to calculate complexes not described in the literature.Paramagnetic complexes of 9-fluorenone and 9,10-
anthraquinone with surface LACoxides were modeled as complexes of the corresponding radical anions
withcation Al (OH) 2+ .When optimizing the geometric structure of complexes without anythe initial
constraints on the structure of the complexes were flat, and the constantshyperfine interaction on 27 Al
atoms is much less thanexperimentally observed constants.In this regard, steric constraints were
imposed in the simulation.It is shown that constants close to the experimental ones are obtained if the
complexeshave a non-planar structure.Thus, based on the calculations performed, the structure was
proposedparamagnetic complexes of probe molecules with LAC of the surface of aluminum
oxide,allowing a satisfactory explanation of the entire set of experimental data.This work was supported
by the Russian Foundation for Basic Research (grant 05-03-33006) and the program"Universities of
Russia" (grant level 05.02.549).211

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QUANTUM-CHEMICAL MODELING OF ELECTRONICABSORPTION SPECTRA OF FLUORENONE-9Frantseva

A.G., Minaev B.F.Cherkasy State Technological UniversityRecently, compounds of the aromatic series of
the fluorenone classused for the synthesis of low molecular weight synthetic drugs (flurenizide,amiksin
and tilorone), stimulating the formation of endogenousinterferon. An integral part of these drugs is
fluorenone-9.When studying the absorption and luminescence spectra of flurenizide [1]it was necessary
to assign the nature of the wave functions of the excitedstates. In order for such an assignment to be
justified, we werethe electronic absorption spectrum of fluorenone-9 was studied based on a
comparison of the calculatedand experimental data [2].Origin T 1 transition describes the local n-π * in
ozbuzhdenie carbonyl group,having the lowest absorption frequency and zero intensity. TransitionΨ 33
→ Ψ 34 from the upper occupied molecular orbital (HOMO) to the lower vacant(LUMO) - the first
characteristic absorption band of fluorenone has a small butnon-zero intensity. In this case, the HOMO
does not contain the contribution of the C = O group, forreflection in the yz plane is asymmetric. LUMO
has a large contribution from oxygen andis symmetric in the yz plane , hence the charge transfer arises,
and the vectorthe dipole moment is directed along the y- axis . States S 3 - S 5 facilitate the transition
fromdouble contributions. The transition Ψ 31 → Ψ 34 does not change the direction of the dipole
vectormoment and is characterized by a large contribution to the C = O group. Excluding carbonylgroup,
the transition Ψ 33 → Ψ 36 occurs . In this case, the excitation is asymmetric andcarries the main
contribution to the side rings of the molecule. Average absolute errorcalculation was 0.07 eV, which
gives good agreement with experiment. Quantumthe chemical calculation was carried out by the
semiempirical method in the AM1 approximation.1. Petrukh L.I., Pronyuk A.V., Mykhalyk O.I. and others
XII National Congress onrespiratory diseases - Moscow, November 11-15, 2002.2. Nurmukhametov R.N.
Absorption and luminescence of aromatic compounds- M .: Chemistry, - 1971, - 216 p.212

Page 213

DETERMINATION OF THE TEMPERATURE DEPENDENCE OF HEAT CAPACITYSINGLE WALL

NANOTUBESKharin A.A., Arkhangelsky I.V., Tarasov B.P. 1 , Muradyan V.E. 1Moscow State University M.V.
Lomonosov,1 Institute of Problems of Chemical Physics RASSingle-wall carbon nanotubes were obtained
by the electric arc method(ONT). The synthesis of HCB was carried out in an EDIG apparatus designed on
the basis of IPCPRAS. Graphite rods were used as electrodes, in one in the center was drilledchannel for
subsequent filling with 3 Co / Ni powder (anode). Evaporation was carried out inatmosphere of helium at
a pressure of 500 Torr. Products of electric arc evaporation metalgraphite electrode condense on the side
walls of the cooled chamber(“Wall” soot), around the cathode (“collar” soot) and directly oncathode
("deposit"). At the bottom of the reactor, a “slag” that does not contain HCT is deposited. Trustthe
product is collar soot because the content of ONT in it is the mosthigh.The HCT purification procedure
includes the stage of fullerene isolationextraction with toluene, alternating stages of acid treatment
andthermal oxidation in air with a gradual increase in temperature, degassing invacuum at high
temperatures.In the temperature range 200 - 500 K, the temperature dependence is determinedheat
capacity for collar soot and HCT samples using the NETZSCH instrumentDSC 204 “Phoenix”, sample
heating rate 10 ° / min. In the measuring cella dynamic helium medium was created at atmospheric
pressure (flow rate 50ml / min). It is shown that the heat capacities of the samples differ by almost three
times in alltemperature range. Experimental data with sufficient degreeaccuracy are described by a
general polynomial of the form... For collarsoot, in the intervaltemperatures from 193 K to 505 K. For
samples of purified HCTdescribedinin the interval 199 K to 483 K. Parallel measurements were carried
out for each samplethree times.2cTbTaC P++=2-6-3Tten35), 010 (Tten0.25)18.93()0.041140.81737(⋅⋅±-⋅⋅±
+±-=pC2-6-3Tten17), 02.39 (Tten0.12)5.18 ()0.01960.41894(⋅⋅±-⋅⋅±+±-=pC213

Page 214

ADSORPTION OF VAPORS OF LINEAR AND BRANCHED ALCOHOLS ONFLUORINATED CARBONKhrycheva

A.D., Glazkova S.V.Moscow State University M.V. LomonosovIn recent decades, the scientific and
technical direction has been actively developing,associated with the production and use of various
fluorinated carbons.However, the number of scientific publications devoted to the study of propertiesthe
surface of such materials is very small.In our work, by gas chromatography (GC), we
investigatedthermodynamic characteristics of the adsorption of a set of n- alkanes and
saturatedfluorinated carbon alcohols (FC). The comparison adsorbent wasselected graphite thermal soot
(GTS), which has a homogeneousnon-polar surface. It is shown that the Henry constant K C and standard
entropyadsorption ∆ S ° of all studied compounds on fluorocarbon is much lower, inwhile the heat of
adsorption q is much higher than on the GTS. Unlike the GTS, on FCthe values of ∆ S ° are significantly
less than those calculated according to the idealtwo-dimensional gas, and the difference increases with
increasing molar massconnections.It turned out that there is a linear relationship between the quantities
∆ S ° and qfor different compounds, according to which the points corresponding to n- alkanes, as well
asdifferent isomers of saturated alcohols, grouped near a straight line,and the deviations from linearity
are within the determination errorquantities q and ∆ S °.It is shown that the values of K Cdrop sharply
when going from linear tobranched alcohols due to a decrease in the number of contacts of the
molecule withthe surface of the adsorbent. It should be noted that the selectivity of the separation of
isomericalcohols on FC, including sec-butyl and isobutyl alcohols, timesthe retentions of which are close
enough is not inferior to the results on the GTSis considered an indispensable adsorbent for solving
practical problems related toseparation of isomers.The data obtained are recommended for predicting
retention andidentification of oxygen-containing compounds in GC.214

Page 215
EXTERNAL CHARGE TRANSFER IN THE SYSTEMDq 2+ - Fe (CN) 6 ] 4-Tsarevsky I.I.Moscow City Pedagogical
UniversitySynthesized and structurally characterized diquat hexacyanoferrate (6.7 -dihydrodipyrido [1,2-
a: 2`, 1`-c] pyrazinidinium, Dq 2+ ). The observed inelectronic absorption spectra of solid Dq 2 [Fe (CN) 6 ]
* 6H 2 O and its aqueoussolutions of the outer-sphere charge transfer band. Spectral
manifestationouter-sphere electron transfer is used to obtain quantitativecharacteristics of the process
of outer-sphere complexation. Found by methodBeneci-Hildebrand [1] stability constants of the ion pair
Dq 2+ , Fe (CN) 6 ] 4-are 6.1 ± 0.5 L / mol (at the ionic strength of the solution of 1 mol / L) and 270 L /
mol (atthe ionic strength of the solution is 10 mmol / l in the absence of added background
electrolytes).According to the Fooss equation [2], using the obtained values of the stability
constants,estimated the distance of electron transfer in the ion pair. 5.4 E. Thisthe value is close to the
values obtained from the data of X-ray structural analysis.So the shortest Fe-N (pyridine ring) distance in
the structureDq 2 [Fe (CN) 6 ] * 6H 2 O is 5.02 Е, and the shortest distance from the iron atom tothe
center of the pyridine ring - 5.62 E. The totality of the results obtainedallows us to conclude that the
shortest distance between cations and anions inDq 2 [Fe (CN) 6 ] does not depend on the phase in which
the ions arecompound.1. HA Beneshi, JH Hildebrand, J. Amer. Chem. Soc., 1949, V. 71, p. 2703.2. RM
Fuoss, J. Amer. Chem. Soc., 1958, V. 80, p. 5059.215

Page 216

ADSORPTION OF METHYLENE COLORS ON THE SURFACEPOWDER OF FLUOROPLAST "FORUM" FROM

AQUEOUS SOLUTIONSO. V. Shangareeva 1 , Fedoseeva V.I., Fedoseev N.F.Permafrost Institute named
after acad. P.I. Melnikov SB RAS,1 Yakutsk State University named after M.K. Ammosov,Permafrost
Institute, fedoseev@mpi.ysn.ruThe properties of multicomponent heterogeneous systems are
determined by the naturesurface properties of dispersed components. These properties determine the
degreethe affinity of system components to each other. The most important physico-chemicalthe
characteristic of dispersed substances is the specific surface area,which can be estimated by adsorption
methods from the gas phase or fromsolution.Fluoroplastic is known as a hydrophobic, chemically inert
material. However, independing on the conditions for its preparation, the surface may contain
functionalgroups that manifest themselves in certain interactions. Fluoroplastic powder“Forum” was
synthesized at the Institute of Chemistry of the Far Eastern Branch of the Russian Academy of Sciences
bythermal destruction of phoroplast-4 with the release of particles of small diameter and
correctspherical shape. It is supposed to be used as a hydrophobicfiller in the study of the
physicochemical properties of frozen water-containingsystems.To estimate the specific surface area of
the studied powder, we used the methodadsorption of dyes from solutions. The adsorbates used are
methylenedyes like methylene blue, as well as rhodamine 6G, which showed the highestaffinity for the
surface of the adsorbent. The adsorption isotherms obtained in this wayobey the Langmuir adsorption
equation. Powder specific surfacethe investigated fluoroplastic is estimated to be 320 (methylene blue)
and 370 m 2 / kg(rhodamine 6G). The difference in the values of the adsorption constant "B"
(respectively,6.75⋅10 3 and 3.77⋅10 4 l / mol) indicates a stronger binding of rhodamine withactive
centers of the fluoroplastic surface and is apparently due to morethe extensive structure of its ion in
comparison with the cation of methylene blue.216

Page 217
CATION-DEPENDENT PHOTOCHEMICAL BEHAVIOR CROWNCONTAINING POLYTOPE RECEPTORShepel N.E.
1 , Fedorov Yu.V. 1 , Fedorova O.A. 1 , Gromov S.P. 1 , Alfimov M.V. 1 ,Saltiel D. 21 Center for
Photochemistry RAS,2 The Florida State University, Department of Chemistry, Tallahassee,
FloridaMacrocyclic ionophores based on polyester derivatives,attract attention due to their ability to
selectively bind metal cationsand the possibility of using as functional units in supramolecularsystems. In
this study, the behavior of photochromic polytopicreceptor 1 based on crown-containing benzobis (2-
styrylthiazole) as well as itscomplexes with alkali and alkaline earth metals usingabsorption; emission
spectroscopy; HPLC, using matrixphotodiode detector and "electrospray" mass spectrometry withusing
high resolution mass spectra in conjunction with HPLC fordetermining the exact molecular
weight.OOOOONSNSOOOOOOOOOONSNSOOOOOOOOOONSNSOOOOOOOOOOOOOOONSNSPhoto-
isomerization1[2 + 2] photo-
cycloadditionPhotochemicalbehavior1substantiallydependsfromprocesscomplexation and the nature of
cations. It was found that 1 forms complexes withmetal perchlorates, namely, [ 1 1 · (M n + ) 1 ] and [ 1 1
· (M n + ) 2 ] (M = Na + , Mg 2+ , Ca 2+ ) and,[ 1 · (M 2+ ) 2 ] and [ 1 2 · (M 2+ ) 2 ] (M = Rb + , Ba 2+ , K + ).
Irradiation with UV light 1 or complexes 1 sMg (ClO 4 ) 2leads to the occurrence of the reaction of trans-
cis- photoisomerization and[2 + 2] photocyclic addition, and for complex 1 with Ba (ClO 4 ) 2 , theonly
one reaction - [2 + 2] photocytoaddition.This work was supported by INTAS (Grant 03-51-4696) and RFBR
(Projects:05-03-32268 and 03-03-32849).217

Page 218

SOME ASPECTS OF INDIRECT CATHODIC AMINATIONAROMATIC COMPOUNDSYudina E.A., Busygina N.V.,

Lisitsyn Yu.A.Kazan State UniversityInterest in the electrochemical amination process is due tothe
fundamental possibility of the synthesis of aromatic mono- and diamino compounds inone technological
stage [1]. A key role in the cathode-initiated processthe mediator system Ti (IV) / Ti (III) plays, therefore,
from the standpoint of the development of ideas aboutits synthetic potential, the purpose of this work
was to establishdependence of the efficiency and selectivity of radical substitution on redoxproperties
and state of titanium ions in aqueous and aqueous-organic solutions of sulfuricacid.As a result of
spectrophotometric, polarographic, kinetic andelectrosynthetic studies carried out both in the absence
andin the presence of organic solvents (CH 3 COOH, CH 3 CN), it was found thatelectrochemical
amination of aromatic substrates using the systemTi (IV) - NH 2 OH must be carried out in electrolytes
with a sulfuric concentrationacids not less than 7 M, in environments with a high content of sulfate
complexesTi (IV). Complexes TiOH 2 (SO 4 ) 2 and TiOH 2 SO 42+ , as well as their derivatives containing
incoordination sphere of solvent molecules, increase the redox potential of the pairTi (IV) / Ti (III) and
thereby reduce the rate of competitive amination reactionreduction of amino radicals with titanium
(III).By the example of the amination process of 4-chloroaniline, it was shown thatconcentrated solutions
of sulfuric acid, in which the complex dominatesTiOH 2 SO 42+ ,availableeffectivehighly
selectivesynthesis1,3-phenylenediamines containing deactivating ortho-, para-orientingdeputies.T 17M
H 2 SO 4implementedsynthesis4-chloro-1,3-phenylenediamine with current efficiencies and 4-
chloroaniline, respectively, 75 and96%; the only by-product of substitution under these conditions is1,4-
phenylenediamine, its current efficiency is 0.3%.1. Lisitsyn Yu.A., Kargin Yu.M. "Electrochemical
aminationunsaturated and aromatic compounds "// Electrochemistry, 2000, T. 36, N 2,S. 103-114.218
Page 219

STUDY OF SINGLET-TRIPLET TRANSITIONS IN A MOLECULEOZONE BY THE METHOD OF MK SSPYashchuk

L.B., Khomenko E.M.Cherkasy State Technological UniversityThe excited triplet states of the ozone
molecule are not importantonly for the spectroscopic and photochemical properties of this molecule,
but alsoto explain its chemical reactivity. In that workthe probabilities of the lower 3 A 2 , 3 B 1 ← X 1 A 1
of the singlet-triplet transitions (S-T) are presentedto individual spin sublevels calculated for the two
lower excitedtriplet terms of the O 3using the multi-configuration methodself-consistent field (MC SSP)
using the theory of quadratic response.Comparison of the results of calculating the intensities of singlet-
triplettransitions when using different basis sets and full activespaces. The assignment of the 3 А 2 ← Х 1
А 1 transition in the absorption spectrum of ozone toWolfe's strip. The results of calculations by the MC
SSP method significantly depend onselected full active space and calculation basis.The transition 3 B 2 ←
X 1 A 1 was obtained very weak, which is consistent with the previoustheoretical works [1], and with
experimental data [2]. Its M x (T z )component of the transition moment is obtained stronger than M z (T
x ), which is almostminor: M x (T z ) = 1,6⋅10 -4 AU for vertical 3 V 2 ← X 1 A 1 excitation in the basiscc-
pVTZ, and M z (T x ) = 2⋅10 -6a.u. Similar calculation results were also obtained withusing other methods.
Based on these calculation results, you canconclude that 3 A 2 ← X 1 A 1 and 3 B 1 ← X 1 A 1 absorption
bands in the O 3 molecule aresufficiently intense and the Wolfe absorption system can be
attributedexclusively to these two transitions. Moreover, the first 3 A 2 ← X 1 A 1 transition
contributesmainly in the long-wavelength region of the Wolfe absorption band.1. Braunstein M, Martin
RL, Hay PJ // J. Chem. Phys. 1995. V. 102. No. 9. P. 3662.2. Bouvier AJ, Wannous G., Churassy S., Bacis R.,
Brion J., Malicet J., Judge RH //Spectrochimica Acta Part A. 2001. V. 57. P. 561.219

Page 220

Author Index, Volume 2(* - speaker)Abakumov A.M.39.81.95.101Abakumov G.A.40,47,140Abisheva A.B.

*136A.A. Abramov128Abramov P.A. *67V.V. Avdeev64E.V. Avdeeva42Avdey A.V. *34Agafonov
V.N.189Ageeva A.F. *137Adamson S.O.199Azhigulova R.N. *138Akzhigitov A.O.152Alekseeva Yu.P.
*35Alferov V.A.141Alfimov M.V.,217Alyabyshev S.V. *139Antina L.A. *6I.S. Antipin147Antipov
E.V.39.79.81.86.101Arapova A.V. *140Ardasheva L.P.52.74Arkhangelsky I.V.64,189,208,213Asachenko E.V.
*7Astafiev D.A. *68E.V. Astashina26Atyaksheva L.F.32Afonichkin V.K.127Babkina E.E. *141Baeshov
A.182,191,192Baeshova S.A.182,192Balashev K.P.55Balashov A.M. *69Baranova O. V. *70Baranova
S.V.31Baskin I.I165Batov D.V.142Batov D.D. *142Batuk O. N. *109,118Bezrukov D.S. *143Beibitova
A.191Bekeneva A.V.177Beketov K.M.170Belov A.S. *144Belousov Yu.A. *71Belyakov M.V. *72Beregalov
A.E. *8Berezin B.D.61,164Berezin D.B.61Berezin M.B.164Bespalova I.V.196Blinova O. A. *110Bobreshova
O.V.145Bobylkina O.V. *145Boyko R.S. *37Bokach N.A.77Boltalin A.I.104Borisov I.M.137Borisova N.V.
*36Borodina I.B. *nineBortnikova M.S. *111Bubnov M.P.140Busygina N.V.218Bykova N.V.162Bykov.
T.A.188Vakulina A.V. *146Validova L.R. *147V.V. Vanovsky *148Varlakova G.A.123Vasiliev A.N.95Veresov
A.G.102Veryaeva E.S. *149Vidyakin M.N.178Vinokurov A.A. *73Viter V.N. *38Vishnevskaya E.E.
*150Vlasova I.E.126Vovk G.V. *74Volykhov A.A. *151Voronov A.S. *10.20Gavrilov A.N. *elevenGavrilov
K.N.13Gainullina E.I. *112Galimova A.Z. *75Gantman M.G. *12A.V. Geyer *152Giricheva
N.I.48.65Gladkova O.S. *205Glazkova S.V.214Glushkov K.V.92Govorov V.A. *39S.V. Golovataya *153220
Page 221

E.P. Golovin63A.V. Golubev *154E.V. Golubina16.21A. V. Gopin *113V.V. Gorbachuk147Gorshkov M.Yu.

*155I. I. Grigoriev *76Grinev T.A. *156Gromov S.P.217A.A. Grosheva *157Grunova E.V. *40Gubaidullina
G.M. *41Guskov V.Yu. *158Gushchin A.L.67P.V. Gushchin *77Davankov V.A.13Davydov V.A.189Danilov
D.N. *42Dvinyaninova N.B.172Dedyulin S.N. *78Dmitriev S.A.123Dorozhkin E.I. *159Drozhzhin O.A.
*79Drozdov A.A.71,100Dunyushkina L.A.155Evkovich I.N. *114Yelensky A.A. *160Eliseeva S.V.
*43Emelyanov A.A.177Eremin V.V.184Eremina Yu.V.25Ermakov A.I.128Ermilov A.Yu.34.69Ermolaeva
M.N.36Efremova M.M. *161Efremova O.A. *80Zhakitova G.U.41Zharnikova N.V. *162Zheglov S.V.
*13Zhirnov A.E. *115Zaikovsky V.V.elevenZatolnaya O.V. *163S.V. Zvezdina *164,180Ziganshin
M.A.147Zimin Yu.S.137Zlomanov V.P.42I. V. Znamenskaya *116Zolin V.F.one hundredZosimova P.A.
*fourteenIvanov E.V.142Islamova N.I.174Istomin S.Ya.79.86A.A. Kabkov *15E.P.
Kazachinskaya165Kayynbaeva R.A. *45Kalashnikova N.A. *166Kalinenko E.V. *167,172Kalyuzhnaya A.S.
*81Kandeev K.V. *168Kapralova V.I.45Karlin Yu.V.120Karlina O.K.111,123Kasimova V.Yu. *169Kachevsky
S.A. *sixteenKashirin I.A.128Kemelbekov U.S. *170Kim Dong Kyu *117Kireev A.S. *17E. N. Kiseleva
*171Kistanova N.S.167Kistanova N.S. *167,172Klementyeva S.V. *173Klyueva M.E.171Kovalev S.V.
*82V.V. Kovalenko *44Kovalenko K.A. *83Kozhanov K.A.140I. V. Kozhemyakin *15.18Kozina O.
L.186Kozlov A.V.174Kozlova E.A. *nineteenKolyagin Yu.G.27Komissarova L.N.58E. S. Kondakova
*84Konkin S.I.13Konnov S.V. *20Konovalov V.V.150Konstantinova K.K. *175Kopylovich M.N.105Kornienko
Z.I.37V.P. Korolev142,177V.V. Korolkov *176Crown D.V. *46Korotkov A.V. *21Kosolapov
A.S.167,172Krasikova R.N.125Krestyaninov M.A.177Kuzmenko N.E.187Kuzmina N.P.69Kukushkin
V.Yu.77.105221

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Kulagina T.G.188Kulikov L.A.113Kulintsov P.I.145S.V. Kurbatova175A. V. Kustov *177B.A. Kukhtin63Lado

A.V. *47Lazareva Yu.N. *178Levacheva I.S. *179Yu.S. Levina *48A.V. Levchenko53Lezhepekov A.V. *85E.V.
Leutkina *49Leushina A.P.42Lefedova O.V.6Leshin V.S.208Lisitsyn Yu.A.218A. A. Logunov *180E.S.
Lokteva16.21Lomakov M.V. *86Lomova T.N.171Losev Ya.V.173Lyashkov V.M.211Magamedbekov R.M.
*181Maerle A.A. *22E.A. Makeeva *50Makshina E.V. *23.44Malysheva E.V.173Mamonov
P.A.165Mamontova Yu.V. *24Mamyrbekova A.K. *182Mansurova A.N. *51Marochkina M.N. *183V.P.
Maryevich51Masalovich M.S. *52L.M. Matveeva *87A.A. Meldianov *184Minaev B.F.146,212Missul A.B.
*88Mitkina T.V. *89Mityaev A.S. *90Mikhailina A.V. *118Mikhailov G.G.203Mikhalina E.V.
*119Mishchenko O. G. *185Molchanova N.G.127Monakov Yu.B.137Yu.S. Moroz *91I.V.
Morozov96Moskalenko N.I.127Moskvin D.N. *92Moskvichev A.A. *186Muradyan V.E.213Muralev A.E.
*93Fly Yu.P. *94Nagorny P.G.37.38K. I. Nevraeva203I.V. Nepopalova *187V. S. Neudachina *53A.D.
Neuymin155Nikischenkova L.V. *188Nikolaev A.L.113Nikolaev A.N. *120Nikolaev I.V. *95Nikulin M.M.
*189Nikulshin P.A. *25Yu.V. Novakovskaya143,200Nosova N.M. *26Nurdillaeva R.N. *190A.K. Nurshimov
*191Omarova A.K. *192Ordomsky V.V. *27Orlova V.A. *121Orlova M.P. *122Ospanov
Kh.K.138Ostashkina E.E. *123Pavlova G.Yu.111Palamarchuk D.V. *96Panin R.V. *54Panova A.G.
*55Pautova I.N. *193Pashkeev I.Yu.203Peretolchin D.V. *28Yu.D. Perfiliev113Pestereva N.N. *56O.S.
Pilipenko8Pimerzin A.A.150A. V. Piskunov47Povroznik V.S. *194Pogrebnyak V.M. *97A.I. Poddel'skiy40V.
Yu. Pozdnyakova *124,133Poluboyartsev D.S. *29O. N. Polyakova155Pombeiro A.J.L.105O. N.
Ponamoreva141K.D. Praliev170D. M. Predtechenskaya *195E. V. Prosvirkina136Putilina M.S. *196222

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V.I. Putlyaev102Pchelova L.G.74Razumkova I.A. *98Rachmanina A.V.189Rakhymzhanova P.191Rezvanova

M.O.153Rome A.V. *197Rogachev A.Yu. *57Rogozhina T.V. *thirtyRoznyatovskaya N.V. *198Rozova
M.G.39.81.101Rumnenko N.D. *199Rusakov D.A. *58Rusin A.D.187Ryzhikov N.N. *125Ryabinkin I.G.
*200Sabodina M.N. *126Savvin S.N.85Savinova E.R.elevenSaltiel D.217Safonova L.P.201Svensson
G.79Svettsova E.V. *201Selivanov D.V. *99Semyonov S.N. *71,100,202Semenova I.A. *203Semenov V.V.
*127Semesko D.G. *204Semin V.A. *128Senyavin V.M.189Sergeev R.V.59Seryakov S.A. *101Sidorenkova
I.V. *60Simonov P.A.elevenSkokan E.V.189Sliva T.Yu.91Smirnova N.N.140,168,183,188Soin A.V. *102Yu.V.
Solovyova205Stepanov N.F.143,200Stoikov I.I.147Suleimanov E.V.154Suleimanov Yu.V. *206A. V.
Sungurov *31Suslova E.V. *103Yu.V. Sukhova *129Syshchenko A.F.177Tarasov B.P.213Tarasov
V.P.64Tarkhanova I.G.13Terekhov A.A. *207Tereshchenko D.S.104Timokhova O.A. *208Titaeva
N.A.129Titov I.V.36Tikhonov E.V.53Tkachenko I.S.17,202Tokareva A.O. *104Toldina O.V. *61A.S.
Toropkina *130Trypolskaya A.A. *62Tronova E.A. *105Troyanov S.I.71.96,100,104Turakulova
A.O.21Tyasto Z.A.119,133Ulyanova E.A. *106Usoltseva N.V.162Fedorov N.V. *63Fedorov
Yu.V.217Fedorova O.A.217Fedoseev N.F.216Fedoseeva V.I.216Fedosov S.A. *32Filaretov A.A.58Filatova
L.Yu. *209Filatova Y.B. *210Fionov A.V.211Fokina I.V. *211Frantseva A.G. *212Fritsky I.O.91Kharin A.A.
*213Khasanova A.B. *131Khaskov M.A. *64Khibiev Kh.S.181Khidirov Sh.Sh.181Khomenko
E.M.146,219Khrustova L.G.127Khrycheva A.D. *214Khursan S.L.204Tsarev V.N.13Tsarevsky I.I. *215Tsirlin
A.A. *107Tsirlina G.A.39Human N.V.189Cherkasov V.K.40.47T.A. Chernakova *132Chernov E.B.60E.V.
Chernova *65Chernysheva M.G. *114,119,124,133Chumarev V.M.51223

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Shagisultanova G.A.52.75Shcherbina N.S. *134O. V. Shangareeva *216Yudina E.A. *218Sharonov

N.Yu.6Yurkov I.I.144Shein A.B.194Yurchenko A.Yu.120Yashchuk L.B. *146,219Shepel N.E. *217Shiryaev
A.A.13224

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TABLE OF CONTENTSBranch "Catalysis" .............................................. ...............fiveDepartment "Inorganic

chemistry - graduate students" ............ 33Department "Inorganic chemistry - students" ..............
66Department "Radiochemistry" .............................................. .... 108Department of Physical
Chemistry ....................................... 135Author's Index, Volume 2 ............................................. .. 220Table
of contents................................................. ......................... 225225