Ukrainian Chemistry Journal

Contents of Volume 81 №3 (2015)

Inorganic and Physical Chemistry

SUBBOTIN V.V., YANKO O.G., KHARKOVA L.B., NIKOLENKO A.S., VOLKOV S.V.
Family of trinuclear cluster chalcogen halides of rhenium
  • Summary: A number of molecular ionic trinuclear cluster chalcogen halide complexes of rhenium(V) of the general composition Re3Chal7Hal7 have been obtained by the interaction of Re2O7, Re2S7, ReOCl4, ReCl4 with chalcogen halide media containing excess chalcogen in a temperature range of 130—280 oC. According to the data of an X-ray structural analysis, these compounds are made up of [Re3(3-Chal)(-Chal2)3Hal6]+Hal– ion pairs (Chal – S, Se; Hal – Cl, Br, AlCl4). The basis of the complexes is a triangular cluster [Re3(3-Chal)], a thermodynamically stable structure with single Re–Re bonds (~2.70Ao ). The structure of the complexes has been confirmed by Raman spectroscopic studies. The Re3S7Cl7 thiochloride is able to form active catalytic centers in the hydrogenation reaction of organic compounds. A mechanism of this process is proposed for m-nitrobenzoic acid hydrogenation as an example.
  • pp.: 3 - 7

REPICH G.G., ORYSYK S.I., SEVERINOVSKAYA O.V., PEKHNYO V.I.
Correlation of spectral analysis and X-ray diffraction study in identifying different types of coordinated tiosemicarbazone in the Ni(II) complex
  • Summary: The novel cationic Ni(II) complex has been synthesized and isolated in the crystalline state involving different types coordination of two molecules of salicylhydrazone allylthiosemicarbazone. Studying of the structure by X-ray analysis showed a presence of short contacts between phenoxyl oxygens of the neighboring complex molecules which indicates a presence of intermolecular hydrogen bonds between these atoms and shows that one of the ligand molecules is coordinated in molecular form without deprotonization of phenoxyl OHgroup. The IR, XPS, UV-Vis and MALDI mass spectrometric characteristics were found that also indicates the stay of ligand molecules at the same time in molecular and anionic forms.
  • pp.: 8 - 15

IVANENKO A.P., KOMPANICHENKO N.M., OMELCHUK A.A.
Synthesis of ZBNL fluorozirconate glass with partial or complete substitution of samarium (II) fluoride for barium (lanthanum) fluorides
  • Summary: The formation conditions of glass and glass-crystalline phases as well as phase transitions in the partial or complete substitution of samarium difluoride for lanthanum and barium fluorides in ZBNL fluorozirconate compositions (%mol.): (53.5)ZrF4—(20)NaF—(20) BaF2—(6.5–x)LaF3—(x)SmF2 (0 х 6.5) (composition I) and (53.5)ZrF4—(20)NaF—(20–x)BaF2—(6.5)LaF3—(x)SmF2 (0 х 20.0) (composition II) have been determined by a differential thermal and an X-ray phase analysis and infrared spectroscopy. In the composition I, colorless resistant glass is formed at a SmF2 content of 0 х 6.5 and in the composition II at 0х 5.0 % mol. At higher samarium difluoride content (5.0 х 20.0), glass-crystalline phases are formed in the composition II. The results of IR spectroscopy indicate the skeleton structure of the synthesized fluorozirconate glass samples (which is formed by ZrFn polyhedra), in which the samarium cations have different position depending on oxidation state.
  • pp.: 16 - 19

FREIK D.M., VOLOCHANSKAYA B.P.
Temperature dependences of the heat capacity of sphalerite crystals of CdS, CdSe, CdTe cadmium chalcogenides
  • Summary: Based on the analysis of the crystal and electronic structure of cubic phase CdX (S, Se, Te) crystals of sphalerite the cluster models have been built for calculation of the geometric and thermodynamic parameters. According to density functional theory (DFT) and using the hybrid valence base set B3LYP the temperature dependence of the specific heat at constant volume CV and pressure CP of the crystals have been approximated analytical from the quantum-chemical calculations data and with using mathematical package Maple 14 have been received. There is compared the results of ab initio calculations and experiment.
  • pp.: 20 - 23

CHERNYSHOVA O.S., ODNOVOLOVA A.M.
Complexformation of copper (II) with DL--alanyl- DL--valine in micellar solutions surfactants
  • Summary: We investigated the effect of the micellar media of anionic (sodium dodecylsulfate, SDS), cationic (cetylpiridinium chloride, CPC) and non-ionic (Brij-35) surfactants on the complex formation of copper (II) with DL--alanyl-DL--valine by using potentiometric method, as well as by applying semi-empirical quantum chemical calculations to study the probable structure of copper (II) complexes with dipeptide. In SDS micellar solutions the formation of two complexes: CuL2 and CuH–1L was observed. However, in aqueous solutions, CPC and Brij-35 solutions the presence of CuH–2L– was also detected. The stability of the complexes depends on the charge of the micelle surface and binding of the particular species by the micellar pseudophase.
  • pp.: 24 - 28

Electrochemistry

KOZIN V.F., BLIZNYUK A.V.
Formation of germanium hydrides in the case of cathodic polarization of germinate anion in alkaline electrolytes
  • Summary: The parer presents the results of an electrosynthesis of germanium hydride with cathodic polarization in alkaline electrolytes. The dependence of the current yield of germanium hydride (CVGH) on hydrogen overpotential, zero-charge potential and cathode material has been established. It has been shown that CVGH increases in the series of cadmium, lead, tin cathodes from 27.7 to 41.9% GeH4. The possibility of raising the rate of germanium hydride production is shown, and experimental data on the preparation of GeH4 and (GeH2)x with high current yield are presented. A mechanism of hydrogen reduction side reactions proceeding during germanium hydride formation on metallic cathodes with high hydrogen overpotential is proposed.
  • pp.: 29 - 35

GRITSAI L.V., OMELCHUK A.A.
Electrochemical reduction of zirconium dioxide in calcium oxide and chloride melts
  • Summary: A method for the direct electrochemical reduction of zirconium dioxide in oxide-chloride melts on liquid gallium cathode has been developed. The optimal conditions of electrolysis have been found, which ensure obtaining fine zirconium powder of not under 99.9% purity. The degree of extraction of zirconium from zirconia is higher in oxide-chloride melts containing sodium cations, which have a lower acid strength.
  • pp.: 36 - 39

Organic Chemistry

RODIK R.V.
Synthesis and properties of trisaminodipropoxy- tert-butylcalixarene
  • Summary: Method of 5,11,17-trisamino-23-tertbutyl- 26,28-dihydroxy-25,27-dipropoxy-calix[4]arene (trisaminocalixarene) synthesis was developed.Method consists in ipso-nitration of corresponded dipropoxytert- butylcalixarene, separation of nitroderivatives and reduction of obtained trinitrocalixarene with hydrazine- hydrate on Ni Raney. Reaction of tris-aminocalixarene with electrophillic reagents trisamido, tricarbamido-, trisulfonylamidino and trisiminocalixarenes were obtained. Latter was transformed to calixarene-trisaminophosphonate.
  • pp.: 40 - 46

BUSHUYEV A.S., KOLBASYUK O.O., LAGUTENKO M.O., GALSTYAN G.A.
Kinetic of oxidation of ethylbenzene by ozone-air mixture in acetic acid
  • Summary: The reaction of ozone with ethylbenzene in the acetic acid was investigated. It is shown, that ozone destruction of an aromatic ring (60 %) to form ozonides, which then transformed into hydroperoxides, aldehydes and carboxylic acids. Among the products of the oxidation of the side chain found acetophenone (34 %), 1-phenylethanol, benzaldehyde and benzoic acid. The chemical scheme of the ethylbenzene oxidation and products of its transformation, which satisfactorily describes the experimental data are determined.
  • pp.: 47 - 51

PISANENKO D.A., GAIDAI A.V., KLIMKO Yu.Ye., AVILOV V.O.
2-N-polybenzylpyrazolium chlorides as constituents of acid corrosion inhibitors
  • Summary: 2-N-Polybenzylpyrazolyl chloride and its 3-methylsubstituted homolog are synthesized and it was studied the influence both these salts individually and these salts in composition which liked preporatory form of inhibitor KI-1 on the steel St.3 corrosion in 20 % HCl at 60 oC and 20% H2SO4 at 80 oC. The geometry was optimized and charges on nitrogen atoms were calculated for cations of model compounds — 2-N-benzylpyrazolyl chloride and its 3-methylsubstituted homolog. The result of calculations was used for explanation how CH3-group influences the inhibing power of these salts.
  • pp.: 52 - 54

Chemistry of High-Molecular Compounds

FAINLEIB А.M., PURIKOVA О.G., GAILLET C., GRANDE D.
Investigation of chemical structure of polycyanurate/polystyrene semi-IPNs
  • Summary: Chemical interaction between components of polycyanurate/polystyrene semi-interpenetration polymer networks (semi-IPNs) formed in situ was investigated. The generation of netted polycyanurate and attendance of linear polystyrene in extracted semi-IPNs sample was confirmed by zol–gel analysis and FTIR spectroscopy. Chemical interaction of semi-IPNs components with imidoate group formation was shown up with solid state 13C NMR spectroscopy.
  • pp.: 55 - 58

BRATYCHAK M.M., IVASHKIV O.P., ASTAKHOVA O.T., GAPONYUK Yu.
Oligomers with hydroxyl groups based on ED-20 epoxy resin
  • Summary: The oligomers containing epoxy, primary hydroxy and secondary hydroxy groups (SHG) at the same time have been synthesized via interaction of 1,4-butandiol or Poly THF-2000 with ED-20 dianic epoxy resin. The effect of catalyst nature and quantity, as well as temperature on the rate of the reaction between ED-20 resin and 1,4-butandiol or Poly THF-2000 oligoether has been examined. SHG has been synthesized and characterized using the catalytic system consisting of chlorine benzyltriethylammonium and KOH. It is proposed to use the synthesized compound as an active additive while forming three-dimensional structures based on ED-20 epoxy resin and 4,4’-diphenylmethanediisocyanate.
  • pp.: 59 - 63

SHTOMPEL V.I., RIABOV S.V., SINELNIKOV S.I., OPANASENKO Ye.A.
The structure peculiarities of the cross-linked copolymers containing -cyclodextrin and their sorption capacity
  • Summary: The supramolecular structure of - CD derivatives and polymers on their base was investigated by X-ray diffraction at small and large angles. Analysis of experimental data showed that the polymers, which include -CD derivatives with different chemical structure have significant differences in their microhete rogeneous structure. The sorption properties of the obtained polymers were studied. The largest value ofmethyl orange adsorption is typical for polymer which based on -CD maleate.
  • pp.: 64 - 67

   

   

   

   

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