Ukrainian Chemistry Journal

Contents of Volume 81 №1 (2015)

Inorganic and Physical Chemistry

CHERNII V.Ya., DOVBII Ya.M., TRETYAKOVA I.N., SEVERINOVSKAYA O.V., VOLKOV S.V.
Synthesis and properties of zirconium and hafnium phthalocyanine complexes with dehydroacetic acid
  • Summary: Novel phthalocyanine complexes of zirconium and hafnium with dehydroacetic acid as outof- plane ligand were synthesized, three methods for their synthesis are offered. Composition, structure and spectral properties of the compounds obtained were established by mass spectrometry, 1H NMR and UV-vis spectroscopy. It was established that the central atom of the phthalocyanine complexes coordinated two dehydroacetic acid ligands in the cis-position.
  • pp.: 3 - 7

MARTSINKO Ye.E., SEIFULLINA I.I., DEMCHENKO P.Yu., GLADYSHEVSKII R.Ye.
Synthesis and X-ray structural investigation of germanium(IV) nickel(II) hydroxyethylidenediphosphonate
  • Summary: 1-hydroxyethylidenediphosphonatogermanate (IV) of nickel (II) has been obtained by stepby- step synthesis method and characterized by inductively coupled plasma atomic emission spectroscopy (elemental analysis), IR absorption spectroscopy and X-ray powder diffraction. It has been established that the new heterometallic complex Ni4[Ge6(-OH)4(-O)2(-Oedph)6] 38H2O (where H4Oedph is 1-hydroxyethylidenediphosphonic acid) is isostructural with the analogous zinc complex [1]. Crystal structure was refined by the Rietveld method: Ge6O86C12P12Ni4, M =2562.18 gmol–1, monoclinic symmetry, space group P21/c, a =11.4147(4), b= =17.2307(8), c=23.5696 (12)Ao , =98.853(4)°, V =4580.5 (3)Ao 3, Z=2 (reliability factors RI = 0,1045, RF =0.0389, Rp =0.0786, Rwp =0.1155).
  • pp.: 8 - 12

GRYTSAI L.V., OMEL’CHUK A.A., SAVCHUK R.N.
Solubility of calcium oxide and zirconium dioxide in eutectic of calcium chloride and alkali metal chloride
  • Summary: The behaviour of calcium oxide in eutectics of CaCl2—MCl and zirconium dioxide in polythermal sections of the ternary systems CaO—CaCl2– MCl (M = Li,Na,K) has been investigation used methods of thermal and X-Ray analysis. It has been shown that equilibrium content of calcium oxide in the melt CaO—CaCl2—LiCl is much higher than similar melt composition CaO—CaCl2—MCl (M = Na,K). It has been established that the solubility of zirconium dioxide in the test melts rises with increasing acidity of the appropriate melt.
  • pp.: 13 - 16


Formation of А6В6О22 compounds with heteroblock slab perovskite-like structure (A = Ca, Ln, B=Ti,Nb,Ta)
  • Summary: Phase ratios in systems Ca2Ta2O7— LnTaO4 , CaLnTiTaO7—LnTaO4 (Ln = La, Pr,Nd, Sm) and CaLaTiNbO7—LaNbO4 are investigated. Formation from the systems of co-precipitated hydroxycarbonates new compound Ca2La4Ti2Ta4O22 with heteroblock layered perovskite-like structure, which heteroblocks includes four-layer block Са22Ti2Ta2O14 and twolayer block Lа2Ta2O8 is established. It is shown that the possibility of crystallochemical stabilization ofmetastable perovskite-like blocks of high pressure modifications in heteroblocks {(4)(2)} of compounds А6В6О22 is determined by relative difference of roentgenographic density of polymorphous modifications.
  • pp.: 17 - 20

REPICH G.G., ORYSYK S.I., PEKHNYO V.I.
Synthesis and crystal structure of Ag(I) complex with phenylacetic acid salicylhydrazone
  • Summary: The Ag(I) complex with O,N,O-coordinated phenylacetic acid salicylhydrazone has been first synthesized and isolated in the crystalline state. The X-ray diffraction studying showed the formation of highly distorted octahedral environment of central Ag(I) ion. It has been found that even in a neutral media the ligand molecule coordinate in molecular form without deprotonation of OH-group of phenoxyl ring that leads to the formation of a cationic type complex. The complex decomposition in DMSO solution was observed due to recoordination of central ion by solvent molecules.
  • pp.: 21 - 25

Electrochemistry

KOZIN L.F., BOGDANOVA A.K.
Overstrain of allocation of hydrogen from an alkaline solution on the electrode modified by a polymetallic alloy from stainless steel
  • Summary: The laws governing hydrogen evolution from a 30% KOH solution at a nickel, niobium-, molybdenum- and tungsten-activated Kh18N10T stainless steel electrode at several temperatures have been established, and its kinetic parameters have been determined. It has been found that hydrogen evolution overpotential at activated electrodes decreases by a factor of 2.2—2.5 depending on temperature. It has been shown that the angular coefficient and charge-transfer coefficient in the Tafel relation H2 — lgik are close to the theoretical values. The kinks on ik—E polarization curves indicate the formation of monohydrides Me—H. The effective activation energies of hydrogen evolution have been calculated. It has been found that the rate of hydrogen ion discharge at activated electrodes is controlled by kinetic restrictions. The values of limiting overpotential and limiting hydrogen evolution current in the activation-free region have been determined. Values of metal-hydrogen bond strength energy for nickel, niobium, molybdenum, tungsten, chromium and iron are presented.
  • pp.: 26 - 35

BYK S.V., BERSIROVA O.L., KUBLANOVSKII V.S.
Electrocatalytic oxidation of ethanol on alloys of nickel and tungsten deposited by induced electrodeposition
  • Summary: For nickel—tungsten alloys, electrodeposited from polyligand citrate-pyrophosphate electrolytes, their high electrocatalytic activity and stability of parameters of coatings in the oxidation reactions of ethanol in 1M KOH have been shown. It was found that the limiting current of ethanol oxidation increases with increasing the concentration of ethanol to 2moll–1; higher concentration probably changes the mechanism of transport of depolarizer or reaction products. It was found that the diffusion activation energy of the process of electrooxidation of ethanol on nickel-tungsten catalyst is 29.2 kJmol–1.
  • pp.: 36 - 39

VARGAL’UK V.F., PLYASOVSKAYA Ye.A., ZAMYATINA A.S.
Тhe features of the electrooxidation of tin in an alkaline medium
  • Summary: An analysis of oxide films electrochemically formed on tin in an alkaline medium was conducted by using the improved coulometric method. It is shown that the qualitative and quantitative composition of the passive film on tin in a wide potential range of its formation Е (from –0.4 to +3.0В) corresponds to the stoichiometrical ratio Sn(ІІ) : Sn(IV)=1:1 and is determined by properties of themechanism of the anodic process, whereby thermodynamically stable end products of the electrooxidation of tin (SnO3 2– ) are bound by an intermediate (Sn2+ ) and form a thin layer of an insoluble salt SnSnO3 on the electrode surface. The assumptions about the nature of tin passivation are indirectly confirmed by the experimental data on the kinetics of catalytic decomposition of hydrogen peroxide on anodized tin electrodes.
  • pp.: 40 - 43

Chemistry of High-Molecular Compounds

SLISENKO O.V., BEI I.N., BUDZINSKAYA V.L., LEBEDEV Ye.V.
Synthesis and properties of lyophillic organic-inorganic hybrid hydrogels
  • Summary: A novel double-network (DN) nanoscaled hydrogels consisting of organic PAAm network and inorganic siloxane network were synthesized by one-pot in situ polymerization. Spectral studies indicate a formation of DN structure of obtained composite hydrogels. Detailed study of the composites showed well-defined structurizing of hybrid hydrogels on molecular and nanolevel as well as intra- and intercomponent interactions via H-bonding. Nanostructurization have a great impact on final properties of the composite hydrogels. Prepared materials are characterized by improved thermal stability and swelling ratio. Swelling degree of hybrid composite hydrogels depends on components ratio and reaches 2700 %.
  • pp.: 44 - 49

TKACHENKO I.М., KOBZAR’ Ya.L., SHEKERA О.V., SHEVCHENKO V.V.
Synthesis of monomers with tetrafluoro-1,4-diphenoxybenzene fragment and different types of reactive groups
  • Summary: The methods of synthesis of new bifunctional aromatic core-fluorinated monomers containing tetrafluoro-1,4-diphenoxybenzene fragment and acetyl, fluorophenylmethanone, hydroxyl, epoxide, brommethyl and azide groups were developed. The structure of the synthesized compounds was determined by IR, 1H NМR and 19F NMR spectrometry techniques.
  • pp.: 50 - 55

KOSYANCHUK L.F., STRATILAT M.S., KOZAK N.V., TODOSIICHUK T.T.
The influence of the phenalenone dyes on the polyurethanes formation
  • Summary: The influence of the phenalenone dyes on the kinetics of polyurethane matrices formation, which differ by nature, molecular weight and functionality of polyurethane components was studied. It was shown that the presence of dyes made a little effect on the reaction of urethane formation. However, the observed changes were due to the nature of the polyurethane component, functionality of used dyes and steric effects that occur in the system.
  • pp.: 56 - 61

UMEROVA S.A., DULINA I.A., RAGULYA A.V.
Effect of plastification on rheological properties of polymer solutions
  • Summary: Structurization features of polymer ethylcellulose in organic solvent terpineol with different concentration of plasticizer dibutyl phthalate by practical rheometry method were investigated. It was established that all solutions were characterized by pseudoplastic flow type and dilatant increasing of viscosity at low shear stresses. It was found that plasticizer addition leads to formation of three-dimencional polymer systems with pseudoplastic-rheopexical—pseudoplastic— pseudoplastic-thixotropical, pseudoplastic-thixotropical, pseudoplastic-rheopexical—pseudoplastic-thixotropical, pseudoplastic—pseudoplastic-thixotropical structurization character.
  • pp.: 62 - 67

   

   

   

   

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