Vol 90, No 6 (2016)

The thermochemical properties of melts of the binary In–La system were studied by the calorimetry method at 1250–1480 K over the whole concentration interval. It was shown that significant negative heat effects of mixing are characteristic features for these melts. Using the ideal associated solution (IAS) model, the activities of components, Gibbs energies and the entropies of mixing in the alloys, and the phase diagram of this system were calculated. They agree with the data from literature.

The dependence of the physicochemical and structural–adsorption properties of natural and acid–thermal modified clinoptilolite, and of Pd(II)–Cu(II) catalysts based on them, on the duration of acid–thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV–Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area (S_sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)–Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO₃ for 0.5 and 1 h.

The operational stability of a mixed oxide catalyst of Mo–V–Te–Nb–O composition in the oxidative dehydrogenation of ethane (ratio of C₂H₆: O₂ = 3: 1) is studied in a flow reactor at temperatures of 340–400°C, a pressure of 1 atm, and a WHSV of the feed mixture of 800 h⁻¹. It is found that the selectivity toward ethylene is 98% at 340°C, but the conversion of ethane at this temperature is only 6%; when the temperature is raised to 400°C, the conversion of ethane is increased to 37%, while the selectivity toward ethylene is reduced to 85%. Using physical and chemical means (XPS, SEM), it is found that the lack of oxidant in the reaction mixture leads to irreversible changes in the catalyst, i.e., reduced selectivity and activity. Raising the reaction temperature to 400°C allows the reduction of tellurium by ethane, from the +6 oxidation state to the zerovalent state, with its subsequent sublimation and the destruction of the catalytically active and selective phase; in its characteristics, the catalyst becomes similar to the Mo–V–Nb–O system containing no tellurium.

The kinetics of the electron transfer reaction of methylene green and titanium trichloride was investigated in different solvents by spectrophotometry at different temperatures. The the reaction rate was determined by monitoring the absorbance as a function of time at λ_max 655 nm. The reaction is pseudo-first order, dependent only on the concentration of titanium trichloride at a fixed concentration of methylene green.

The effect of an aqueous alcoholic solvent was studied in the acidic range of pH from 4 to 7. It was observed that the reaction rate increased with an increase in polarity of the reaction medium. The the reaction rate was high in acidic conditions and decreased with a further increase in acidity. The increase in temperature increased the rate of the electron transfer reaction of methylene green and titanium trichloride. The activation energy (E_a) was calculated by the Arrhenius relation. The absence of any reaction intermediate was confirmed by spectroscopic and kinetic investigations. A plausible mechanism for the reaction in line with outer-sphere reaction pathway has been proposed. Thermodynamic parameters such as the activation energy (E_a), enthalpy change (ΔH), free energy change (ΔG), and entropy change (ΔS) were also evaluated

Analytical dependences of a volume’s properties on the differences between the geometric structures of initial monosystems are obtained for binary systems simulated by a grain medium. The effect of microstructural parameter k (the ratio of volumes of molecules of mixed components) on the concentration behavior of the relative excess molar volume of different types of real binary solutions is analyzed. It is established that the contribution due to differences between the volumes of molecules and coefficients of the packing density of mixed components is ~80–100% for mutual solutions of n-alkanes and ~55–80% of the experimental value of the relative excess molar volume for water solutions of n-alcohols.

The region of the frequency dispersion of the bulk viscosity coefficient η_V(ω) of solutions of electrolytes is studied as a function of the nature of the decay of the stress tensor in the momentum and configuration space, the analytical expressions of which are derived by means of kinetic equations. Numerical calculations of η_V(ω) for a water solution of NaCl are performed over a wide range of frequencies, temperatures, and densities using a selection of the potentials of intermolecular interaction Φ{in{itab}}(|\(\vec r\)|) and radial distribution function {itg}{in{itab}}(|\(\vec r\)|). It is shown that the region of frequency dispersion η_V(ω) based on the power law of the decay of the stress tensor is wide (~10⁵ Hz), while the region based on the exponential law is narrow (~10² Hz).

The complexing of protonated chitosan with dodecyl sulfate ions in water solutions is studied using IR spectroscopy data and quantum-chemical calculations. It is established that the electrostatic interaction between the protonated amino groups of chitosan and dodecyl sulfate ions is apparent in the IR spectrum as a band at 833 cm⁻¹. The need to consider the effect the solvent has on the formation of hydrogen-bound ion pairs [CTS⁺ ⋅ C₁₂H₂₅O₃^-] is shown via a quantum-chemical simulation of the equilibrium geometry and the energy characteristics of complexing and hydration.

To characterize the structural, thermochemical and electronic aspects in complexes of leucine, vanillin and mechlorethamine with α-, β-, and γ-cyclodextrins (CDs), a density functional theory (DFT) study has been conducted in combination with quantum theory of atoms in molecules (QTAIM) analysis. The QTAIM method has been utilized to explore the nature of various possible interactions between leucine, vanillin and mechlorethamine with CDs in terms of bond critical points (BCPs). HOMO and LUMO and atomic charges studies show charge transfer occurs between drugs and cyclodextrins. This behavior has been also investigated via QTAIM charge analysis. On the other hand, based on QTAIM electronic energy indicators we have discussed electrostatic character of interactions between vanillin, leucine and mechlorethamine with inner surface CDs in the coordination sphere.

The adsorption of anionic surfactant sodium dodecylbenzenesulfonate (SDBS) from aqueous solution on the hydrophilic surfaces of aluminum oxide and iron oxide nanoparticles is studied via UV spectrophotometry, electrophoretic light scattering, and isothermal microcalorimetry. It is shown that the isotherms of the adsorption of SDBS on the surfaces of both oxides in the area of concentrations up to 0.6 mmol/L is linear. It is found that the positive zeta potential of the surfaces of the particles falls to zero and shifts toward the range of negative values due to adsorption. The adsorption of SDBS is characterized by positive enthalpy values over the investigated range of concentrations, while the loss of energy during adsorption indicates it is of an entropic nature. It is concluded that the probable cause of the increase in entropy is the dehydration of SDBS molecules during on surface adsorption. The obtained results are discussed in terms of the formation of hemimicelles of surfactant on the hydrophilic surfaces of metal oxide nanoparticles in an aqueous medium.

Mesoporous MgO was obtained via the hydrothermal synthesis using both ionogenic and non-ionogenic surfactants as structure-directing templates. The materials prepared were characterized by SEM, BET-N₂, XRD, and TG-DTA techniques. MgO particles are spherical 20-μm aggregates of primary oxide particles well shaped as rectangular parallelepipeds. Magnesium oxide samples have the specific surface area of 290–400 m²/g and pore sizes of 3.3–4.1 nm. Their mesoporous structure remained unchanged after calcination up to 350°C. Catalytic activity of mesoporous MgO was studied in acetone condensation reaction.

Orthorhombic molybdenum trioxide (α-MoO₃) nanobelts have been successfully synthesized by hydrothermal method at 180°C for 20 h. The prepared α-MoO₃ samples were investigated by X-ray diffraction, Fourier transform IR spectroscopy, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy methods. It was found that α-MoO₃ nanobelts grow along the c-axis, with ±(100) top or bottom surfaces and ±(010) side surfaces. The prepared α-MoO₃ nanobelts were used as cathode materials for Li-ion batteries. They exhibit specific capacity of 1340 and 1250 mA h g^–1 at a current density of 100 and 400 mA/g, respectively.

The theory of the ion exchange kinetics on strong acid cationites with the participation of weak electrolytes is discussed. The kinetics of desorption of benzocaine in the protonated and molecular forms from strong acid cationites, sulfonated polycalixarene, and KU-23 30/100 sulfocationite, is studied experimentally. It is shown that the flow of protonated benzocaine from cationite upon desorption proceeding by the ion-exchange mechanism is more intense than upon desorption of nonionized benzocaine molecules. It is established that the diffusion coefficient of benzocaine cations is (1.21 ± 0.23) × 10⁻¹² m²/s in KU-23 30/100 sulfocation and (0.65 ± 0.06) × 10⁻¹³ m²/s in sulfonated polycalixarene, while the diffusion coefficient of benzocaine molecules is (0.65 ± 0.15) × 10⁻¹⁴ m²/s in sulfonated polycalixarene.

The size dependence of the linear tension of round two-dimensional equilibrium drops in the vapor phase on a homogeneous surface of an adsorbent is studied at the pressure of saturated two-dimensional vapor. The calculations are based on the lattice gas model in a quasi-chemical approximation with allowance for the correlation effects of the nearest interacting molecules. Methods for calculating linear tension using the equimolecular reference line are considered. Temperature dependences of the linear tension are studied for metastable and equilibrium drops. It is found that the differences between the thermodynamic properties of two types of drops are slight over a wide range of variation in drop radii.

The results of our study of solid-phase microextraction of substances using a centrifuge for determining the microquantities of hydrocarbon impurities in water are presented. The cartridge diameter, sorbent mass, and solvent volume were shown to affect the percent extraction of substances and the analytical signal intensity. The relationship between the cartridge geometry, the sorbent mass, and the solvent volume was considered.

Conductometry is used to investigate the electric conductivity of Cu(NO₃)₂ ⋅ 3Н₂О solutions in dimethyl sulfoxide in the 0.01–2.82 M range of concentrations and at temperatures of 288–318 K. The limiting molar conductivity of the electrolyte and the mobility of Cu²⁺ and NO₃^- ions, the effective coefficients of diffusion of copper(II) ions and nitrate ions, and the degree and constant of electrolytic dissociation are calculated for different temperatures from the experimental results. It is established that solutions containing 0.1–0.6 M copper nitrate trihydrate in DMSO having low viscosity and high electrical conductivity can be used in electrochemical deposition.

Equilibrium processes in the Ga(NO₃)₃–H₂O–NaOH system are simulated with allowance for the formation of precipitates of various compositions using experimental data from potentiometric titration and theoretical studies. The values of the instability constants are calculated along with the stoichiometric compositions of the resulting compounds. It is found that pH ranges of 1.0 to 4.3 and 12.0 to 14.0 are best for the deposition of gallium chalcogenide films.

The reaction energy transfer to electrons and release of electrons from traps under the action of the recombination of H atoms on the surface of light-sum-storing crystals (Zn₂SiO₄–Mn, ZnS, ZnS,CdS–Ag) was studied. This effect is associated with the reaction energy accommodation via the electronic channel. The transfer of electronic excitations to the atomic recombination event is independent of the reaction rate, but depends on the electron transition energy in a solid. The possibility of electronic excitation per heterogeneous recombination event of H atoms increased exponentially as the electron transition energy decreased.

The adsorption of alkenyl succinic anhydride from a solution in carbon tetrachloride on a fine magnetite surface at a temperature of 298.15 K is studied using fine magnetite, which forms the basis of magnetic fluids, as the adsorbent. An adsorption isotherm is recorded and interpreted in terms of the theory of the volume filling of micropores (TVFM). Adsorption process parameters are calculated on the basis of the isotherm. It is shown that at low equilibrium concentrations, the experimental adsorption isotherm is linear in the TVFM equation coordinates.

Adipic acid–glutaric acid, glutaric acid–sebacic acid, and adipic acid–sebacic acid binary systems are studied, along with an adipic acid–glutaric acid–sebacic acid ternary system. It is shown all of these systems are eutectic. Phase equilibria for the diagram elements of the binary systems and the ternary system are described. It is concluded that the above low-melting compounds can be recommended for use as working bodies in heat accumulators, and for preparing electrolytes used in the thin-layer anodic oxidation of aluminum alloys.