Volume 91, Nº 3 (2017)

Equations describing local thermal and caloric equations of state in heterogeneous systems at any degree of their states’ deviation from equilibrium are derived. The state of a system is described by equations of the transfer of mixture components; these generalize the equations of classical non-equilibrium thermodynamics for strongly nonequilibrium processes. The contributions from reactions and external fields are taken into account. The equations are derived using the lattice gas model with discrete molecular distributions in space (on a scale comparable to molecular dimensions) and continuous molecular distributions (at short distances inside cells) during their translational and vibrational motions. For simplicity, it is assumed that distinctions between the sizes of mixture components are small. Contributions from potential functions of intermolecular interaction (of the Lennard-Jones type) to some coordination spheres are considered. The theory provides a unified description of the dynamics of distributions of concentrations and pair functions of mixture components in three aggregate states, and at their interfaces. Universal expressions for the local components of the pressure tensor and internal energy inside multicomponent bulk phases and at their interfaces are obtained. Local components of the pressure tensor and the internal energy are universally expressed through local unary and pair distribution functions (DFs) in any nonequilibrium state. The time evolution of the unary and pair DFs themselves is determined from the derived system of equations of mass, momentum, and energy transfer that ensure the transition of the system from a strongly nonequilibrium state to both the local equilibrium state described within traditional nonequilibrium thermodynamics and the complete thermodynamic equilibrium state postulated by classical thermodynamics.

Complete phase diagrams for mixtures of low-density polyethylene with p- and m-xylene are plotted by optical means in developing the concept of which partially crystalline polymers are microstructured liquids. It is shown that in contrast to the ones presented in the literature, both diagrams contain the solubility boundary curve of the low-molecular weight component in the polymer, above which the polyethylene has the structure of a single-phase gel (crosslinks formed by crystallites and amorphous regions saturated with xylene). At the figurative point on the diagrams, a situation is observed in which the dissolution of all the liquid contained in the initial two-phase system in the polymer is accompanied by its simultaneous complete amorphization. The parameters of the figurative point allow us to estimate the thermodynamic affinity of different alkylbenzenes toward polyethylene.

The reaction of metal exchange between Cd(II) octa(4-bromophenyl)porphyrinate with СuCl₂ and ZnCl₂ in DMFA and DMSO is studied by means of spectrophotometry. The kinetic parameters of the metal exchange reaction are calculated, a stoichiometric reaction mechanism is proposed. The effect the natures of the solvent, salt solvate, and the chemical modification of tetrapyrrole macrocycle have on the kinetic parameters of the metal exchange reaction are revealed.

Carbon nanomaterials with the structure of graphene and different compositions of the surface groups are used as catalysts for the conversion of С₂–С₄ aliphatic alcohols. The conversions of ethanol, propanol- 1, propanol-2, butanol-1, butanol-2, and tert-butanol on carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are investigated. Oxidized and nonoxidized multiwalled carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are synthesized. X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning and transmission electronic microscopies, Brunauer–Emmett–Teller method, derivatographic analyses, and the pulsed microcatalytic method are used to characterize comprehensively the prepared catalysts. It was established that all of the investigated carbon nanomaterials (with the exception of nondoped carbon nanoflakes) are bifunctional catalysts for the conversion of aliphatic alcohols, and promote dehydration reactions with the formation of olefins and dehydrogenation reactions with the formation of aldehydes or ketones. Nanoflakes doped with nitrogen are inert with respect to secondary alcohols and tert-butanol. The role of oxygen-containing and nitrogen-containing surface groups, and of the geometrical structure of the carbon matrix of graphene nanocarbon materials in the catalytic conversion of aliphatic alcohols, is revealed. Characteristics of the conversion of aliphatic alcohols that are associated with their structure are identified.

The catalytic activity of phthalocyanine metal complex immobilized on the surface of a porous polyamide membrane is studied in the oxidation reaction of n-propyl mercaptan. Since noncatalytic oxidation is possible in the presence of oxygen, the kinetics of n-propyl mercaptan oxidation is analyzed as its aqueous alkaline solution passes through unmodified membranes. Characteristics of the catalyst’s performance are selected to evaluate the efficiency of the catalytic process. It is shown that the modified membranes with pore diameters of 1 and 2 μm are the most effective catalysts.

The high efficacy of iron-containing catalysts based on SiO₂–Al₂O₃ systems obtained via sol–gel method in the oxidative destruction of carmoisine azo dye in aqueous solutions is demonstrated. It is found that the stability of the catalysts with respect to the leaching of iron ions into a solution during catalysis grows along with the aluminum content in the composition of aluminosilicate supports. It is concluded that the synthesized catalysts are promising materials for purifying wastewaters contaminated with organic dyes.

The state of tetra(1,2,5-thiadiazolo)porphyrazine in a dimethyl sulfoxide medium is investigated. Relatively high stability is observed for the resulting proton-transfer complex, and a chemical structure is proposed for it. It is shown that the nature of the substituent in the porphyrazine macrocycle influences the kinetic parameters of the destruction of tetra(1,2,5-thiadiazolo)porphyrazine, tetra(5-tert-butylpyrazino) porphyrazine, octaethyltetrapyrazinoporphyrazine, and octaphenyltetrapyrazinoporphyrazine in a nitrogen-containing base–dimethylsulfoxide system. The effect the NH acidity of the porphyrazine macrocycle and the nature of the nitrogenous bases have on the reaction rate and activation parameters of the destruction of β,β-annelated porphyrazine proton-transfer complexes is established.

A series of modified porous activated carbon (AC) catalysts prepared by impregnation were investigated for the low-temperature (≤250°C) selective catalytic reduction (SCR) of NO_x with NH₃ with simultaneous removal of SO₂. The effects of various preparation conditions and reaction conditions on NO and SO₂ conversions were observed, such as support type, active components, copper loading, calcination temperature and presence of H₂O and O₂. The modified AC catalysts were characterized by BET, XRD, TG and TPX methods. The activity test results showed that the optimal catalyst is 15% Cu/WCSAC which can provide 52% NO conversion and 68% SO₂ conversion simultaneously at 175°C with a space velocity of 30000 h^‒1, and the optimal calcination temperature was 500°C. The presence of H₂O could inhibit NO conversion and promote the SO₂ conversion. The effect of O₂ (0–5%) was evaluated, and the NO and SO₂ conversions were best when the concentration of O₂ was 3%. Research demonstrated that Cu/WCSAC catalyst was a kind of potential catalysts due to the amorphous phase, high specific areas and high active ability.

HNbMoO₆ layered oxide was obtained by the ion-exchange from LiNbMoO₆ prepared by solid state reaction (SSR). The micro-structure, textural characteristics and acidity of the as-prepared catalyst were characterized by powder X-ray diffraction (XRD), laser Raman spectroscopy (LRS) and ammonia temperature- programmed desorption (NH3-TPD). Catalytic performance was evaluated in the regioselective nitration of toluene with a novel nitration system containing acetic anhydride and CCl₄. The optimal nitration conditions comprise the application of 95 wt % HNO₃, HNO₃-to-toluene molar ratio of 2.5, catalyst pretreatment temperature of 503 K, reaction temperature of 313 K, and reaction time of 2.5 h. The toluene conversion rate and para-selectivity were also attributable to the strong acidity and the appropriate interlayer distance of the studied catalyst.

It is shown via X-ray diffraction that aqueous solutions of scandium chloride form ionic associates in a wide range of concentrations. It is established that the Sc³⁺ ion coordination number increases upon dilution to 8.2 at an unchanged Sc³⁺–OH² distance of 0.215 nm. The second coordination sphere of the cation forms at an average distance of 0.420 nm. The number of solvent molecules in the sphere logically increases during dilution. It is concluded that the anion does not form its own sphere in highly concentrated solutions. This coordination sphere begins to form only in solutions with moderate concentrations at a distance of 0.315 nm, and it contains six water molecules in diluted solutions.

The optical and electrical properties of inverted emulsions based on sodium bis(2-ethylhexyl) sulfosuccinate (AOT) containing nanoparticles of cadmium sulfide are studied. The particle size of the synthesized samples is determined from UV spectroscopy data. The state of solubilized water in invert emulsions is found to change in the presence of cadmium sulfide due to the formation of aqua complexes. The shape of AOT micelles and the structures formed by drying the invert AOT emulsions are shown to be affected by the degree of hydration and the solubilization of CdS particles.

Solutions of endohedral Gd@C₈₂(C_2v) and Ho@C₈₂(C_2v) metallofullerenes are studied by means of visible and near-IR spectroscopy upon their conversion from neutral to the anionic form via a redox reaction with the electron donor potassium perchlorotriphenylmethide K(18-crown-6)[C(C₆Cl₅)₃]. The concentrations of the studied solutions of endohedral Gd@C₈₂(C_2v) and Ho@C₈₂(C_2v) metallofullerenes in o-dichlorobenzene were determined from the spectroscopic data, and their molar extinction coefficients are calculated.

Gram quantities of a new adduct based on light fullerene tris-malonate samarium salt С₆₀ [C₆₀(=C(COO)₂)₃]Sm₂ are obtained via the reaction of ion exchange. The obtained adduct is studied by means of electron and infrared spectroscopy, X-ray and elemental analysis, electron microscopy, and thermogravimetry. The polythermal solubility of [C₆₀(=C(COO)₂)₃]Sm₂ in water is determined in ampoules via saturation within 20–70°C. The composition of crystalline hydrate [C₆₀(=C(COO)₂)₃]Sm₂ · 36Н₂О, which exists in equilibrium with the saturated solution, is estimated.

The possibility of changing the hydrophilic (polar) surfaces of toroid nanocluster polyoxomolibdates to hydrophobic (nonpolar) surfaces via the modification of Mo₁₃₈ nanoclusters by surfactant molecules (dodecylpyridinium chloride) as a result of the interaction between these compounds in solutions is demonstrated. Benzene and methanol are used as molecular probes (indicators of the condition of nanocluster surfaces). Comparative characteristics of the equilibrium sorption of benzene and methanol vapors on the initial and modified surfaces of the solid polyoxometalate, and data on the sorption of organic molecules on the surfaces of Rhodamine B-modified nanoclusters of the toroid (Mo₁₃₈) and keplerate (Mo₁₃₂) types are obtained.

The dependence of a sensor’s response to hydrogen on the temperature and hydrogen pressure in an indium oxide nanostructured film is measured. A theory of sensor’s response to reducing gases in nanostructured semiconducting oxides with high concentrations of electrons in the conduction band is developed (using the example of In₂O₃). It is shown that the capture of conduction electrons by adsorbed oxygen redistributes the electrons in nanoparticles and reduces the surface electron density and the conductivity of a system; the conductivity is proportional to the electron density in nanoparticle contacts, i.e., to the surface electron density. It is found that atomic oxygen ions react with reducing gases (H₂, CO) during adsorption of the latter: electrons are released and enter the volumes of nanoparticles; the conductivity of the system grows, creating the sensory effect. Using a model developed earlier to describe the distribution of conduction electrons in a semiconductor nanoparticle, a kinetic scheme corresponding to the above scenario is built and corresponding equations are solved. As a result, a theoretical dependence of a sensor’s sensitivity to temperature is found that describes the experimental data well.

Monolithic chromatographic columns for HPLC with sorbent based on 1-vinylimidazole are prepared. It is shown that changing the 1-vinylimidazole content in the initial solution allows us to change the polarity of columns. An example of aromatic hydrocarbons separation is presented.

The effect light has on a silicon liquid crystal–single crystal contact at different temperatures of the surface doping of silicon, and when BaTiO₃ nanoparticles are added to the composition of a liquid crystal, is studied. The mechanism of the emergence of the photo-EMF in the liquid crystal–silicon structure is explained.

Kinetic regularities of the photolysis of thiocyanate solutions using of mono- and polychromatic UV radiation sources with different spectral ranges are studied. Comparative experiments aimed at investigating the role of photochemical action during the oxidation of thiocyanates with persulfates and additional catalytic activation with iron(III) ions are performed. The rate of conversion and the initial rate of thiocyanate oxidation are found to change in the order UV < UV/S₂O₈²⁻ < S₂O₈²⁻/Fe³⁺ < UV/S₂O₈²⁻/Fe³⁺. A synergistic effect is detected when using the combined catalytic method for the destruction of thiocyanates by the UV/S₂O₈²⁻/Fe³⁺ oxidation system. This effect is due to the formation of reactive oxygen species, as a result of both the decomposition of persulfate and the reduction of inactive Fe³⁺ intermediates into Fe³⁺.