卷 90, 编号 10 (2016)

The temperature dependence of the heat capacity of triphenylantimony dibenzoate Ph₃Sb(OC(O)Ph)₂ is studied in the range of 6–480 K by means of precision adiabatic vacuum calorimetry and differential scanning calorimetry. The melting of the compound is observed in this temperature range, and its standard thermodynamic characteristics are identified and analyzed. Ph₃Sb(OC(O)Ph)₂ is obtained in a metastable amorphous state in a calorimeter. The standard thermodynamic functions of Ph₃Sb(OC(O)Ph)₂ in the crystalline and liquid states are calculated from the obtained experimental data: C_p^°(T), H°(T)–H°(0), S°(T), and G°(T)–H°(0) for the region from T → 0 to 480 K. The standard entropy of formation of the compound in the crystalline state at T = 298.15 K is determined. Multifractal processing of the low-temperature (T < 50 K) heat capacity of the compound is performed. It is concluded that the structure of the compound has a planar chain topology.

Comparative studies on the temperature dependence of the dehydrogenation of cis- and trans-isomers of perhydro-m-terphenyl are performed in a flow catalytic reactor. Rate constants and equilibrium constants of all elementary acts of this reaction are calculated on basis of experimental data using the KINET 0.8 program for the mathematical modeling of the kinetics of complex reactions. The resulting data indicate that perhydro-m-terphenyl cis- and trans-isomers structural differences have no appreciable effect on dehydrogenation.

A novel and green procedure for benzaldehyde synthesis by potassium ferrate oxidation of benzyl alcohol employing zeolite catalysts was studied. The prepared oxidant was characterized by SEM and XRD. The catalytic activity of various solid catalysts was studied using benzyl alcohol as a model compound. USY was found to be a very efficient catalyst for this particular oxidation process. Benzaldehyde yields up to 96.0% could be obtained at the following optimal conditions: 0.2 mL of benzyl alcohol, 4 mmol of K₂FeO₄, 0.5 g of USY zeolite; 20 mL of cyclohexene, 0.3 mL of acetic acid (36 wt %), 30°C temperature, 4 h reaction time.

Solubility isotherms of water–sulfonol–hydrochloric (or sulfuric) acid and water–sodium dodecyl sulfate–hydrochloric acid systems at 75°C and a water–sodium dodecyl sulfate–sulfuric acid system at 50°C are constructed. Regions of two-phase liquid equilibrium suitable for use in extraction are found. Concentration parameters for extraction are determined. The interfacial distribution of a series of metal ions with and without such additional complexing reagents as diantipyrylmethane and diantipyrylheptane is studied.

The results of the experimental and theoretical studies of the concentration dependence of surface tension of aqueous solutions of the 1,4-dioxane–acetone–water and glycerol–ethanol–water ternary systems were given. The studies were performed by the hanging-drop method on a DSA100 tensiometer. The maximum error of surface tension was 1%. The theoretical models for calculating the surface tension of the ternary systems of organic solutions were analyzed.

The dielectric spectra of 1,3-butanediol in the temperature range of 298–423 K are analyzed using a variety of theoretical approaches. It is shown that the dielectric spectra of 1,3-butanediol are described by the Davidson–Cole equation. Conclusions as to possible mechanisms of dispersion are drawn using the Debye theory. The relaxation times of 1,3-butanediol, calculated in different ways, are compared. The dipole moments of clusters are calculated for the first time using the Dissado–Hill cluster model.

Quantum chemical calculations were performed at different levels of theory (SCF, DFT, MP2, and CCSD(T)) to determine the geometry and electronic structure of the HOH···CH₄ complex formed by water and methane molecules, in which water is a proton donor and methane carbon (sp³) is an acceptor. The charge distribution on the atoms of the complex was analyzed by the CHelpG method and Hirshfeld population analysis; both methods revealed the transfer of electron charge from methane to water. According to the natural bond orbital (NBO) analysis data, the charge transfer upon complexation is caused by the interaction between the σ orbital of the axial С–H bond of methane directed along the line of the O–H···C hydrogen bridge and the antibonding σ* orbital of the О–H bond of the water molecule. Topological analysis of electron density in the HOH···CH₄ complex by the AIM method showed that the parameters of the critical point of the bond between hydrogen and acceptor (carbon atom) for the O–H···C interaction are typical for Н-bonded systems (the magnitude of electron density at the critical point of the bond, the sign and value of the Laplacian). It was concluded that the intermolecular interaction in the complex can be defined as an Н bond of O–H···σ(С–H) type, whose energy was found to be 0.9 kcal/mol in MP2/aug-cc-pVQZ calculations including the basis set superposition error (BSSE).

The effect of two oxidizers (an oxygen–ozone mixture and hydrogen peroxide) on the kinetics of the oxidative degradation of polyvinyl alcohol in aqueous solutions is studied. Degradation of the polymer is proved not only by a reduction in the weight of oxidized fractions, but in the intrinsic viscosity of their aqueous solutions as well (and thus the average molecular weight of the resulting fractions). It is shown that the degree of the destructive reactions of polyvinyl alcohol grows along with the duration of the process, increasing the initial concentrations of H₂O₂ and raising the temperature. These results can be used in obtaining oxidized fractions of polyvinyl alcohol that have predetermined molecular weights.

Thermodynamic characteristics of the adsorption of alkanes, alcohols, arenes, and esters on graphitized carbon black with a deposited monolayer (0.17%) of 5-hydroxy-6-methyluracil are studied by means of inverse gas chromatography at infinite dilution. It is established that size effects (violation of the additivity of molar changes in internal energy and the entropy of adsorption for pairs of molecules of one homologous series that differ by one methyl group) are observed when organic molecules are adsorbed on the surface of the resulting adsorbent. The size effects are similar to those observed when 1% 5-hydroxy-6-methyluracil is deposited on graphitized carbon black. It is concluded that the observed violation of additivity is associated with cavities in the supramolecular structure.

The adsorption and structural features of Al–5% Pb alloy powder before and after reacting with water are analyzed. Results from studying the morphology and phase composition of the oxidation products are presented, and the specific surface area and porosity of the powders are calculated. It is shown experimentally that water treatment of Al–5% Pb alloy powder even at room temperature leads to the formation of new phases and affects the powder’s morphology. It is established that a major role in the properties of the watertreated powders is played by nanopores that form between crystallites on a particle’s surface during waterinduced oxidation and subsequent thermal dehydration.

Physicochemical studies of a new ZnTe–ZnS semiconductor system are conducted. It is found that at certain ratios of binary components, substitutional solid solutions with a cubic sphalerite structure are formed in this system. Interrelated laws governing changes in the bulk (crystal chemical, structural) and surface (acid–base) properties with varying system composition are identified. It is assumed they can be attributed to the nature of the active (acid–base) sites. The presented data, observed patterns, and an interpretation of them are used not only to confirm earlier proposed mechanisms of atomic–molecular interaction on diamond-like semiconductors, but to search for promising materials for use in highly sensitive selective sensors for environmental and medical purposes as well.

In this paper, mesoporous silica with large specific surface area was used to immobilize laccase by the glutaraldehyde cross-linking method, and after screening and optimization experiments, the best enzyme immobilization process conditions were found (25°C, pH 5.4, 4% glutaraldehyde and 0.2 g/L laccase, treatment time 6 h). After that, the removal and degradation ratio of 2,4-dichlorophenol (abbreviated as DCP) under different conditions were also studied. After the degradation process was performed for 6 h at 30°C, pH 5.4, and DCP initial concentration of 50 mg/L in the presence of 0.1 g of immobilized laccase, the removal ratio and the degradation ratio were 42.28 and 15.93%, respectively. Compared with free laccase, the reusability of immobilized laccase is significantly improved.

It is established that the efficiency of the freezing-out extraction of monocarboxylic acids С₃–С₈ and sorbic acid from water into acetonitrile increases under the action of centrifugal forces. The linear growth of the partition coefficient in the homologous series of С₂–С₈ acids with an increase in molecule length, and the difference between the efficiency of extracting sorbic and hexanoic acid, are discussed using a theoretical model proposed earlier and based on the adsorption–desorption equilibrium of the partition of dissolved organic compounds between the resulting surface of ice and the liquid phase of the extract. The advantages of the proposed technique with respect to the degree of concentration over the method of low-temperature liquid-liquid extraction are explained in light of the phase diagram for the water–acetonitrile mixture.

The use of TiO₂ films for treatment of biomethanated spent wash is reported. The films of TiO₂ were formed and photocatalytic performance of the prepared films in degradation of methylene blue and biomethanated spent wash were studied. Photocatalytic use of these films was found to be effective for degradation of biomethanated spent wash. The photocatalyst was used up for 20 cycles without significant reduction in activities showing long life of the catalyst.

A novel Re(I) complex with the acenaphtho[1,2-b]pyrazino[2,3-f][1,10]phenanthroline (APPT) ligand Re(APPT)(CO)₃Br (abbreviated as Re-APPT) was used to fabricate organic light emitting diodes (OLEDs). From the electroluminescence (EL) spectra of the device at different bias voltages, it could be found that the EL maxima shifted approximately 30 nm. For OLEDs with 5% Re-APPT doped emissive layer, turn-on voltage of 6 V, maximum luminance of 7631 cd/m² and a current efficiency up to 2.36 cd/A were obtained. We suppose that a direct charge trapping took the dominant position in the EL process. Trapping contributed mostly to this relatively higher luminance.

A possible mechanism of nuclear transformations in biological systems in vivo is proposed. Reasons why there is no ionizing radiation that could be detrimental to native systems during the corresponding nuclear reactions are given. It is established that the initial stage of these processes is associated with that of ATP hydrolysis, which initiates the action of the inner-shell electron of an atom participating in the reaction on its nucleus according to the mechanism of weak nuclear interaction. This results in the formation of a nucleus in a metastable state with a disturbed nucleon structure and a charge one unit lower than that of the initial nucleus. It is also assumed that the atom participating in the reaction is adsorbed near the mouth of one of the transport ATPases in the cell’s cytoplasmic membrane, and the reason for the initiating impact the electron has on the nucleus is due to the emergence of a local electric field formed during ATP hydrolysis near the ion channel of a donor–acceptor pair of charges that is opposite to the direction of the average membrane field. It is concluded that as a result of the key role of weak nuclear interaction in these processes, the energy of nuclear transformations in biological systems in vivo is released through the emission of neutrino–antineutrino pairs that are harmless to living organisms.

Times of metastable droplet relaxation to their equilibrium state are calculated at saturated vapor pressures, depending on the droplet size. It is shown that for small droplets with radius R = 6 molecular diameters (or ~2 nm) the relaxation times are ~1 ns (which is comparable to the characteristic flight times of rarefied gas molecules). For large droplets with radius R ~ 800 molecular diameters, the relaxation times are as long as 10 μs. At a fixed droplet radius (6 ≤ R ≤ 800), the range of variation in relaxation time from the melting point to the critical temperature does not exceed one order of magnitude: the lower the temperature, the slower the relaxation process.

The composition of condensed products resulting from the combustion of thermite mixtures (Al + Fe₂O₃) in air is studied by precise methods. It is shown that during combustion, calcium is formed and stabilized in amounts of maximal 0.55 wt %, while is missing from reactants of 99.7 wt % purity. To explain this, it is hypothesized that a low-energy nuclear reaction takes place alongside the reactions of aluminum oxidation and nitridation, resulting in the formation of calcium (Kervran–Bolotov reaction).

It is shown that the gas chromatographic separation of enantiomers on columns with achiral nonpolar stationary phases is principally possible as a result of the dynamic modification of stationary phases by sorbates under analysis. It is found that a number of key characteristic features is intrinsic to such separation: it can be only partial, it does not occur for all chromatographic columns, and it is observed only for some compounds and only within narrow ranges of quantities of sorbates that are close to the limits of mass overload of chromatographic systems. These characteristic features are illustrated by the examples of separating (1R,5R)-(+)- and (1S,5S)-(−)-α-pinenes on a WCOT column with an RTX-5 phase. The main characteristic feature of the separation of enantiomers as a result of the dynamic modification of stationary phases is the nonconformity of peaks in chromatograms with two individual enantiomers, compared to other ways and means for their separation; the first eluting peak belongs to the enantiomer that predominates in a mixture irrespective of its configuration, while the second peak corresponds to the racemic mixture of enantiomers; i.e., the ratio of peak areas in chromatograms does not correspond to the actual ratio of enantiomers in samples under analysis and is strongly distorted as a result of their incomplete separation. It is concluded that the separation of racemic mixtures in achiral systems is fundamentally impossible under any conditions, and this is one of the key criteria of the validity of the considered concept as a whole.