Vol 90, No 3 (2016)

The thermal stability of 5,10,15-triphenylcorrole as the simplest representative of meso-substituted corroles and its complexes with d-metals (Cu³⁺, Mn³⁺, Mn⁴⁺, Co³⁺, Co⁴⁺, and Zn²⁺) is studied for the first time via thermogravimetry in oxidizing and inert atmospheres. It is shown that corroles, both as free ligands and in the form of metal complexes, are less thermally stable than porphyrins with a similar structure. It is found that if the free ligands of porphyrins are thermally more stable with respect to thermal oxidation than d-metal complexes, the thermal stability of metal corroles can be both lower and higher than those of free ligands. It is concluded that the order of thermal stability of compounds MnCor < CoCor < H₃Cor < ZnCorH < CuCor is reversed upon moving from an oxidizing to an inert medium. It is shown that corroles complexes with many d-metals (Co, Mn, and others) readily participate in extracoordination reactions with electron-donating solvents, e.g., DMF, as is indicated by spectrophotometry and thermogravimetry.

Study of the combustion and explosion of hydrogen‒carbon oxide‒air mixtures shows that the sharpness of a chain thermal explosion depends on the frequency of branching in a given branch of a reaction chain. It is established that varying the СО: Н₂ concentration allows us to observe and eliminate the degeneration of an explosion while maintaining the regimes of ignition and deflagration.

Kinetics of N-chloromethylamine decomposition in an aqueous base medium and chloroform at different temperatures is studied. The decomposition of N-chloromethylamine is found to obey a second order equation in an aqueous base medium at an equimolar ratio of the reagents and a first order equation in chloroform with excess base. The activation energy of N-chloromethylamine decomposition in the both solvents is determined. A mechanism for the reaction is proposed. N-Chloromethylamine is shown to have approximately equal stability in these solvents within the studied temperature range.

Role of added chloride ions on the shift of reaction pathway of oxidation of aromatic ketones (acetophenone, desoxybenzoin) by dichloroisocyanuric acid (DCICA) was studied in aqueous acetic acid—perchloric acid medium. Participation of enolic and protonated forms of ketones in the rate determining steps is manifested from zero and first orders with respect to the oxidant in absence and presence of added chloride ions, respectively. Positive and negative effects of acid and dielectric constant on the reaction rate were observed. The observations deduce plausible mechanisms involving (i) rate-determining formation of enol from the conjugate acid of the ketone (SH⁺) in the absence of added chloride ions and (ii) rapid formation of molecular chlorine species from HOCl (hydrolytic species of DCICA) in the presence of added chloride ions, which then interacts with SH⁺ in a rate-determining step prior to the rapid steps of product formation. The order of Arrhenius parameters substantiate the proposed plausible mechanisms based on order of reactants both in presence and absence of added chloride ions.

Water−ethylene glycol mixtures containing from 0.002 to 0.998 mole fractions of ethylene glycol at T = 298.15 K and P = 0.1 and 100 MPa are simulated by means of classical molecular dynamics. Such structural and dynamic characteristics of hydrogen bonds as the average number and lifetime, along with the distribution of molecules over the number of hydrogen bonds, are calculated; their changes are analyzed, depending on the mixture’s composition and pressure. It is shown that the components are characterized by a high degree of interpenetration and form a uniform infinite hydrogen-bonded cluster over the range of concentrations. It is found that the higher the concentration of ethylene glycol, the greater the stability of all hydrogen bonds. It is concluded that an increase in pressure lowers the number of hydrogen bonds, while the average lifetime of the remaining hydrogen bonds grows.

The boiling temperature and the corresponding vapor phase composition in the existence domain of liquid solutions were calculated from the partial pressures of saturated vapor of the components and lead selenide over liquid melts in the lead–selenium system. The phase diagram was complemented with the liquid–vapor phase transition at atmospheric pressure and in vacuum of 100 Pa, which allowed us to judge the behavior of the components during the distillation separation.

Enthalpies of dissolution are determined thermochemically under standard conditions, and the solvation enthalpies of n-hexane, n-decane, and n-hexadecane in a mixed methanol–hexamethylphosphor-triamide (HMPT) solvent are calculated. Experimental data are compared to values obtained from model calculations. It is shown that positive deviations of the enthalpies of dissolution of alkanes in a МеОН–HMPT mixture from additivity in the range enriched with methanol are due to changes in the bulk properties of the mixed solvent, while negative deviations of enthalpies of dissolution from additivity in the range enriched with HMPT are due to the selective solvation of alkanes by HMPT.

The acid dissociation constants of form pK₁ = 7.34 ± 0.01, pK₂ = 7.84 ± 0.01, pK₃ = 8.77 ± 0.01, pK₄ = 9.49 ± 0.01, and pK₅ = 10.70 ± 0.02 of cationic amikacin are determined by pH-metric titration at 25°C against the background of 0.1 mol/L KNO₃. K₁, K₂, K₃, and K₄ correspond to the dissociation of protons coordinated to amino groups, while K₅ characterizes the dissociation of the hydroxyl hydrogen atom, testifying to the amphoteric character of amikacin molecules. Applying density functional theory (DFT) with the B3LYP hybrid functional and the 6-311G**++ basis set, the partial charges on the atoms of an amikacin molecule are calculated. It is concluded that the dissociation of H(55)hydrogen atom occurs with a greatest partial charge of +0.53631.

The kinetics of the reaction between one-electron-reduced cobalamin (cobalamin(II), Cb(II)) and the two-electron-oxidized form of vitamin C (dehydroascorbic acid, DHA) with amino acids in an acidic medium is studied by conventional UV–Vis spectroscopy. It is shown that the oxidation of Cbl(II) by dehydroascorbic acid proceeds only in the presence of sulfur-containing amino acids (cysteine, acetylcysteine). A proposed reaction mechanism includes the step of amino acid coordination on the Co(II)-center through the sulfur atom, along with that of the interaction between this complex and DHA molecules, which results in the formation of ascorbyl radical and the corresponding Co(III) thiolate complex.

The C–H bond dissociation enthalpies (BDEs) of the 26 N, O, S-containing mono-heterocyclic compounds were evaluated using the composite high-level ab initio methods G3 and G4. The C–H BDEs for 32 heterocyclic compounds were calculated using 8 types of density functional theory (DFT) methods. Comparing with the experimental values, the BMK method gave the lowest root mean square error (RMSE) of 7.2 kJ/mol. Therefore, the C–H BDEs of N-fused-heterocyclic compounds at different positions were investigated by the BMK method. By NBO analysis two linear relationships between the C–H BDEs of quinoline and isoquinoline with natural charges qC/e in molecules and with natural charges qC/e in radicals were found. The substituent effects on C_(α)–H BDEs in N-fused-heterocyclic compounds were also discussed. It was found that there are two linear relationships between the C_(α)–H BDEs of quinoline and isoquinoline derivatives with natural charges qC_(α)/e for the EDGs and CEGs substituents.

A kinetic model for the precipitation of a dispersed compound from solutions is formulated, based on a description of the evolution in the function of its particle distribution according to its states during precipitation. A boundary problem about the precipitation of a compound during the evaporation of a solvent from a solution under conditions in which the rate of aggregate formation is high is considered. The solution to this boundary problem can be used to describe the formation of a film of polystyrene during the evaporation of its solution in toluene and o-xylene deposited onto a substrate.

Debates continue on the applicability of the Young–Laplace equation for droplets, vapor bubbles and gas bubbles in nanoscale. It is more meaningful to find the error range of the Young–Laplace equation in nanoscale instead of making the judgement of its applicability. To do this, for seven liquid argon drops (containing 800, 1000, 1200, 1400, 1600, 1800, or 2000 particles, respectively) at T = 78 K we determined the radius of surface of tension R_s and the corresponding surface tension γ_s by molecular dynamics simulation based on the expressions of R_s and γ_s in terms of the pressure distribution for droplets. Compared with the two-phase pressure difference directly obtained by MD simulation, the results show that the absolute values of relative error of two-phase pressure difference given by the Young–Laplace equation are between 0.0008 and 0.027, and the surface tension of the argon droplet increases with increasing radius of surface of tension, which supports that the Tolman length of Lennard-Jones droplets is positive and that Lennard-Jones vapor bubbles is negative. Besides, the logic error in the deduction of the expressions of the radius and the surface tension of surface of tension, and in terms of the pressure distribution for liquid drops in a certain literature is corrected.

A material with an electrically ОН^–-conductive porous layer of cyclam-substituted PVC filled with active coal containing NaOH aqua complexes with aza-crown ligands and cross-linked with the surface of cellulose tissue fibers has been synthesized. The structure of the material was studied. Its sorption capacity in vapors and liquid benzene and hexane, specific resistance, potential of ОН^- transfer from solution to layer, and rate constants of ОН^– travel in the layer of the material as an electrochemical bridge in vapors and liquid benzene and hexane were determined. The aqua complexes decomposed in the layer with formation of Н₂ during the cathodic polarization of the bridge and О₂ during the anodic polarization; the composition of the complexes was regenerated due to the motion of ОН^–.

The possibility of the ion-exchange of Na⁺ and K⁺ cations contained in OFF-type zeolite for H⁺, Ni²⁺, Cu²⁺, Co²⁺, and La³⁺ cations is investigated. Chemical and phase compositions, the morphology of crystals, and the adsorption properties of synthesized samples are studied via X-ray fluorescence and X-ray diffraction analysis, IR spectroscopy, scanning electron microscopy, and adsorption measurements.

The adsorption of anionic complexes of erbium with Trilon B on D-403 anionite is studied at ionic strengths of 1 and 2 mol/kg (NaNO₃) and temperatures of 298 and 343 K. The values of the stability constants of complex ions of REE with Trilon B and the Gibbs energies of complexation are calculated. The values of the Gibbs energy and the enthalpy and entropy of ion exchange are determined. Using the obtained thermo-dynamic and sorption characteristics, the possible separation of anionic complexes of erbium and cerium with Trilon B is demonstrated via frontal ion-exchange chromatography. A series of sorption capacities of anionic complexes of cerium, yttrium, and erbium is presented using the values of the Gibbs energy of ion exchange.

The temperature dependences of the induced dichroic ratios (DRs) of azo dyes after their photoalignment in thin films 80 to 200 nm thick are studied. It is found that the DR values of layers containing dyes of the benzeneazodiphenyl series fall from 6.0 to 1.6 as the temperature rises from 60 to 130°C, respectively. A reduction in induced DR as the temperature rises (from 20 to 100°C) is also observed for the thin films of the dyes of benzeneazo-5,5’-dioxodibenzothiophene group. The absence of induced DR after irradiation with polarized light at 100°C indicates there is no alignment of molecules at this temperature.

The thermal treatment of sodium sulfate was found to affect its optical and luminescent properties when activated with trivalent rare-earth ions. The influence of crystal water molecules on radiation processes in sodium sulfate was studied. The interactions of atomic hydrogen with ions and radicals were calculated by the semiempirical MNDO quantum-chemical method. The hydrogen atom was found to form stable complexes with all ions and radicals. The ions and radicals of the sulfate subsystem play the role of traps for hydrogen atoms and escape recombination, giving rise to recombination luminescence at 150 K during UV excitation of the crystalline hydrate.

Refined thermodynamic functions (entropy, enthalpy increments, and reduced Gibbs energy) of scandium trifluoride ScF₃ in the crystalline and liquid states in the temperature range 5–2500 K are presented.