Vol 90, No 2 (2016)

In order to propose mechanisms of complicated chemical systems, it is necessary to study simpler subsystems. The mechanism we have proposed for the Bray–Liebhafsky (BL) oscillating reaction is based on kinetic studies of several reactions of iodine compounds between them and with hydrogen peroxide. Because the reactants of the non-catalysed Briggs–Rauscher (BR) oscillating reaction are the same as those of the BL reaction plus malonic acid, we propose now to extend the mechanism of the BL reaction to the BR reaction. With this aim, we add radical reactions of iodine compounds and of malonic acid. The choice of these reactions is based on our recent study of the unusual kinetics of the iodate reduction by high concentrations of hydrogen peroxide.

The orbital ordering of Ti(III) ions is observed via EPR spectroscopy for the catalytic system TiCl₄ + TIBA in an isopentane solution with an excess of organoaluminum compound. A model of the alternating ground states of 3d¹ ions (d_xy and \(d_{z^2 }\) is proposed for the ordered structures. Ti(III) ions with the d_xy ground states are mono- and dialkylated.

Proton transfer along the hydrogen bond in complexes of DMF with Н₃РО₄, Н₃РО₃, СН₃Н₂РО₃, and their dimers has been investigated by the B3LYP/6-31++G** method in combination with the C-PCM model. When the О_acid···О_DMF distance (R) in the scanning procedure is not fixed, the energy profile in all cases has a single well. When this distance is fixed, there can be a proton transfer in all of the complexes in the gas phase at R > 2.6 Å; if solvation is taken into account, proton transfer can take place at R > 2.4 Å (R > 2.5 Å for DMF complexes with СН₃Н₂РО₃ and its dimer). The height of the energy barrier to proton transfer increases with increasing R. Proton transfer is energetically most favorable in the DMF–phosphoric acid complexes. The structural and energetic characteristics of the hydrogen-bonded complexes calculated on the basis of the solvation model are compared with the same parameters for the complexes in the gas phase.

In the present work the complexation process between Ag⁺ and Mg²⁺ cations and 4-hydroxyphenyl-2,5-bis(2-benzofuranyl)pyridine (HBFPY) ligand was studied in pure dimethylformamide (DMF), ethanol (EtOH), acetonitrile (AN) and in (DMF-EtOH), (AN-EtOH) and (DMF-AN) binary mixed solvent solutions at different temperatures using the conductometric method. Also in this work the complexation reaction between Ca²⁺, K⁺ cations and HBFPY ligand, was studied in pure dimethylformamide (DMF), propanol (PrOH), 1,4-dioxane (DOX), ethanol (EtOH) and in DMF-PrOH, DMF-DOX and DMF-EtOH binary mixed solvent solutions at different temperatures using the conductometric method. The conductance data show that the stoichiometry of the complexes formed between this ligand and the studied cations is 1 : 1 [ML]. In most cases, addition of HBFPY to solutions of these cations, causes a continuous increase in the molar conductivities which indicates that the mobility of complexed cations is more than the uncomplexed ones. The stability constants of the complexes were obtained from fitting of molar conductivity curves using a computer program, GENPLOT. The stability constant of [Mg(HBFPY)]²⁺ complex in various neat solvents at 15°C decreases in order: EtOH > DMF > AN and the stability constant of [Ag(HBFPY)]⁺ complex in various neat solvents at 35°C decreases in order: DMF > EtOH. The values of standard enthalpy changes (ΔH°_c) for complexation reactions were obtained from the slope of the Van’t Hoff plots and the changes in standard entropy (ΔS°_c) were calculated from the relationship ΔH°_c,295.15= ΔH°_c–298.15ΔS°_c.

The heats of solution of crystalline serine and isoserine in water and potassium hydroxide solutions are measured via direct calorimetry at 298.15 K. The standard enthalpies of formations of amino acids and products of their dissociation in aqueous solution are calculated.

The enthalpies of the reactions between solutions of Co(NO₃)₂ and solutions of glycine (Gly) and L-histidine (His) are determined via direct calorimetry at different pH values and metal: ligand ratios using KNO₃ as a background electrolyte (T = 298.15 K, I = 0.2–1.0). The enthalpy changes upon the formation of cobalt glycinate complexes and Co²⁺ mixed-ligand complex, viz., glycine–L-histidine, were calculated. The standard thermodynamic parameters (Δ_rH°, Δ_rG°, Δ_rS°) of complexation are determined. The CoGlyHis complex is shown to be stable toward decomposition into homogeneous complexes.

The acid−base equilibrium constants for glycyl-glycyl-glycine (triglycine) in water–ethanol solvents containing 0.0, 0.1, 0.3, and 0.5 mole fractions of ethanol are determined by potentiometric titration at 298.15 K and an ionic strength of 0.1, maintained with sodium perchlorate. It is established that an increase in the ethanol content in the solvent reduces the dissociation constant of the carboxyl group of triglycine (increases pK₁) and increases the dissociation constant of the amino group of triglycine (decreases pK₂). It is noted that the weakening of the acidic properties of a triglycinium ion upon an increase of the ethanol content in the solvent is due to the attenuation of the solvation shell of the zwitterionic form of triglycine, and to the increased solvation of triglycinium ions. It is concluded that the acid strength of triglycine increases along with a rise in the EtOH content in the solvent, due to the desolvation of the tripeptide zwitterion and the enhanced solvation of protons.

The solubilities of thiourea in methanol-water mixtures with mass fraction of methanol of 0.54, 0.65, 0.76, 0.88, and 1.00 were determined. The experimental data were approximated with the modified Apelblat equation. The dissolution enthalpy and entropy were calculated from the experimental data and the nature of interactions between the solvent and solute were discussed. The obtained solubility data can be used for development of various technological processes involving thiourea, particularly for the synthesis of isopropyl mercaptan.

The phase equilibria in the ternary system NaCl–SrCl₂–H₂O at 288.15 K were studied with the isothermal equilibrium solution method. The phase diagram and refractive index diagram were plotted for this system at 288.15 K. The phase diagram contains one invariant solubility point, two univariant solubility curves, and two crystallization fields of NaCl and SrCl₂ · 6H₂O. The refractive indices of the equilibrium solution change regularly with w(NaCl) increase. The calculated refractive index data are in good agreement with the experimental data. Combining the experimental solubility data of the ternary system, the Pitzer binary parameters for NaCl at 288.15 K and SrCl₂ at 298.15 K, the Pitzer mixing parameters θ_{Na, Sr}, Ψ_{Na, Sr, Cl} and the solubility equilibrium constants Ksp of solid phases existing in the ternary system at 288.15 K were fitted using the Pitzer and Harvie-Weare (HW) models. The mean activity coefficients of sodium chloride and strontium chloride, and the solubilities for the ternary system at 288.15 K were presented. A comparison between the calculated and measured solubilities shows that the predicted data agree well with the experimental results.

Density functional theory (DFT) and MP2 calculations have been employed to study of 3-amino-4-nitrofurazan molecule using the standard 6-311++G(d,p) basis set. The chemical properties of the 3-amino-4-nitrofurazan have been extensively studied. The geometries of molecules in the gas phase were optimized and compared with the crystallography of this substance. The results suggest that A form is the most stable form in the gas phase and it is the predominant tautomer in solution according to the DFT and MP2 calculations, respectively. In addition, variation of dipole moments in the gas phase, the specific solvent effects with addition of one molecule of water near the electrophilic centers of tautomers, the transition state of proton transfer assisted by a water molecule, the NBO charges of atoms and the potential energy surface were investigated. The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are presented.

In the Auger electron spectra (AES) simulations, we define theoretical modified kinetic energies of AES in the density functional theory (DFT) calculations. The modified kinetic energies correspond to two final-state holes at the ground state and at the transition-state in DFT calculations, respectively. This method is applied to simulate Auger electron spectra (AES) of 2nd periodic atom (Li, Be, B, C, N, O, F)-involving substances (LiF, beryllium, boron, graphite, GaN, SiO₂, PTFE) by deMon DFT calculations using the model molecules of the unit cell. Experimental KVV (valence band electrons can fill K-shell core holes or be emitted during KVV-type transitions) AES of the (Li, O) atoms in the substances agree considerably well with simulation of AES obtained with the maximum kinetic energies of the atoms, while, for AES of LiF, and PTFE substance, the experimental F KVV AES is almost in accordance with the spectra from the transitionstate kinetic energy calculations.

Structural organization models are developed using radial distribution functions obtained earlier via XRD analysis for aqueous solutions of dysprosium chloride over a wide range of concentrations under standard conditions. The optimum variants are selected by calculating the theoretical functions for each model and comparing how they agree with experimental functions. Quantitative characteristics of the nearest surrounding of Dy³⁺ and Cl^– ions, e.g., coordination numbers, interparticle distances, and varieties of ion pairs, are established. It is shown that the average number of water molecules in the first coordination sphere of a cation falls from 8.5 to 6 as the concentration grows; the structure of the system over the range of concentrations is determined by noncontact ion associates.

Density functional theory (DFT) methods were used to analyze the effects of molecular structure and ring currents on the NMR chemical shielding tensors and NQR frequencies of harmine and harmaline alkaloids in the gas phase. The results demonstrated that NMR tensors and NQR frequencies of ¹⁵N nuclei in these compounds depend on chemical environment and resonance interactions. Hence, their values are obviously different in the mentioned structures. The interpretation of natural bond orbital (NBO) data suggests that in harmine structure, the lone pair participation of N₉ in π-system electron clouds causes to development of aromaticity nature in pyrrole ring. However, the chemical shielding around N₉ atom in harmine structure is higher than in harmaline, while in harmaline structure, lone pair participation of N₂ in π-system electron clouds causes to development of aromaticity nature in pyridine ring. Hence, chemical shielding around N₂ atom in harmaline structure is higher than in harmine. It can be deduced that by increasing lone pair electrons contribution of nitrogen atoms in ring resonance interactions and aromaticity development, the values of NMR chemical shielding around them increase, while χ and q_zz values of these nuclei decrease.

Modified flocculation magnesium silicate is prepared by a hydrothermal process at 120°C for 18 h after adding Al₂(SO₄)₃ into the magnesium silicate gel. Compared with standard magnesium silicate with 328.116 m² g^–1 surface area, this modified magnesium silicate has a bigger BET surface area of 536.803 m² g^–1 and a lower interlayer water content. Modified magnesium silicate exhibits high β-carotene adsorption with a maximum adsorption capacity of 364.96 mg g^–1. It is shown that when suspended in organic solvent, this material can be used effectively for carotenoid separation. Furthermore, our results suggest that modified magnesium silicate may be a promising candidate as an absorbent in the decoloring of oil.

The surface reactions of dimethyl ether (DME) on industrial alumina (γ-Al₂O₃) were studied by chromatographic analysis of the products at the outlet of the flow reactor and (independently) by diffuse reflectance IR spectroscopy. The major products of the reactions at 250°С were found to be methanol formed in the reaction of DME with hydroxyl groups (the 3720 and 3674 cm^–1 bands in the diffuse reflectance spectrum) and various methoxy groups (the 1121, 1070, 695, and 670 cm^–1 bands in the differential spectra). The presence of molecularly adsorbed methanol was confirmed by experiments with methanol fed in a high-temperature IR cell. The interaction of the resulting methanol molecule with the hydroxyl group led to the formation of a water molecule in the gas phase and a methoxy group on the oxide surface. Strong adsorption of molecular DME was revealed, which was favored by an increase in the temperature of the preliminary calcination of oxide from 250 to 450–500°С; treatment of alumina with water vapor after its preliminary contact with DME led to a recovery of the hydroxyl coating and a replacement of molecularly adsorbed DME with hydroxyl. The thermal effect recorded in a flow reactor was positive during the adsorption of DME and negative during the desorption of weakly bonded DME. Schemes of formation of methoxy groups in the interaction of DME and methanol with surface hydroxyls were suggested.

The relationship between the thermodynamic properties of Zr–Si liquid alloys and their propensity to amorphization is studied. The temperature–concentration dependences of the thermodynamic properties of melts are presented using the concept of associated solutions. It is shown that the range of amorphization coincides with the range of the predominant concentration of Zr₃Si associative groups with low formation entropy.

The enthalpy of solution of LаОНMoO₄ and Cs₂MoO₄ in aqueous HCl at 298 К has been determined by solution calorimetry, and the standard enthalpy of formation of lanthanum hydroxomolybdate has been calculated. The enthalpies of solution of NaLa(MoO₄)₂ and Na₅Lа(MoO₄)₄ in molybdate melt at 973 K have been determined by high-temperature melt solution microcalorimetry, and the high-temperature enthalpies of the double molybdates in the 298–1000 K range have been measured by the mixing method. The standard enthalpies of formation of the double molybdates have been calculated using data available from the literature. The low-temperature heat capacity of NaLa(MoO₄)₂ in the 60–300 K range has been measured on an adiabatic vacuum calorimeter. The basic thermodynamic properties of NaLa(MoO₄)₂, Na₅Lа(MoO₄)₄, and LаОНMoO₄ have been calculated.

The thermal conductivity of water and glycerol is investigated via the transient hot wire method by adding small amounts of copper nanoparticles to solutions. At a 0.2% copper nanoparticle concentration, the thermal conductivity coefficient rises to 25% for the Cu + glycerol system, and to 35% for Cu + water system. A mechanism and mathematical model for describing the nanoparticle aggregation effect on the thermal properties of nanofluids are proposed, based on an analysis of the accumulated experimental data. It is shown that the enhancement of nanofluid thermal conductivity at low nanoparticle concentrations is directly proportional to their volume fraction and thermal conductivity coefficient, and (in accordance with the literature data) is inversely proportional to the radius and the aggregation ratio. The proposed model describes the existing experimental data quite well. The results from this work can be applied to the rapid cooling of electronic components, in the power engineering for ensuring the rapid and effective transfer of thermal energy in a nuclear reactor, and in the oil industry for thermal stimulation.

The mechanism and kinetics of the decomposition of the Mo₁₃₂ nanocluster polyoxomolybdate (POM) with a keplerate structure in aqueous solutions, including those containing calcium ions, were studied. The destruction mechanism of POM and the lifetime of Mo₁₃₂ depend on the initial concentration of its solutions, and this, in turn, is related to the thermodynamic factors. The destruction of keplerate can be described as an autocatalytic process. The calcium ions stabilize POM to different degrees depending on their content in solution.

The polarity of an MCM-41 adsorbent surface and organosilylated composites based on it with grafted trimethylsilane and dimethylphenylsilane groups is studied via inverse gas chromatography at infinite dilution. The dispersion and specific components of the value proportional to the Helmholtz adsorption energy are calculated, and a comparative analysis of the surface polarity of MCM-41 and its modified analogs relative to the commercially available C-120 silica gel is performed. The electrostatic and donor–acceptor components of the specific Helmholtz adsorption energy are calculated through linear decomposition of the adsorption energy. It is established that MCM-41 is less polar than C-120. The modification of the initial adsorbent surface leads to a reduction in polarity, due mainly to the weakening of induction and orientation interactions. It is concluded that the surfaces of the modified samples retain the ability to form hydrogen bonds.

The behavior of [1,2-bis(tert-butylperoxy)ethyl]benzene (I) on Pt electrode is studied by means of cyclic voltammetry (CVA). A comparison of the electrochemical properties of I and the properties of previously studied bridge-type 1,2,4,5-tetraoxane ((1,4)-1,4-dimethyl-7-(4-methylbenzyl)-2,3,5,6-tetraoxabicyclo[2.2.1]heptane) (II) shows that the biperoxide studied in this work is reduced on a Pt electrode at lower cathodic potentials and is resistant to electrooxidation.

This study is focused on characterization of the low temperature properties of the YSZ/STO/YSZ superlattice film deposited onto unilateral polished SrTiO₃ (STO) monocrystalline substrates using pulsed laser deposition (PLD). The phase composition, structure, surface morphology and electrical properties of the oxygen ion conducting electrolyte YSZ/STO/YSZ multilayers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The minimum conductivity activation energy of YSZ/STO/YSZ is 0.76 eV at 300–500°C. The YSZ/STO/YSZ superlattice film shows an enhancement in conductivity by three orders of magnitude compared to bulk YSZ at a temperature of 300°C.

The effect of the carrier frequency of the exciting laser pulse on the kinetics of intramolecular photoinduced charge transfer in the multi-channel stochastic model is studied. It is shown that the population of different states of high-frequency intramolecular modes upon varying the frequency of the excitation pulse can considerably alter the rate constant of ultrafast charge transfer. It is found that a negative vibrational spectral effect is expected in the vicinity of a barrier-free area (the rate constant of photoinduced charge transfer decreases along with the carrier frequency of the excitation pulse), while a positive effect is predicted in areas of high and low exergonicity (an inverse dependence). It is concluded that the value of the spectral effect falls along with the time of vibrational relaxation. For ultrafast photo-induced charge transfer, however, it remains considerable up to relaxation times of 100 fs.

The luminescent properties of europium(III) and terbium(III) complexes with para- and ortho-ethoxybenzoic acids are studied. The excitation energies of the triplet states of ligands are determined, a hypothesis is made about the efficient luminescence of europium(III) and terbium(III) complexes, the geometry of the coordination polyhedron of a europium complex is established, and the luminescence quantum yields of the complexes in solution are determined.

Aspects of the methodology and language of chemistry and physics are discussed. Chemistry defines the chemical properties of any substance from the results of its interaction with other substances using the logic of relations. Therefore, describing the properties of substances means using sets of different ideas, including ones that are opposite in meaning. Consequently, depending on the nature of reagents with respect to which properties are established, substances show chemical dualism. This dualism was established in chemistry long before the discovery of wave–particle dualism, to understand which N. Bohr proposed the complementarity principle in 1927. The methodology of natural sciences corresponds to the principle of complementarity and the need to use it to understand the world and record the results in the linguistic reality of several languages.