Thermodynamic analysis of the structure of aqueous solutions of C<Subscript>12</Subscript>–C<Subscript>18</Subscript> hydrocarbons

Thermodynamic cycles including the increments \(\Delta G_{CH_2 }^0 , \Delta H_{CH_2 }^0 \), and \(T\Delta S_{CH_2 }^0 \) were constructed for dissolution, evaporation, hydrophobic hydration of C₅–C₉ hydrocarbons, and transfer from vapor (\(\Delta G_{CH_2 }^0 \) = ?0.7 kJ·mol^?1, \(\Delta H_{CH_2 }^0 \) = 2.9 kJ·mol^?1, \(T\Delta S_{CH_2 }^0 \) = 3.6 kJ·mol^?1) and water (\(\Delta G_{CH_2 }^0 \) = ?1.4 kJ·mol^?1, \(\Delta H_{CH_2 }^0 \) = 5.8 kJ·mol^?1, \(T\Delta S_{CH_2 }^0 \) = 7.2 kJ·mol^?1) to micelles of C₁₂–C₁₈ hydrocarbons. The formation of bistable hydrated micelles of C₁₂–C₁₈ is explained by a transition between the order-disorder states in an assembly of small (nano) systems of water. The extensive parameters of small systems and critical phenomena predicted by fluctuation theory are discussed.     

Synthesis and examination of antimicrobial properties of aminomethylated derivatives C<Subscript>6</Subscript>–C<Subscript>7</Subscript> of alicyclic diols

Synthesis of C₆–C₇ alicyclic diols was studied by a catalytic oxidation of cyclohexene, norbornene and their methyl derivatives in the presence of heterogenized molybdenum-containing catalysts. By a triple condensation of the diols with formaldehyde and secondary amines a synthesis of their aminomethylated derivatives with various substituents at nitrogen atom was examined. Antimicrobial properties of the synthesized amino alcohols in M-10 oil as additives with fungicidal and bactericidal activities were studied.     

Enthalpy of solution of VOCl<Subscript>3</Subscript> in dilute sodium hydroxide solutions and the standard enthalpy of formation of the HVO<Stack><Subscript>4</Subscript><Superscript>2−</Superscript></Stack> ion

The calorimetric enthalpies of solution of liquid vanadium oxytrichloride in dilute sodium hydroxide solutions were measured at 298.15 K and ionic strengths I = 0.5, 1.0, or 1.5 (NaClO₄). The standard enthalpy of formation of the HVO ₄ ^2? ion was calculated from the measured data.     

Regime of superhigh reactivity of the YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6 + δ</Subscript> superconductor toward the components of air

Physicochemical features of the YBa₂Cu₃O_{6 + δ} superconductor synthesized via ceramic route and subjected to a kind of modification by long-term exposure to an atmosphere with low pH₂O have been studied by X-ray diffraction, thermal analysis, and magnetometry. The resulting material had a high degree of saturation with air components at room temperature and 30% humidity, up to 1.5 wt % in 30 days, which is not inherent in YBa₂Cu₃O_{6 + δ}.     

Effect of mechanical activation of reagents’ mixture on the high-temperature synthesis of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiB<Subscript>2</Subscript> composite powder

A powder mixture of Al/TiO₂/H₃BO₃ = 10/3/6 in molar ratio was used in this study to form the Al₂O₃–TiB₂ ceramic composite via thermite reactions (combustion synthesis). As no combustion synthesis occurred for an unmilled sample in a furnace, the mixture was milled in a planetary ball-mill for various milling times, and the as-milled samples were in situ synthesized in the furnace at a heating rate of 10 °C/min. The differential scanning calorimetry (DSC) measurements were performed with the same heating rate on the unmilled and the as-milled samples to evaluate the influences of the milling on the mechanisms and efficiencies of reactions. Although no combustion synthesis occurred for the unmilled sample in the furnace, two exothermic peaks were detected in its DSC curve after the melting of the Al. For the as-milled samples, significant changes revealed in the DSC curves, suggest that the milling process before the combustion synthesis changed the mechanisms and efficiencies of reactions. In addition, the intensity and the temperature of the exothermic peaks in the DSC curves changed by increasing the milling time. According to the XRD analyses, by enhancing the milling time, the purity of the final products would increase, confirming that the efficiency of the reactions increased. Finally, the microstructures of the as-milled and as-synthesized samples were examined by a SEM, and it was shown that the morphology of the reactant powders was altered by increasing the milling time.     

Effect of acid–base characteristics of ZrO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript> on catalytic properties in carboxylation of methanol

We have established that the calcination temperature for ZrO₂–Y₂O₃ catalysts changes their acid–base spectrum, which determines the direction of the conversions in the mixture MeOH + CO₂. For samples with predominance of acid sites, the major product is dimethyl ether. As the content of base sites increases, methyl formate is formed. Activity in dimethyl carbonate synthesis is exhibited only by samples in which the basicity is higher than the acidity or close to it.     

Theoretical study of the activation barriers of elementary reactions of hydrogenation of aluminide clusters X@Al<Subscript>12</Subscript> and X@Al<Stack><Subscript>12</Subscript><Superscript>−</Superscript></Stack> with dopants X = Al,Si, and Ge

The transition states and activation barriers h of elementary reactions of addition of the H₂ molecule to aluminide clusters Al₁₃, Al ₁₃ ^? , Al₁₃H ₂ ^? , Al₁₃H ₄ ^? , Si@Al₁₂, Ge@Al₁₂, and LiAl₁₃ were calculated within the B3LYP approximation of the density functional theory using 6–31G* and 6–311+G* basis sets. The barriers h for all diamagnetic clusters were found to be high (～30–40 kcal/mol). The outer-sphere cation Li⁺ decreases while the endohedral electronegative dopants Si and Ge increase the barrier by a few kcal/mol. The hydrogenation barrier of the neural paramagnetic cluster Al₁₃, which has free valence, decreases to ～20 kcal/mol. The addition of a hydrogen atom or a Cl₂ molecule to both paramagnetic and diamagnetic aluminum clusters occurs without a barrier. The first stage of the reaction (addition of H₂ to an Al-Al edge) is in all cases the critical stage of aluminide hydrogenation. The barrier h of this reaction is several times higher than the barriers to migration of hydrogen atoms over the metal cage. The migration of H atoms occurs simultaneously with considerable distortions of the Al₁₃ cage even to the extent that it changes its structural motif. The addition of the H₂ molecule to the Al@TiAl₁₁ cluster containing the peripheral titanium atom occurs with a small barrier, whereas the barrier to elimination of H₂ from the dihydride Al@TiAl₁₁H₂ is reduced to ～15 kcal/mol. Based on the calculations, the conclusion was drawn that the elementary reactions of hydrogenation and dehydrogenation for Ti-doped aluminide clusters should occur considerably faster and under milder conditions than for homonuclear aluminides.     

Thermodynamics of dissolution of lead oxide in NaOH–Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> melts

The solubility of lead oxide in NaOH + (20%)Na₂CO₃ and NaOH + (40%)Na₂CO₃ melts was studied by the isothermal saturation method. The model mechanisms of dissolution were considered. The thermodynamic parameters were calculated.     

Use of integrated intensities of X-ray powder diffraction patterns of Mg<Subscript>1 − x</Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O solid solutions for the quantitative determination of their composition

X-ray diffraction spectra were obtained for polycrystalline samples of Mg_{1 ? x} Zn _x O solid solutions (x = 0.3, 0.5, 0.6, and 0.7) by X-ray powder diffraction. The theoretical integrated intensity ratio between the 111 and 002 reflections was plotted versus the percentage of zinc in the solid solutions. The possibility of extracting information on polycrystalline samples (the composition and the presence of microstructural features) from comparison of the theoretical and experimental integrated intensity ratios between the 111 and 002 reflections was investigated. The Le Bail procedure for the extraction of integrated intensities from X-ray powder diffraction patterns, followed by the use of these intensities in calculations with the SHELX-97 program package, was tested for the determination of the zinc fraction in polycrystalline samples of Mg_{1 ? x} Zn _x O solid solutions.     

Effect of pressure on the oxidative cracking of C<Subscript>2</Subscript>—C<Subscript>4</Subscript> alkanes

The influence of pressure on the oxidative cracking of light alkanes C₂—C₄ was investigated. An elevated pressure reduces the temperature of oxycracking of light alkanes but with further increase in pressure the effect is reduced. The applied pressure decreases the temperature of the total conversion of oxygen while the maximum conversion of alkanes is not influenced. The pressure above atmospheric promotes oxidative cracking reactions but weakly affects thermal processes. At deep conversion of light alkanes, the selectivity towards main products is nearly invariable at the utilized pressures.     

On the role of interlayer atoms and molecular water in formation of crystal structure of salts of uranoarsenic acid HAsUO<Subscript>6</Subscript> · 4H<Subscript>2</Subscript>O

A number of uranoarsenates of alkali metals (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄⁺), alkaline-earth metals (Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺), and rare-earth metals (Y³⁺, La³⁺, Ln³⁺) of the composition M ^k (AsUO₆) _k · nH₂O were prepared by ion exchange in the M ^k -HAsUO₆ · 4H₂O system. On the basis of the data of X-ray diffraction, IR spectroscopy, thermal analysis, and elemental analysis, molecular water and the nature of the interlayer atom M ^k were found to play the key role in structure formation for the compounds.     

Fragments of the coherent phase diagram and the kinetics of growth of elastically strained layers of Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Hg<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Te solid solutions

The influence of the elastic component of the Gibbs energy of mixing on phase formation in the Cd-Hg-Te system was studied by a comparison of calculated dependences of layer parameters on growth conditions performed with and without the inclusion of mechanical strains in the growth system. The appearance of elastic strains between a layer and a substrate of the initial binary compounds insignificantly decreased the growth rate and almost did not influence the composition of the growing layer. The approximation of coherent conjugation of phases in the presence of elastic strain in the system and the assumption of the existence of chemical phase equilibrium at the interphase boundary give similar results for material growth. Both approaches quite satisfactorily describe the experimental data on layer growth under various temperature-time conditions.     

Study of the effect of methods for liquid-phase synthesis of nanopowders on the structure and physicochemical properties of ceramics in the CeO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Two alternative chemical synthesis methods—cryotechnological coprecipitation of hydroxides and cocrystallization of salts—were used for preparing (CeO₂)_1–x (Y₂O₃) _x nanopowders (x = 0.10, 0.15, 0.20) with a mean coherent scattering domain size of ~7–11 nm and S _sp = 2.1–97.5 m²/g. From these nanopowders, ceramic nanomaterials with mean coherent scattering domain sizes of ~61–85 nm were synthesized. It was studied how the phase composition, microstructure, and electrical transport properties of the produced samples depend on the Y₂O₃ content of a CeO₂-based solid solution and on the synthesis method. It was shown that, in the series (CeO₂)_1–x (Y₂O₃) _x (x = 0.10, 0.15, 0.20), the solid solution (CeO₂)_0.90(Y₂O₃)_0.10 has the highest ionic conductivity with the ion transport number t _i = 0.73 (600°C). In its physicochemical characteristics, this ceramic can be used as a solid electrolyte of intermediate-temperature fuel cells.     

Formation of the center of ignition in a CH<Subscript>3</Subscript>Cl–Cl<Subscript>2</Subscript> mixture under the action of UV light

The dependence of temperature on time is investigated using a microthermocouple at different distances from a UV light source in a mixture of chlorine and chloromethane. These relationships give an idea of the size and location of a center of photoignition. It is found that if the size of the reaction vessel in the direction of the luminous flux is much greater than the dimensions of the ignition center, the thermal expansion of a reacting gas mixture has a huge impact on such photoignition parameters as the critical concentration limits and the critical intensity of UV radiation. It is found that by increasing the length of the vessel, some chlorinated combustible mixtures lose the ability to ignite when exposed to UV light.     

Phase Diagram of the NaNO<Subscript>2</Subscript>—KNO<Subscript>3</Subscript> System in the 0 to 1 Molar Fraction Range of Concentrations of KNO<Subscript>3</Subscript>

The temperature dependence of the phase composition of KNO₃—NaNO₂ mixtures in the 0 to 1 molar fraction range of concentrations of KNO₃ is investigated. A phase diagram of the KNO₃—NaNO₂ binary system in the range of concentrations from 0 to 1 molar fractions of KNO₃ is drawn on the basis of DTA results. The composition of the eutectic mixture and its melting temperature is determined experimentally.     

Study of kinetics and thermodynamics of the dehydration reaction of AlPO<Subscript>4</Subscript> · H<Subscript>2</Subscript>O

The kinetics and thermodynamics of the thermal dehydration of aluminum phosphate monohydrate, AlPO₄ · H₂O were studied using thermogravimetry (TG-DTG-DTA) at four heating rates in dry air atmosphere. The activation energies of the dehydration step of AlPO₄ · H₂O were calculated through the methods of Friedman (FR) and Flynn–Wall–Ozawa (FWO) and the possible conversion function has been estimated through the Achar and Li–Tang equations. The independent activation energies on extent of conversions and the better kinetic model of the dehydration reaction for AlPO₄ · H₂O indicate single kinetic mechanism and the F _2.05 model as a simple n-order reaction of “chemical process or mechanism no-invoking equation”, respectively. The positive values of ΔH^# and ΔG^# for the dehydration reaction show that it is endothermic and non-spontaneous process and it is connected with the introduction of heat. The kinetic and thermodynamic functions calculated for the dehydration reaction by different techniques and methods were found to be consistent.     

Kinetics and thermodynamics of thermal decomposition of NH<Subscript>4</Subscript>NiPO<Subscript>4</Subscript>·6H<Subscript>2</Subscript>O

The single phase NH₄NiPO₄·6H₂O was synthesized by solid-state reaction at room temperature using NiSO₄·6H₂O and (NH₄)₃PO₄·3H₂O as raw materials. XRD analysis showed that NH₄NiPO₄·6H₂O was a compound with orthorhombic structure. The thermal process of NH₄NiPO₄·6H₂O experienced three steps, which involves the dehydration of the five crystal water molecules at first, and then deamination, dehydration of the one crystal water, intramolecular dehydration of the protonated phosphate groups together, at last crystallization of Ni₂P₂O₇. In the DTA curve, the two endothermic peaks and an exothermic peak, respectively, corresponding to the first two steps’ mass loss of NH₄NiPO₄·6H₂O and crystallization of Ni₂P₂O₇. Based on Flynn–Wall–Ozawa equation, and Kissinger equation, the average values of the activation energies associated with the thermal decomposition of NH₄NiPO₄·6H₂O, and crystallization of Ni₂P₂O₇ were determined to be 47.81, 90.18, and 640.09 kJ mol⁻¹, respectively. Dehydration of the five crystal water molecules of NH₄NiPO₄·6H₂O, and deamination, dehydration of the crystal water of NH₄NiPO₄·H₂O, intramolecular dehydration of the protonated phosphate group from NiHPO₄ together could be multi-step reaction mechanisms. Besides, the thermodynamic parameters (ΔH ^≠, ΔG ^≠, and ΔS ^≠) of the decomposition reaction of NH₄NiPO₄·6H₂O were determined.     

Effect of the sequence of chemical transformations on the spatial segregation of components and formation of periclase-spinel nanopowders in the MgO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–H<Subscript>2</Subscript>O System

Specific features of the process in which oxide nanopowders are formed in a hydrothermal treatment of coprecipitated magnesium and iron oxides were studied. It was shown that the rate at which oxide nanoparticles are formed increases when reagents structurally close to the final product are used. It was found that, with the hydrothermal treatment of coprecipitated magnesium and iron hydroxides at 450°C combined with the subsequent thermal treatment in air at temperatures of 400–600°C, it is possible to obtain a homogeneous mixture of nanocrystalline powders based on an iron-containing spinel phase and magnesium oxide.     

Preparation and bioevaluation of <Superscript>99m</Superscript>Tc–carbonyl complex of guanine

The aim of this study is to prepare radiolabeled guanine with ^99mTc(CO)₃⁺ core. For this purpose, guanine has been radiolabeled with ^99mTc(CO)₃⁺ core. Quality control study of radiolabeled guanine molecule with ^99mTc(CO)₃⁺ core was performed by thin layer radio chromatography (TLRC) and high performance liquid radio chromatography (HPLRC). The results showed that the radiolabeling yield was quite high (94 ± 3%). Beside that ^99mTc(CO)₃–Gua complex has showed good in vitro stability during the 24 h period. Radiopharmaceutical potential of this complex was evaluated in Wistar Albino Rats. It was concluded that ^99mTc(CO)₃–Gua could be used as a nucleotide radiopharmaceutical for in vivo applications.