Effect of solvent type on the formation rate of benzyl cation intermediate in acidolysis of lignin

The purpose of this study was to examine how the type of solvent among aqueous 1,4-dioxane, tetrahydrofuran, ethanol, iso-propyl alcohol, or ethylene glycol and its content (mol%) affect the formation rate of benzyl cation intermediate (BC) in the acidolysis of lignin, using a simple model compound, 1,2-dimethoxy-4-methoxymethylbenzene. Because the BC forms from the model compound via two steps, i.e., protonation of the benzyl methoxymethyl group as the pre-equilibrium step and liberation of the methanol as the rate-determining step, the observed variation of the formation rate with type of solvent and solvent content originates from the effects on both steps undistinguishably. The formation rate of BC decreased with increasing mol% of any of the organic solvents for a range of relatively low mol%, but increased with it for relatively high mol%. The formation rate varied more in the ether than in the alcohol systems. These results seem to be regulated by the effect of changing the mol% on the pre-equilibrium step, i.e., on the proton activity, rather than on the rate-determining step. Two reaction products, 4-alkoxymethyl-1,2-dimethoxybenzene and 4-hydroxymethyl-1,2-dimethoxybenzene, exclusively formed in the aqueous alcohol systems. The former compound was confirmed to be thermodynamically more stable and kinetically the more favorable product.

SYNTHESIS AND STUDY OF GAS-SENSITIVE NANOSTRUCTURES OF THE Zn-Sn-O SYSTEM

Наностержни оксида цинка синтезированы гидротермальным методом. Проведена обработка полученных образцов в водно-спиртовом растворе станната калия и мочевины при 170°С в течение 30 и 60 минут. В результате получены наноструктуры Zn - Sn - O. Химический состав поверхности образцов ZnO и Zn - Sn - O исследован с помощью рентгеновской фотоэлектронной спектроскопии. Проанализирована их чувствительность к парам изопропилового спирта (1000 мд) при температурах 120 °С, 180°С, 250 °С. Показано перераспределение электронной плотности при формировании композитных наноструктур Zn - Sn - O, проявляющееся в химическом сдвиге пиков O1s и Zn2p. Это свидетельствует о перестроении химических связей при замещении атомов цинка оловом. Обнаружено, что чувствительность композитных структур к парам изопропилового спирта значительно превышает чувствительность ZnO во всем исследуемом температурном диапазоне. Улучшение газочувствительных свойств связано с наличием в образцах системы Zn - Sn - O поверхностных центров различного типа, принимающих участие в адсорбции и окислении изопропилового спирта. Zinc oxide nanorods were synthesized by the hydrothermal method. The obtained samples were processed in an aqueous-alcohol solution of potassium stannate and urea at 170 °C during different times. As a result, Zn - Sn - O nanostructures were obtained. The surface chemical composition of ZnO and Zn - Sn - O was studied using the X-ray photoelectron spectroscopy. Its sensitivity to vapors of isopropyl alcohol (1000 ppm) at 120 °C, 180 °C, 250 °C was analyzed. The electron density redistribution during the Zn - Sn - O composite nanostructures formation manifests itself in the chemical shift of the O1s and Zn2p peaks. It confirm the rearrangement of chemical bonds when zinc atoms are replaced by tin ones. It was found that the sensitivity of composite structures to isopropyl alcohol vapors significantly exceeds that of ZnO in the entire temperature range under study. The improvement of gas-sensitive properties is associated with the presence of various types of surface centers in the Zn - Sn - O samples that participate in the adsorption and oxidation of isopropyl alcohol.

Hydrogenation of Para-Nitrotoluene on Catalytic Systems Containing Oxides of Rare Earth Elements

This work is devoted to the study of the activity of 1% platinum catalysts containing rare earth element oxides (OREE) - Gd2O3, Ce2O3 and aluminum oxide as a carrier in the hydrogenation reactions of nitro compounds on the example of n-nitrotoluene. These catalytic systems in the conditions of liquid-phase hydrogenation provide high selectivity of the process and practically quantitative yield. The process was controlled by the potentiometric method, the reaction rate was judged by the amount of hydrogen absorbed per unit time. It is found that 20% and higher aqueous alcohol solutions can be used as a solvent during hydrogenation. It was found that the initial hydrogenation rate for 1% Pt/Gd2O3 is 3.2 times higher, and for 1% Pt/Ce2O3 Cerium it is 1.6 times higher relative to the 1% Pt/Al2O3 comparison catalyst.

Оbtaining isovaleric acid extraction from plant raw material

The paper presents a mathematical description of the process of obtaining isovaleric acid by the method of extraction of roots and rhizomes of valerian, taking into account its chemical structure and the nature of the extractant. The traditional case of the extraction process, the straight line of equilibrium in the case of using an aqueous alcohol solution as an extractant and the unconventional case of using desalinated water as an extractant, which is represented by a convex equilibrium line, is substantiated. The cause of the unconventional case is the phenomenon of formation of associations between diphilic molecules of isovaleric acid and dipole molecules with water. The possibility of using ion exchange was investigated to isolate isovaleric acid from the extract of biologically active compounds. The identity of isovaleric acid obtained in this way by the gas method was confirmed chromatography.

ENCAPSULATION OF VITAMIN AEVIT OIL SOLUTION WITH β-CYCLODEXTRIN

The present work aimed at encapsulation of fat-soluble vitamin Aevit (vitamins A and E, oil) with β-cyclodextrin. Inclusion complex of vitamins A and E with β-cyclodextrin was prepared in an aqueous alcohol medium by ultrasonic treatment. The surface morphology of the resulting clathrate inclusion complexes was described using a scanning electron microscope. The results of thermographic measurements on a differential scanning calorimeter are presented. The spectral properties of the inclusion complex are characterized by 1H and 13C NMR spectroscopy data. The experimental results confirmed the existence of a complex of inclusion of β-cyclodextrin with vitamin Aevit (2:1). The activation energy of the thermooxidation destruction reaction of the clathrate complex β-cyclodextrin:vitamin Aevit was calculated, kinetic parameters of thermal destruction of clathrate were determined. These parameters were determined based on the Freeman-Carroll, Sharpe-Wentworth, Ahar and Coates-Redfern methods. The use of the above models made it possible to graphically establish the thermodynamic parameters of the thermal decomposition of β-cyclodextrin and its clathrate with vitamin. The data of thermographic measurements on a differential scanning calorimeter showed that the thermal destruction of the Aevite clathrate with β-cyclodextrin begins with the removal of water molecules from the β-cyclodextrin cavity, then the “guest” substance and the cyclic oligosaccharide are destroyed.

Integrated modifying zinc-containing additive for construction silicate compositions

Sodium silicate binders are a promising binder base for obtaining effective granular thermal insulation materials. Increasing water resistance, first of all, will expand the scope of their application in construction. At the same time, the features of the modification of sodium silicate binders by compounds of polyvalent metals have not been fully studied, the interaction with which leads to the formation of hardly soluble silicates. The purpose of this work was to develop a modifying complex based on a zinc-containing compound - zinc acetate to increase the water resistance and thermal characteristics of the porous granular material. The proposed modifying additive is a complex consisting of zinc acetate and an organic alcohol solvent. It is shown that the properties of porous granular material can be controlled by changing the composition of the zinc acetate solvent. Qualitative and quantitative dependences of the properties of porous granules (strength, water resistance, density, thermal conductivity) on the type of zinc-containing solution and its content in the compositions have been obtained. The concept of the mechanism of formation of sparingly soluble complexes during the modification of sodium silicate binders with zinc-containing aqueous-alcoholic solutions has been developed. X-ray phase analysis showed that the sodium silicate system modified with an aqueous alcohol solution of zinc acetate, in contrast to an aqueous solution of zinc acetate, is completely in an amorphous state. We believe that compounds of the Zn2SiO4H2O, ZnSiO3 type are in the amorphous state. The obtained research results made it possible to determine the rational composition of granular heat-insulating material with increased operational and functional characteristics (ρ = 200-280 kg / m3, λ = 0.052-0.063 W / (m °C), R = 1.3-1.8 MPa, Kr = 0.89-0.92, W = 16- 18 %).

DETECTION OF FALSIFICATION OF HORILKA BY ADMITTANCE SPECTROSCOPY

The methods of quality control of horilka by electrical parameters, in particular, dielectric constant, specific conductivity, and imitation components are analyzed. The research results of individual samples of alcohol solutions and horilkas of different brands by the method of admittance spectroscopy were also analyzed. Based on this, methods for detecting falsification of horilka products by the method of admittance spectroscopy are proposed. The reactive component of the control object's ad is selected as an informative parameter. Two types of falsification are analyzed. The first is the falsification of the original horilka by replacing it with an aqueous-alcohol solution. The second - by replacing one brand of horilka with another. The analysis of the obtained results of researches of two types of objects on reactive components of their admittance in the frequency range 100 Hz100 kHz showed the following: characteristic features of dependencies of reactive components on frequency are revealed; they have been found to have extreme values at different frequencies. The reactive component of the admittance of aqueous-alcohol solutions reaches an extreme value at the beginning of the range. The same component of the original horilkas of different brands has extreme values at the end of the range. Based on this, methods for prompt detection of falsifications are proposed.