Pub Date : 2019-01-10DOI: 10.6060/IVKKT.20196201.5768
N. Nikulina, G. Vostrikova, A. Dmitrenkov, S. Nikulin
From the literature data it is known that in industrial and civil construction it is widely used expanded polystyrene as a heat-insulating material, which is in demand on the market. In order to solve a number of ecological problems, in this work attempts have been made to chemically combine two types of polymer waste (by-products of petrochemistry in the presence of expanded polystyrene) to obtain impregnating compounds at the molecular level by carrying out their joint destruction and applying wood products for protective treatment. Obtained wood-polymer composites from natural wood (birch) and wood fiber boards (DVP) were investigated for resistance to water and moisture. Indicators of tests of wood for water absorption and swelling in the radial and tangential directions indicate that the samples under investigation have increased hydrophobic properties. Modified fiberboards acquire, in addition to increased hydrophobic properties and higher strength parameters. This is due to the cross-linking of oligomer molecules in wood structures with the formation of a wood-polymer framework and the formation of hydrogen and ether bonds between the wood components and the oxidized modified oligomer. The formation of such bonds makes it possible to reduce such a shortage of impregnating compositions as washability from products during their operation. Reducing the uncertainty of the oligomeric modifier reduces its hydrophilic properties. Integrated use of waste and by-products allows to purposefully dispose of them and use them for protective processing of materials, which include wood components, which contributes to the increase of the service life of products.
{"title":"MODIFICATION OF LOW-MOLECULAR COPOLYMER FROM BY-PRODUCTS OF BUTADIENE RUBBER BY SECONDARY EXPANDED POLYSTYRENE","authors":"N. Nikulina, G. Vostrikova, A. Dmitrenkov, S. Nikulin","doi":"10.6060/IVKKT.20196201.5768","DOIUrl":"https://doi.org/10.6060/IVKKT.20196201.5768","url":null,"abstract":"From the literature data it is known that in industrial and civil construction it is widely used expanded polystyrene as a heat-insulating material, which is in demand on the market. In order to solve a number of ecological problems, in this work attempts have been made to chemically combine two types of polymer waste (by-products of petrochemistry in the presence of expanded polystyrene) to obtain impregnating compounds at the molecular level by carrying out their joint destruction and applying wood products for protective treatment. Obtained wood-polymer composites from natural wood (birch) and wood fiber boards (DVP) were investigated for resistance to water and moisture. Indicators of tests of wood for water absorption and swelling in the radial and tangential directions indicate that the samples under investigation have increased hydrophobic properties. Modified fiberboards acquire, in addition to increased hydrophobic properties and higher strength parameters. This is due to the cross-linking of oligomer molecules in wood structures with the formation of a wood-polymer framework and the formation of hydrogen and ether bonds between the wood components and the oxidized modified oligomer. The formation of such bonds makes it possible to reduce such a shortage of impregnating compositions as washability from products during their operation. Reducing the uncertainty of the oligomeric modifier reduces its hydrophilic properties. Integrated use of waste and by-products allows to purposefully dispose of them and use them for protective processing of materials, which include wood components, which contributes to the increase of the service life of products.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":"1 1","pages":""},"PeriodicalIF":0.9,"publicationDate":"2019-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44234025","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-30DOI: 10.6060/ivkkt201962fp.5517
A. V. Kotomkin, N. P. Rusakova, V. Turovtsev, Yu. D. Orlov
On the basis of quantum-chemical calculations the properties of trifluoro-substituted hydrocarbon molecules CnH2n+1-CF3 (n ≤ 9) received from their electron density distribution were considered. The geometry optimization of ten structures was carried out. The surfaces of zero flow electron charge density gradient were specified, and the basins of atomic groups and fluorine atoms were found. The electron integral parameters (charges q(R), energies E(R) and volumes V(R)) of atomic groups in trifluoroalkane molecules were calculated and analyzed. The relationship between the length of the hydrocarbon chains and the transferability of the properties of the selected groups (CF3, CH3, CH2) was revealed, that is reflected in their transferable parameters. For the studied homologous series the qualitative group electronegativity scale was made up and inductive effect (I - effect) of fluorine containing group was considered. The attenuation of I – effect in CnH2n+1-CF3 (n ≥ 6) within molecular fragments CF3-(CH2)4 and CH3-CH2 was identified. In this regard, the appearance of the «unperturbed» CH2 group was registered at n > 6. The «standard» (or «transferable») value of the total group energy E(R) was introduced and computing of the relative group energy ΔE(R) was described. It was shown, that the reduction of the volumes of the nearest СН2 to the СF3 was caused by the electron density redistribution. The comparative analysis of the group charges q(R) in CnH2n+1-CF3 (n ≤ 9) with corresponding q(R) in monofluorine alkanes, monofluorine alkane radicals, difluorine alkanes and difluorine alkane radicals was performed. The comparison of the charges of relevant groups and fluorine-containing fragments of the fluoro-substituted nonane and their radicals was presented as graphic dependence, which provides an understanding of the attenuation of I – effect from СF3.
{"title":"ELECTRON PARAMETERS OF 1,1,1 – TRILUOROALKANES","authors":"A. V. Kotomkin, N. P. Rusakova, V. Turovtsev, Yu. D. Orlov","doi":"10.6060/ivkkt201962fp.5517","DOIUrl":"https://doi.org/10.6060/ivkkt201962fp.5517","url":null,"abstract":"On the basis of quantum-chemical calculations the properties of trifluoro-substituted hydrocarbon molecules CnH2n+1-CF3 (n ≤ 9) received from their electron density distribution were considered. The geometry optimization of ten structures was carried out. The surfaces of zero flow electron charge density gradient were specified, and the basins of atomic groups and fluorine atoms were found. The electron integral parameters (charges q(R), energies E(R) and volumes V(R)) of atomic groups in trifluoroalkane molecules were calculated and analyzed. The relationship between the length of the hydrocarbon chains and the transferability of the properties of the selected groups (CF3, CH3, CH2) was revealed, that is reflected in their transferable parameters. For the studied homologous series the qualitative group electronegativity scale was made up and inductive effect (I - effect) of fluorine containing group was considered. The attenuation of I – effect in CnH2n+1-CF3 (n ≥ 6) within molecular fragments CF3-(CH2)4 and CH3-CH2 was identified. In this regard, the appearance of the «unperturbed» CH2 group was registered at n > 6. The «standard» (or «transferable») value of the total group energy E(R) was introduced and computing of the relative group energy ΔE(R) was described. It was shown, that the reduction of the volumes of the nearest СН2 to the СF3 was caused by the electron density redistribution. The comparative analysis of the group charges q(R) in CnH2n+1-CF3 (n ≤ 9) with corresponding q(R) in monofluorine alkanes, monofluorine alkane radicals, difluorine alkanes and difluorine alkane radicals was performed. The comparison of the charges of relevant groups and fluorine-containing fragments of the fluoro-substituted nonane and their radicals was presented as graphic dependence, which provides an understanding of the attenuation of I – effect from СF3.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":"1 1","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71162771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-30DOI: 10.6060/ivkkt.20196201.5727
Zaira N. Verdieva, A. Alkhasov, Nadinbeg N. Verdiev, G. A. Rabadanov, Patimat A. Arbukhanova, E. Iskenderov
The liquidus surface of the system (LiF)2-Li2SO4-Li2CO3 was studied by the calculated and differential thermal method of physicochemical analysis. An analysis of the systems of lower dimensionality of the facets of the investigated object showed that the most informative, for the experimental study, is the sections located in the crystallization field of lithium fluoride. A study of the DTA of a number of compositions located at the initially chosen polythermal section in the lithium fluoride crystallization field, the ratios of lithium sulfate and carbonate in the eutectic are determined. The composition of the triple eutectic was revealed by studying a non-invariant cut from the vertex of the triangle (LiF), through a point showing a constant ratio of sulfate and lithium carbonate in the eutectic, to the fusion of the thermal effects of the primary and tertiary crystallizations. The complexity of the study was that lithium carbonate is the most fusible component in the system, and according to the literature, after the melting of lithium carbonate, decomposition begins, which greatly complicates the interpretation of research results. In order to avoid the decomposition of lithium carbonate, each experimentally studied composition was heated to the melting temperature of lithium carbonate and kept in isothermal mode, at a temperature below its melting. Thus, the theoretical melting calculations and the region of location of the non-invariant composition have been extrapolated, allowing to limit the number of experimentally studied samples, and the subsequent experimental investigation of DTA of two polythermal sections revealed a eutectic composition crystallizing at 476 ° C and containing LiF-20 eq.%, Li2SO4 - 51 eq.%, Li2CO3 – 29 eq.%. The discrepancies between theoretical calculations and experimental studies are 8.3% in temperature and 5.05% in composition.
{"title":"PHASE EQUILIBRIUM IN SYSTEM (LiF)2 – Li2CO3 – Li2SO4","authors":"Zaira N. Verdieva, A. Alkhasov, Nadinbeg N. Verdiev, G. A. Rabadanov, Patimat A. Arbukhanova, E. Iskenderov","doi":"10.6060/ivkkt.20196201.5727","DOIUrl":"https://doi.org/10.6060/ivkkt.20196201.5727","url":null,"abstract":"The liquidus surface of the system (LiF)2-Li2SO4-Li2CO3 was studied by the calculated and differential thermal method of physicochemical analysis. An analysis of the systems of lower dimensionality of the facets of the investigated object showed that the most informative, for the experimental study, is the sections located in the crystallization field of lithium fluoride. A study of the DTA of a number of compositions located at the initially chosen polythermal section in the lithium fluoride crystallization field, the ratios of lithium sulfate and carbonate in the eutectic are determined. The composition of the triple eutectic was revealed by studying a non-invariant cut from the vertex of the triangle (LiF), through a point showing a constant ratio of sulfate and lithium carbonate in the eutectic, to the fusion of the thermal effects of the primary and tertiary crystallizations. The complexity of the study was that lithium carbonate is the most fusible component in the system, and according to the literature, after the melting of lithium carbonate, decomposition begins, which greatly complicates the interpretation of research results. In order to avoid the decomposition of lithium carbonate, each experimentally studied composition was heated to the melting temperature of lithium carbonate and kept in isothermal mode, at a temperature below its melting. Thus, the theoretical melting calculations and the region of location of the non-invariant composition have been extrapolated, allowing to limit the number of experimentally studied samples, and the subsequent experimental investigation of DTA of two polythermal sections revealed a eutectic composition crystallizing at 476 ° C and containing LiF-20 eq.%, Li2SO4 - 51 eq.%, Li2CO3 – 29 eq.%. The discrepancies between theoretical calculations and experimental studies are 8.3% in temperature and 5.05% in composition. \u0000 ","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43970803","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-30DOI: 10.6060/ivkkt.20196201.5745
Maria М. Kuzminykh, V. Panteleeva, A. B. Shein
The kinetics of hydrogen evolution reaction on FeSi2-electrode in 1.0 M NaOH solution has been studied using methods of polarization and impedance measurements. With the help of diagnostic criteria for the hydrogen evolution reaction mechanisms based on the analysis of the dependence of the parameters of the equivalent electric circuit on overvoltage, it was established that the reaction of hydrogen evolution on iron disilicide in the alkaline electrolyte proceeds along the discharge - electrochemical desorption route, where desorption is the rate-determining stage. Both stages are irreversible, the transfer coefficients of the stages are equal (α1 = α2 = α), simultaneously the hydrogen absorption reaction by the electrode material proceeds in the diffusion mode (in the whole investigated range of potentials). It was found that the adsorption of atomic hydrogen is described by the equation of the Langmuir isotherm. The influence of various methods of modifying of the surface of FeSi2-electrode on the kinetics and mechanism of the cathodic process has been studied. It was found that the modification of the disilicide surface by hydrogenation at a current density of i = 30 mA/cm2, an anodic etching in 0.5 M H2SO4 at the potential E = 0.4 V relative to the standard hydrogen electrode, an anodic etching in 1.0 M NaOH at the potential E = 0.1 V, chemical etching in 5.0 M NaOH at 70 °C reduce the overvoltage of hydrogen evolution, but the mechanism of the cathodic process does not change as a result of the modification. Reduction of the overvoltage of hydrogen evolution on iron disilicide is due to the action of two factors: the development of the surface and the change in the composition of the surface layer of the electrode. It has been concluded that FeSi2 in the alkaline electrolyte is a promising electrode material that exhibits activity in the electrolytic hydrogen evolution reaction.
{"title":"CATHODIC HYDROGEN EVOLUTION ON IRON DISILICIDE. I. ALKALINE SOLUTION","authors":"Maria М. Kuzminykh, V. Panteleeva, A. B. Shein","doi":"10.6060/ivkkt.20196201.5745","DOIUrl":"https://doi.org/10.6060/ivkkt.20196201.5745","url":null,"abstract":"The kinetics of hydrogen evolution reaction on FeSi2-electrode in 1.0 M NaOH solution has been studied using methods of polarization and impedance measurements. With the help of diagnostic criteria for the hydrogen evolution reaction mechanisms based on the analysis of the dependence of the parameters of the equivalent electric circuit on overvoltage, it was established that the reaction of hydrogen evolution on iron disilicide in the alkaline electrolyte proceeds along the discharge - electrochemical desorption route, where desorption is the rate-determining stage. Both stages are irreversible, the transfer coefficients of the stages are equal (α1 = α2 = α), simultaneously the hydrogen absorption reaction by the electrode material proceeds in the diffusion mode (in the whole investigated range of potentials). It was found that the adsorption of atomic hydrogen is described by the equation of the Langmuir isotherm. The influence of various methods of modifying of the surface of FeSi2-electrode on the kinetics and mechanism of the cathodic process has been studied. It was found that the modification of the disilicide surface by hydrogenation at a current density of i = 30 mA/cm2, an anodic etching in 0.5 M H2SO4 at the potential E = 0.4 V relative to the standard hydrogen electrode, an anodic etching in 1.0 M NaOH at the potential E = 0.1 V, chemical etching in 5.0 M NaOH at 70 °C reduce the overvoltage of hydrogen evolution, but the mechanism of the cathodic process does not change as a result of the modification. Reduction of the overvoltage of hydrogen evolution on iron disilicide is due to the action of two factors: the development of the surface and the change in the composition of the surface layer of the electrode. It has been concluded that FeSi2 in the alkaline electrolyte is a promising electrode material that exhibits activity in the electrolytic hydrogen evolution reaction.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47105260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-30DOI: 10.6060/ivkkt.20186201.5767
Abdullakh B. Ittiev, R. Kumykov
Non-previously described new bis (3-nitropthalimide) arylenes activated with two carbonyls and containing flexible “bridging” groups, in particular dichloroethylene and ketones between the phthalimide fragments of the dinitrocompounds were obtained. The reactivity of the dinitrophthalimides used is determined, first of all, by the position of (3 or 4) nitro groups, and not by the nature of the Ar residue; monomers containing nitro groups in position 3 are more reactive than systems containing nitro groups in position 4. The interaction of synthesized bis (nitropthalimide) arylenes containing central dichloroethylene and ketone groups between phthalimide fragments and bis-phenolate derivatives of chloral was carried out. Synthesis of polyetherphthalimides using the process of polynitro substitution was carried out under modified conditions with complete absence of moisture. In general, the reactions of polynitro substitution proceed rapidly under relatively mild conditions; when dipolar aprotic solvents or a mixture of them with toluene are used, relatively high molecular weight polymers are formed. It has been established that the rate of dissolution of monomers is an important factor affecting the reaction rate; this determines the possibility of the formation of relatively high-molecular polymers, even with some deviation from the equimolarity of the monomers. As the general conditions for the synthesis of polyetherphthalimides based on synthesized bis (3-nitropthalimide) arylenes and bis-phenols, the optimal conditions were: reaction temperature -60 °C, reaction time -1 h with equimolar monomer ratio and concentration of each of them 0.25 mol/l. The influence of moisture on the synthesis of polyetherimides using the reaction of nucleophilic polynitro substitution was studied. It is shown that the process in the maximally dry system in the DMSO medium or (DMSO / toluene) leads to the formation of polymers with hr at least 0.63 dl/g. All the polymers obtained are readily soluble in dipolar and aprotic solvents. The structure of all the obtained intermediates and monomers was confirmed by elemental analysis and IR spectroscopy. An analysis of the primary thermal characteristics of the polymers obtained showed that they are characterized by relatively high and near destruction temperatures was found that the largest oxygen index (CI) in polymers, where more macromolecules contain more dichloroethylene fragments, and the lowest CI in polymers with a high oxygen content. It is shown that the polymers obtained have satisfactory deformation-strength characteristics. A feature of synthesized polyetherphthalimides is a significant difference between the temperatures of intensive destruction and softening temperatures, which determines the possibility of their processing into products by injection molding.
{"title":"PREPARATION OF NEW POLYETHERPHTHALIMIDES BASED ON CHLORAL DERIVATIVES USING NUCLEOPHILIC POLYNITRO SUBSTITUTION REACTIONS","authors":"Abdullakh B. Ittiev, R. Kumykov","doi":"10.6060/ivkkt.20186201.5767","DOIUrl":"https://doi.org/10.6060/ivkkt.20186201.5767","url":null,"abstract":"Non-previously described new bis (3-nitropthalimide) arylenes activated with two carbonyls and containing flexible “bridging” groups, in particular dichloroethylene and ketones between the phthalimide fragments of the dinitrocompounds were obtained. The reactivity of the dinitrophthalimides used is determined, first of all, by the position of (3 or 4) nitro groups, and not by the nature of the Ar residue; monomers containing nitro groups in position 3 are more reactive than systems containing nitro groups in position 4. The interaction of synthesized bis (nitropthalimide) arylenes containing central dichloroethylene and ketone groups between phthalimide fragments and bis-phenolate derivatives of chloral was carried out. Synthesis of polyetherphthalimides using the process of polynitro substitution was carried out under modified conditions with complete absence of moisture. In general, the reactions of polynitro substitution proceed rapidly under relatively mild conditions; when dipolar aprotic solvents or a mixture of them with toluene are used, relatively high molecular weight polymers are formed. It has been established that the rate of dissolution of monomers is an important factor affecting the reaction rate; this determines the possibility of the formation of relatively high-molecular polymers, even with some deviation from the equimolarity of the monomers. As the general conditions for the synthesis of polyetherphthalimides based on synthesized bis (3-nitropthalimide) arylenes and bis-phenols, the optimal conditions were: reaction temperature -60 °C, reaction time -1 h with equimolar monomer ratio and concentration of each of them 0.25 mol/l. The influence of moisture on the synthesis of polyetherimides using the reaction of nucleophilic polynitro substitution was studied. It is shown that the process in the maximally dry system in the DMSO medium or (DMSO / toluene) leads to the formation of polymers with hr at least 0.63 dl/g. All the polymers obtained are readily soluble in dipolar and aprotic solvents. The structure of all the obtained intermediates and monomers was confirmed by elemental analysis and IR spectroscopy. An analysis of the primary thermal characteristics of the polymers obtained showed that they are characterized by relatively high and near destruction temperatures was found that the largest oxygen index (CI) in polymers, where more macromolecules contain more dichloroethylene fragments, and the lowest CI in polymers with a high oxygen content. It is shown that the polymers obtained have satisfactory deformation-strength characteristics. A feature of synthesized polyetherphthalimides is a significant difference between the temperatures of intensive destruction and softening temperatures, which determines the possibility of their processing into products by injection molding. \u0000 ","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":"1 1","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71162580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-30DOI: 10.6060/ivkkt201962fp.5756
D. Gurulev, L. Palatkina, N. A. Kuznetsova, V. I. Porkhun
In order to determine the effect of the polarity of solvents on the reactivity and the course of the reactions of semihinone radicals, their complexes, this study of 2,6-diphenyl-1,4-benzoquinone, (class of substituted benzoquinones) and its dimer D was carried out. It was found that in the NMR spectrum of the dimer solution, with increasing temperature, the lines widen, and there is one wide line close to the chemical shift to the protons of the meta-groups of quinone. The NMR spectrum of a solution D in deuterochloroform at low temperatures contains lines corresponding to the aromatic part of the protons in the meta position, respectively (7.05 M.d, 6.89 M.d.). That is, the exchange process between the non-equivalent parts of the diamagnetic dimer molecule of the preceding dissociation takes place with the constant of the velocity k-1, coinciding in order of the inverse spin-spin relaxation time. The value of k-1 increases by more than an order of magnitude with the increasing polarity of the solvent. This effect is due to the stronger solvent solvation of the activated complex in the transition state compared to the molecule. The reaction of dimerization of semiquinone radicals is diffusion-controlled, since the values of ∆H1≠ in all solvents differ from the activation energy of viscosity by no more than 1 kcal/M and the values of the velocity constant in 5-8 times differ from the diffusion rate constant calculated by Debye. The solvation of radicals leads to a decrease in the diffusion coefficients of radicals and, possibly, to the shielding of the reaction center, which causes a decrease in k1. With the decrease of the constant in the specified number of solvents, the stability of the radical increases, which is manifested in a symbiotic increase in the equilibrium constant K. The reason for the increase of the direct constant k1 in solvents with high permittivity is explained.
{"title":"ELEMENTARY ACTS OF PHOTOREACTIONS OF 2,6-DIPHENYL-1,4-BENZOQUINONE IN VARIOUS SOLVENTS","authors":"D. Gurulev, L. Palatkina, N. A. Kuznetsova, V. I. Porkhun","doi":"10.6060/ivkkt201962fp.5756","DOIUrl":"https://doi.org/10.6060/ivkkt201962fp.5756","url":null,"abstract":"In order to determine the effect of the polarity of solvents on the reactivity and the course of the reactions of semihinone radicals, their complexes, this study of 2,6-diphenyl-1,4-benzoquinone, (class of substituted benzoquinones) and its dimer D was carried out. It was found that in the NMR spectrum of the dimer solution, with increasing temperature, the lines widen, and there is one wide line close to the chemical shift to the protons of the meta-groups of quinone. The NMR spectrum of a solution D in deuterochloroform at low temperatures contains lines corresponding to the aromatic part of the protons in the meta position, respectively (7.05 M.d, 6.89 M.d.). That is, the exchange process between the non-equivalent parts of the diamagnetic dimer molecule of the preceding dissociation takes place with the constant of the velocity k-1, coinciding in order of the inverse spin-spin relaxation time. The value of k-1 increases by more than an order of magnitude with the increasing polarity of the solvent. This effect is due to the stronger solvent solvation of the activated complex in the transition state compared to the molecule. The reaction of dimerization of semiquinone radicals is diffusion-controlled, since the values of ∆H1≠ in all solvents differ from the activation energy of viscosity by no more than 1 kcal/M and the values of the velocity constant in 5-8 times differ from the diffusion rate constant calculated by Debye. The solvation of radicals leads to a decrease in the diffusion coefficients of radicals and, possibly, to the shielding of the reaction center, which causes a decrease in k1. With the decrease of the constant in the specified number of solvents, the stability of the radical increases, which is manifested in a symbiotic increase in the equilibrium constant K. The reason for the increase of the direct constant k1 in solvents with high permittivity is explained. \u0000 ","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41841448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-30DOI: 10.6060/ivkkt.20196201.5766
Juliya V. Loskutova, N. Yudina, V. A. Daneker
The goal of this work is to study the influence of low-frequency acoustic field and polymer additive on structural and mechanical properties of problematic quick-freezing oil. The results were acquired by methods of rotational viscosimetry and finding phase transition temperatures by using optical density of infrared light as well as optical microscopy method. Highly paraffinic low-resin oil (Tomsk region) was exposed to low-frequency acoustic field (f = 50 Hz, 1 and 3 min of processing at 0 °С), a chemical reagent, the complex-action polymer additive D-210 (0.05% mass concentration in oil) and complex physical-chemical processing This work studies external influence on viscosity, temperature and energy characteristics, phase transition temperature as well as structure of oil residue. It was shown that in the case of problematic oil at a temperature close to freezing point, the acoustic influence leads to increase of viscosity and temperature properties. After adding the additive to processed oil during the complex processing, the thixotropic structure is destroyed, which is followed by a sharp decrease in viscosity, cloud point and freezing point. There is also a decrease in energy parameters, such as activation energy of viscous flow and internal energy of a disperse system. To determine the temperature of spontaneous crystallization we plotted the differential curves of viscosity coefficient dependence on the temperature of the medium. Study of the microstructure of the oil residue had shown that it contains small linear single-crystal and spherical formations prior to acoustic processing. After processing, however, such formations display a significant growth. The structure of the residue after complex processing is represented by many large plate paraffin crystallites.
{"title":"INFLUENCE OF LOW-FREQUENCY ACOUSTIC FIELD AND POLYMER ADDITIVE ON STRUCTURAL AND MECHANICAL PROPERTIES OF OIL","authors":"Juliya V. Loskutova, N. Yudina, V. A. Daneker","doi":"10.6060/ivkkt.20196201.5766","DOIUrl":"https://doi.org/10.6060/ivkkt.20196201.5766","url":null,"abstract":"The goal of this work is to study the influence of low-frequency acoustic field and polymer additive on structural and mechanical properties of problematic quick-freezing oil. The results were acquired by methods of rotational viscosimetry and finding phase transition temperatures by using optical density of infrared light as well as optical microscopy method. Highly paraffinic low-resin oil (Tomsk region) was exposed to low-frequency acoustic field (f = 50 Hz, 1 and 3 min of processing at 0 °С), a chemical reagent, the complex-action polymer additive D-210 (0.05% mass concentration in oil) and complex physical-chemical processing This work studies external influence on viscosity, temperature and energy characteristics, phase transition temperature as well as structure of oil residue. It was shown that in the case of problematic oil at a temperature close to freezing point, the acoustic influence leads to increase of viscosity and temperature properties. After adding the additive to processed oil during the complex processing, the thixotropic structure is destroyed, which is followed by a sharp decrease in viscosity, cloud point and freezing point. There is also a decrease in energy parameters, such as activation energy of viscous flow and internal energy of a disperse system. To determine the temperature of spontaneous crystallization we plotted the differential curves of viscosity coefficient dependence on the temperature of the medium. Study of the microstructure of the oil residue had shown that it contains small linear single-crystal and spherical formations prior to acoustic processing. After processing, however, such formations display a significant growth. The structure of the residue after complex processing is represented by many large plate paraffin crystallites. \u0000 ","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49422326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-30DOI: 10.6060/ivkkt.20196201.5783
S. Natareev, D. Zakharov, A. A. Sirotkin, S. Belyaev
The objective of this study is to elaborate the analytical theory of ion exchange in the field of solving the boundary value problems of non steady state mass transfer in solids with a canonical form taking into account a change in the concentration of the solution and the character of movement of the phases in a flow apparatus. The mathematical description of the process of ion-exchange solution purification on ionite particles of cylindrical shape in a batch flow apparatus was developed. At the developing mathematical description the following assumptions were used: the ionite is monodisperse, uniform initial distribution of substances in the ionite, the ion exchange equilibrium is described by Henry equation, the rate of the process is limited by both internal and external diffusion, the flow pattern of the liquid phase in the apparatus is described by the perfect mixing model, the solution with the constant volumetric flow rate and the constant concentration of the substance is supplied to the apparatus, kinetic and hydrodynamic process parameters are constants. Mathematical description includes the following equations: the diffusion equation of ionite, isotherm equation ion exchange, the equation for average concentration of the substance in the ionite, the material balance equation for a perfect mixing flow apparatus, initial and boundary conditions. To solve boundary value problem, we use the integral Laplace transformations. The obtained equation allows to analyze the effect of the volumetric flow rate of the solution supplied to a flow apparatus, the ratio of the volumes of solid and liquid phases in the apparatus, the diameter of the particle, and other parameters of the process on the concentration distribution of a substance along the internal coordinate of the solid. The developed mathematical model is used to study the desorption of copper ions from the modified polycaproamide fiber with sulfuric acid solution.
{"title":"ION EXCHANGE ON A FIBROUS ION EXCHANGER IN A FLO-TYPE CAPACITIVE APPARATUS","authors":"S. Natareev, D. Zakharov, A. A. Sirotkin, S. Belyaev","doi":"10.6060/ivkkt.20196201.5783","DOIUrl":"https://doi.org/10.6060/ivkkt.20196201.5783","url":null,"abstract":"The objective of this study is to elaborate the analytical theory of ion exchange in the field of solving the boundary value problems of non steady state mass transfer in solids with a canonical form taking into account a change in the concentration of the solution and the character of movement of the phases in a flow apparatus. The mathematical description of the process of ion-exchange solution purification on ionite particles of cylindrical shape in a batch flow apparatus was developed. At the developing mathematical description the following assumptions were used: the ionite is monodisperse, uniform initial distribution of substances in the ionite, the ion exchange equilibrium is described by Henry equation, the rate of the process is limited by both internal and external diffusion, the flow pattern of the liquid phase in the apparatus is described by the perfect mixing model, the solution with the constant volumetric flow rate and the constant concentration of the substance is supplied to the apparatus, kinetic and hydrodynamic process parameters are constants. Mathematical description includes the following equations: the diffusion equation of ionite, isotherm equation ion exchange, the equation for average concentration of the substance in the ionite, the material balance equation for a perfect mixing flow apparatus, initial and boundary conditions. To solve boundary value problem, we use the integral Laplace transformations. The obtained equation allows to analyze the effect of the volumetric flow rate of the solution supplied to a flow apparatus, the ratio of the volumes of solid and liquid phases in the apparatus, the diameter of the particle, and other parameters of the process on the concentration distribution of a substance along the internal coordinate of the solid. The developed mathematical model is used to study the desorption of copper ions from the modified polycaproamide fiber with sulfuric acid solution.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42767229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-30DOI: 10.6060/IVKKT.20196201.5753
G. Z. Raskildina, E. A. Yakovenko, Luisa M. M. Mryasova, S. S. Zlotskii
The herbicidal activity of esters and amides based on commercially available phenoxy chlorides and 2,4-dichlorophenoxyacetic acids was studied. Esters of 2,2-methyl-4-hydroxymethyl-1,3-dioxolane, 5-ethyl-5-hydroxymethyl-1,3-dioxane and 1,3-dioxolan-4-ylmethanol and 1,3-dioxane-5 -ol (glycerin formulas), as well as amides containing gem-dichlorocyclopropane and 1,3-dioxolane fragments were obtained. The acid chlorides, 1,3-dioxacycloalkanes and secondary amines were prepared according to standard basic methods. Esters and amides were synthesized from these starting compounds in a short time and with a quantitative yield (more than 90%). As a result of the synthesis of a mixture of 1,3-dioxolan-4-ylmethyl phenylacetate and 1,3-dioxan-5-yl phenylacetate, the content of the 5-ring cyclic derivative over the 6-chain structure was predominant, which is obviously associated with greater activity in the esterification reaction of primary alcohol than secondary. The screening results showed that the activity relative to wheat of the 1,3-dioxalane ester of 2,4-dichlorophenoxyacetic acid is superior to the Octagon-Extra standard. With respect to peas, derivatives of 2,4-dichlorophenoxyacetic acid and 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane are close to the standard for inhibition of shoot mass. The results of N-benzyl-N-[(2,2-dichlorocyclopropyl) methyl] -2-phenoxyacetamide and N-[(2,2-dichlorocyclopropyl) methyl]-N-(1,3-dioxolan-4-ylmethyl)-2-phenoxyacetamide with respect to peas and wheat also showed a marked herbicidal effect, close in value to the reference one. The test results of synthesized benzamides on wheat showed that, at a concentration of 100 mg/l, the compounds act approximately the same as the reference preparation at a dose of 50 mg/l. The obtained results prove the prospects of creating herbicidal preparations based on phenoxy- chlorides and 2,4-dichlorophenoxyacetic acids containing 1,3-dioxacycloalkane fragments. Therefore, these objects are very attractive for further study and synthesis of biologically active compounds containing the above pharmacophore groups.
{"title":"SYNTHESIS AND HERBICID ACTIVITY OF ARYLOXYACETIC ACIDS AND AMIDES OF ARYLOXY ACETIC ACIDS CONTAINING CYCLOACETAL FRAGMENT","authors":"G. Z. Raskildina, E. A. Yakovenko, Luisa M. M. Mryasova, S. S. Zlotskii","doi":"10.6060/IVKKT.20196201.5753","DOIUrl":"https://doi.org/10.6060/IVKKT.20196201.5753","url":null,"abstract":"The herbicidal activity of esters and amides based on commercially available phenoxy chlorides and 2,4-dichlorophenoxyacetic acids was studied. Esters of 2,2-methyl-4-hydroxymethyl-1,3-dioxolane, 5-ethyl-5-hydroxymethyl-1,3-dioxane and 1,3-dioxolan-4-ylmethanol and 1,3-dioxane-5 -ol (glycerin formulas), as well as amides containing gem-dichlorocyclopropane and 1,3-dioxolane fragments were obtained. The acid chlorides, 1,3-dioxacycloalkanes and secondary amines were prepared according to standard basic methods. Esters and amides were synthesized from these starting compounds in a short time and with a quantitative yield (more than 90%). As a result of the synthesis of a mixture of 1,3-dioxolan-4-ylmethyl phenylacetate and 1,3-dioxan-5-yl phenylacetate, the content of the 5-ring cyclic derivative over the 6-chain structure was predominant, which is obviously associated with greater activity in the esterification reaction of primary alcohol than secondary. The screening results showed that the activity relative to wheat of the 1,3-dioxalane ester of 2,4-dichlorophenoxyacetic acid is superior to the Octagon-Extra standard. With respect to peas, derivatives of 2,4-dichlorophenoxyacetic acid and 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane are close to the standard for inhibition of shoot mass. The results of N-benzyl-N-[(2,2-dichlorocyclopropyl) methyl] -2-phenoxyacetamide and N-[(2,2-dichlorocyclopropyl) methyl]-N-(1,3-dioxolan-4-ylmethyl)-2-phenoxyacetamide with respect to peas and wheat also showed a marked herbicidal effect, close in value to the reference one. The test results of synthesized benzamides on wheat showed that, at a concentration of 100 mg/l, the compounds act approximately the same as the reference preparation at a dose of 50 mg/l. The obtained results prove the prospects of creating herbicidal preparations based on phenoxy- chlorides and 2,4-dichlorophenoxyacetic acids containing 1,3-dioxacycloalkane fragments. Therefore, these objects are very attractive for further study and synthesis of biologically active compounds containing the above pharmacophore groups.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47564544","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-12DOI: 10.6060/IVKKT.20186112.5838
T. Izvekova, N. A. Kobeleva, A. Gushchin, M. S. Gerasimova, V. Grinevich
The paper presents the results of measurements of the content of benzo(a)pyrene (BaP) in the snow cover in the territory of the Ivanovo city. It was revealed that the concentration of BaP at the controlled points is 2.7 times higher than the background level on average. The degree of pollution of the snow cover in Ivanovo is much less than in Moscow (the level of excess varies in the range 2.3 - 89 times). The intake levels (from 0.02 μg/m2 to 3.76 μg/m2) and deposition density (0.02 - 1.88 ng/m2 · day-1) of BaP are estimated that are commensurate with the values typical for such areas, as urban areas of Germany and Canada. Interpolation the BaP concentrations in snow is allowed to reveal anomalies in the city with BaP content of 35 ng/l, which is 7 times higher than the average value for the whole city. The obtained data made it possible to estimate the BaP concentration in atmospheric air, which on the average is 0.7· 10-6 mg/m3, which is 0.7 fraction of the maximum permissible concentration. The values of individual carcinogenic risk for public health were calculated, which amounted to 0.6·10-6 and 1.6·10-6, which corresponds to negligible individual risk (for the adult population) or corresponds to the maximum allowable level (for children), respectively. The obtained results allowed to evaluate the environmental risk from pollution of the snow cover with BaP, the level of which corresponds to a moderate one, however, indicates a potential public health hazard related to the ability of the BаP to accumulate in environmental objects. It is established that the most likely source of BaP is automobile transport. The contribution of the fuel and energy complex should be much less.
{"title":"INFLUENCE OF BENZO(A)PYRENE ON ENVIRONMENTAL QUALITY AND POPULATION HEALTH (BY EXAMPLE OF IVANOVO)","authors":"T. Izvekova, N. A. Kobeleva, A. Gushchin, M. S. Gerasimova, V. Grinevich","doi":"10.6060/IVKKT.20186112.5838","DOIUrl":"https://doi.org/10.6060/IVKKT.20186112.5838","url":null,"abstract":"The paper presents the results of measurements of the content of benzo(a)pyrene (BaP) in the snow cover in the territory of the Ivanovo city. It was revealed that the concentration of BaP at the controlled points is 2.7 times higher than the background level on average. The degree of pollution of the snow cover in Ivanovo is much less than in Moscow (the level of excess varies in the range 2.3 - 89 times). The intake levels (from 0.02 μg/m2 to 3.76 μg/m2) and deposition density (0.02 - 1.88 ng/m2 · day-1) of BaP are estimated that are commensurate with the values typical for such areas, as urban areas of Germany and Canada. Interpolation the BaP concentrations in snow is allowed to reveal anomalies in the city with BaP content of 35 ng/l, which is 7 times higher than the average value for the whole city. The obtained data made it possible to estimate the BaP concentration in atmospheric air, which on the average is 0.7· 10-6 mg/m3, which is 0.7 fraction of the maximum permissible concentration. The values of individual carcinogenic risk for public health were calculated, which amounted to 0.6·10-6 and 1.6·10-6, which corresponds to negligible individual risk (for the adult population) or corresponds to the maximum allowable level (for children), respectively. The obtained results allowed to evaluate the environmental risk from pollution of the snow cover with BaP, the level of which corresponds to a moderate one, however, indicates a potential public health hazard related to the ability of the BаP to accumulate in environmental objects. It is established that the most likely source of BaP is automobile transport. The contribution of the fuel and energy complex should be much less.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41559248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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