Pub Date : 2018-08-21DOI: 10.6060/IVKKT201861008.5737
A. S. Mkhitaryan, Z. Papanyan, L. Gabrielyan, S. Markarian
The quantum chemical study of the hydration of diethyl sulfone was performed by using Gaussian 09 software package. The conformational analysis of the isolated molecule of diethyl sulfone is performed by the restricted Hartree-Fock (RHF) and the density functional theory (DFT/B3PW91) methods with 6-311++G(d,p) extended basis set. The analysis of the potential energy surface revealed the existence of four stable conformers of diethyl sulfone with different degrees of degeneracy. The nature of stationary points on the potential energy surface is verified by the complete gas phase optimization and the vibrational analysis. The global minimum is the conformer with two (CCSC) dihedral angles equal 180°. The fractional population distribution of different conformers is determined by Boltzmann distribution. The average energy of the diethyl sulfone molecule in vacuum is calculated. To account the effect of solvent the self-consistent reaction field (SCRF) method, particularly, solvent model based on electron density (SMD), was employed. It is shown, that solvent affects on the relative population of conformers. The thermodynamic parameters, in particular enthalpy, for the conformers of diethyl sulfone are determined both in the gas phase and in the aqueous solution. The average energy of diethyl sulfone in water is calculated. It is shown, that although the dissolution of crystalline diethyl sulfone in water is an endothermic process, the hydration of diethyl sulfone molecules occurs with the release of heat. The heat of dissolution of diethyl sulfone calculated by the density functional theory is consistent with the experimental data.
{"title":"HEAT OF HYDRATION OF DIETHYLSULFONE BY QUANTUM CHEMICAL CALCULATION","authors":"A. S. Mkhitaryan, Z. Papanyan, L. Gabrielyan, S. Markarian","doi":"10.6060/IVKKT201861008.5737","DOIUrl":"https://doi.org/10.6060/IVKKT201861008.5737","url":null,"abstract":"The quantum chemical study of the hydration of diethyl sulfone was performed by using Gaussian 09 software package. The conformational analysis of the isolated molecule of diethyl sulfone is performed by the restricted Hartree-Fock (RHF) and the density functional theory (DFT/B3PW91) methods with 6-311++G(d,p) extended basis set. The analysis of the potential energy surface revealed the existence of four stable conformers of diethyl sulfone with different degrees of degeneracy. The nature of stationary points on the potential energy surface is verified by the complete gas phase optimization and the vibrational analysis. The global minimum is the conformer with two (CCSC) dihedral angles equal 180°. The fractional population distribution of different conformers is determined by Boltzmann distribution. The average energy of the diethyl sulfone molecule in vacuum is calculated. To account the effect of solvent the self-consistent reaction field (SCRF) method, particularly, solvent model based on electron density (SMD), was employed. It is shown, that solvent affects on the relative population of conformers. The thermodynamic parameters, in particular enthalpy, for the conformers of diethyl sulfone are determined both in the gas phase and in the aqueous solution. The average energy of diethyl sulfone in water is calculated. It is shown, that although the dissolution of crystalline diethyl sulfone in water is an endothermic process, the hydration of diethyl sulfone molecules occurs with the release of heat. The heat of dissolution of diethyl sulfone calculated by the density functional theory is consistent with the experimental data.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48933406","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 : 2018-08-21DOI: 10.6060/IVKKT201861008.5726
N. V. Ksandrov, O. R. Ozhogina
The problem of NH3 extraction from wet gases and returning it to the process may take place in the technologies which use aqueous ammonia solutions. The extraction of non-ferrous metal oxides forming soluble ammoniates from industrial wastes with the solution of ammonium chloride and ammonia in water is an example of such technologies. The oxides of non-ferrous metals are then precipitated, driving the mixture of water vapor and ammonia off the solution. Waste purification reduces the pollution of natural water resources and expands the raw material base of metallurgy of copper and zinc. To return NH3 to the waste treatment it is efficient to use adsorption of ammonia from the gas-vapor mixture. The silica gel used in ammonia plants is not applicable to absorption NH3 from wet gases. The data on the adsorption NH3 from the gas-vapor mixture with hydrophobic activated coals are not sufficient for practical purposе. The dependence of the equilibrium adsorption capacity of activated coal AG-3 on ammonia wapors on their partial pressure at 0.1−15 kPa and a tempеrature of 288−323 K in the sorption of ammonia from wet gases is studied with a dynamic method. The micropore volume of the coal samples is equal to 0.31±0.02 cm3/g. The presented equation provides the calculation of the sorption capacity of coal in the studied range of adsorption parameter change with an average error less than 5% for each isotherme. The heat of adsorption is equal to 37 -39 kJ/mol which is larger than the heat of condensation of ammonia vapors by about 20 kJ/mol, which is typical for physical adsorption. During the regeneration of the coal which absorbed the ammonia the adsorption capacity was stable.
{"title":"ADSORPTION OF AMMONIA WITH ACTIVATED COAL AG-3","authors":"N. V. Ksandrov, O. R. Ozhogina","doi":"10.6060/IVKKT201861008.5726","DOIUrl":"https://doi.org/10.6060/IVKKT201861008.5726","url":null,"abstract":"The problem of NH3 extraction from wet gases and returning it to the process may take place in the technologies which use aqueous ammonia solutions. The extraction of non-ferrous metal oxides forming soluble ammoniates from industrial wastes with the solution of ammonium chloride and ammonia in water is an example of such technologies. The oxides of non-ferrous metals are then precipitated, driving the mixture of water vapor and ammonia off the solution. Waste purification reduces the pollution of natural water resources and expands the raw material base of metallurgy of copper and zinc. To return NH3 to the waste treatment it is efficient to use adsorption of ammonia from the gas-vapor mixture. The silica gel used in ammonia plants is not applicable to absorption NH3 from wet gases. The data on the adsorption NH3 from the gas-vapor mixture with hydrophobic activated coals are not sufficient for practical purposе. The dependence of the equilibrium adsorption capacity of activated coal AG-3 on ammonia wapors on their partial pressure at 0.1−15 kPa and a tempеrature of 288−323 K in the sorption of ammonia from wet gases is studied with a dynamic method. The micropore volume of the coal samples is equal to 0.31±0.02 cm3/g. The presented equation provides the calculation of the sorption capacity of coal in the studied range of adsorption parameter change with an average error less than 5% for each isotherme. The heat of adsorption is equal to 37 -39 kJ/mol which is larger than the heat of condensation of ammonia vapors by about 20 kJ/mol, which is typical for physical adsorption. During the regeneration of the coal which absorbed the ammonia the adsorption capacity was stable.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49609945","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 : 2018-08-21DOI: 10.6060/ivkkt201861008.5742
V. G. Badelin, G. N. Tarasova, E. Tyunina, Svetlana A. Bichkova
Drug – macromolecular interactions are an important phenomenon in multicomponents physiological media, such as blood, membranes, intra- and extracellular fluids, etc. The investigation of the mechanisms and driving forces for the molecular processes of the complexes formation, drug transport, and their delivery to target-cells is one of the priority tasks of chemistry, biology and pharmacology. It is imperative that one first investigate the properties of model compounds of macromolecules in an aqueous medium before beginning studies of the more complex systems. The features of their behavior essentially determine the biological activity of macromolecules. One of the well recognized approaches to the study of molecular interactions in fluids is the use of spectroscopic methods. As part of the longer term objective to investigate different aspects of interaction processes between model substances of protein and drug precursor, we report the results of spectroscopic investigation of aqueous solutions containing heterocyclic compounds – L-hystidine, nicotinic acid and uracil at fixed pH value. The electronic absorption spectrums of L-histidine were obtained for aqueous solutions with nicotinic acid and uracil at pH = 7.3 and T=296 K by UV spectroscopy. The spectral characteristics of the interaction between L-histidine and nicotinic acid or uracil were determined. The binding constants and the stoichiometry of the complexes were calculated on the basis of the saturation curves. The calculation of the equilibrium mixture of ionic forms of the studied amino acid as a function of the pH of the medium was carried out according to the computer program RRSU. The forms of reagents existence in an aqueous solution with pH = 7.3 have been determined. The specific features of the interactions of histidine with nicotinic acid and uracil were founded. It was shown that the interaction of histidine with uracil leads to the somewhat more stable complex formation than one with nicotinic acid.
{"title":"INVESTIGATION OF INTERACTION BETWEEN L-HISTIDINE AND HETEROCYCLIC SUBSTANCES IN AQUEOUS SOLUTIONS BY UV SPECTROSCOPY","authors":"V. G. Badelin, G. N. Tarasova, E. Tyunina, Svetlana A. Bichkova","doi":"10.6060/ivkkt201861008.5742","DOIUrl":"https://doi.org/10.6060/ivkkt201861008.5742","url":null,"abstract":"Drug – macromolecular interactions are an important phenomenon in multicomponents physiological media, such as blood, membranes, intra- and extracellular fluids, etc. The investigation of the mechanisms and driving forces for the molecular processes of the complexes formation, drug transport, and their delivery to target-cells is one of the priority tasks of chemistry, biology and pharmacology. It is imperative that one first investigate the properties of model compounds of macromolecules in an aqueous medium before beginning studies of the more complex systems. The features of their behavior essentially determine the biological activity of macromolecules. One of the well recognized approaches to the study of molecular interactions in fluids is the use of spectroscopic methods. As part of the longer term objective to investigate different aspects of interaction processes between model substances of protein and drug precursor, we report the results of spectroscopic investigation of aqueous solutions containing heterocyclic compounds – L-hystidine, nicotinic acid and uracil at fixed pH value. The electronic absorption spectrums of L-histidine were obtained for aqueous solutions with nicotinic acid and uracil at pH = 7.3 and T=296 K by UV spectroscopy. The spectral characteristics of the interaction between L-histidine and nicotinic acid or uracil were determined. The binding constants and the stoichiometry of the complexes were calculated on the basis of the saturation curves. The calculation of the equilibrium mixture of ionic forms of the studied amino acid as a function of the pH of the medium was carried out according to the computer program RRSU. The forms of reagents existence in an aqueous solution with pH = 7.3 have been determined. The specific features of the interactions of histidine with nicotinic acid and uracil were founded. It was shown that the interaction of histidine with uracil leads to the somewhat more stable complex formation than one with nicotinic acid.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48211832","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 : 2018-08-21DOI: 10.6060/ivkkt20186108.5718
S. Andreev, E. S. Belyaev, A. O. Ivanova, Elvina A. Novikova, A. Ishchenko
Chlorhexidine digluconate has been widely used in lenticular compositions, skin antiseptics and other ready-to-use disinfectants. This is due to its low toxicity, as well as a wide range of antimicrobial effects. A commonly used method for the analysis of commercially available chlorhexidine digluconate (usually available as a 20% aqueous solution) is high-performance liquid chromatography. In this article, the main methods of analysis used to determine chlorhexidine digluconate in disinfectants and skin antiseptics are considered. A new simple technique for the determination of chlorhexidine digluconate in technical products and disinfectants based on acid-base titration in alcohol-ketone is developed. It is shown that in this medium hydrochloric acid interacts with two nitrogen atoms of the chlorhexidine digluconate molecule. The end point of the titration is established by the transition of the blue color to green in the presence of bromophenol blue. The range of measured concentrations is from 0.1 to 2.0 mass%. The relative error of the method is 2.5% with the confidence probability P = 0.95. A comparison of the diode array detector and the charged aerosol detector for the determination of chlorhexidine digluconate has been performed. It is shown that a charged aerosol detector can be used to analyze chlorhexidine digluconate in cases where it is difficult to analyze with an ultraviolet or diode array detector. However, the sensitivity of the detector of charged aerosols is significantly lower than that of the diode matrix, and the linearity range is smaller. All methods were tested on model samples, as well as on samples of disinfectants, skin antiseptics, soaps and wipes with antibacterial effect.
{"title":"DETERMINATION OF CHLORHEXIDINE DIGLUCONATE IN DISINFECTANTS","authors":"S. Andreev, E. S. Belyaev, A. O. Ivanova, Elvina A. Novikova, A. Ishchenko","doi":"10.6060/ivkkt20186108.5718","DOIUrl":"https://doi.org/10.6060/ivkkt20186108.5718","url":null,"abstract":"Chlorhexidine digluconate has been widely used in lenticular compositions, skin antiseptics and other ready-to-use disinfectants. This is due to its low toxicity, as well as a wide range of antimicrobial effects. A commonly used method for the analysis of commercially available chlorhexidine digluconate (usually available as a 20% aqueous solution) is high-performance liquid chromatography. In this article, the main methods of analysis used to determine chlorhexidine digluconate in disinfectants and skin antiseptics are considered. A new simple technique for the determination of chlorhexidine digluconate in technical products and disinfectants based on acid-base titration in alcohol-ketone is developed. It is shown that in this medium hydrochloric acid interacts with two nitrogen atoms of the chlorhexidine digluconate molecule. The end point of the titration is established by the transition of the blue color to green in the presence of bromophenol blue. The range of measured concentrations is from 0.1 to 2.0 mass%. The relative error of the method is 2.5% with the confidence probability P = 0.95. A comparison of the diode array detector and the charged aerosol detector for the determination of chlorhexidine digluconate has been performed. It is shown that a charged aerosol detector can be used to analyze chlorhexidine digluconate in cases where it is difficult to analyze with an ultraviolet or diode array detector. However, the sensitivity of the detector of charged aerosols is significantly lower than that of the diode matrix, and the linearity range is smaller. All methods were tested on model samples, as well as on samples of disinfectants, skin antiseptics, soaps and wipes with antibacterial effect.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":"1 1","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71162658","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 : 2018-08-21DOI: 10.6060/IVKKT20186108.5721
A. M. Dunaev, I. V. Rumyantsev, I. B. Agapova, V. Grinevich, K. Vergel, S. Gundorina
Air and soil quality assessment at the Rodniki town, Ivanovo Region, was performed using physical chemical analysis and biomonitoring techniques: soil and snow analysis, moss biomonitoring, fluctuating asymmetry (IFA) for the silver birch (Betula pendula Roth.). Elemental content in moss, soil and snow samples was determined by neutron activation analysis (NAA) and atomic absorption spectrometry (AAS). A total of 40 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Zr, Mo, Ag, In, Sb, I, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb, Lu, Hf, Ta, W) was determined by NAA. To determine concentrations of Pb, Cd, and Cu AAS technique was used. To reveal potential sources of element-pollutants the descriptive statistics and factor analysis were applied in OriginPro 8 and SPSS 17.0 software packages for Windows. To evaluate the contribution to the metal content in moss from anthropogenic sources, enrichment factors (EF) were calculated. Distribution maps were prepared to point out areas most affected by pollution and to characterize the main deposition patterns of pollutants. To create GIS maps QGIS software was used. The complex assessment of the air and soil quality of the Rodniki town and its vicinity showed an acceptable level of the contamination. It was established that the main source of pollution is the machine-building plant situated in the north of the town. This plant causes soil contamination by Zn, As, Fe, and Co. The IFA values successfully confirm the obtained concentration data. Besides, it was established that the soil contamination has a bigger influence on IFA than atmospheric pollution. Measures for nature conservation are suggested.
{"title":"PHYSICAL AND CHEMICAL AND BIOLOGICAL MONITORING IN CENTRAL RUSSIA: INVESTIGATION OF QUALITY OF ATMOSPHERIC AIR AND SOIL IN TERRITORY OF RODNIKI CITY","authors":"A. M. Dunaev, I. V. Rumyantsev, I. B. Agapova, V. Grinevich, K. Vergel, S. Gundorina","doi":"10.6060/IVKKT20186108.5721","DOIUrl":"https://doi.org/10.6060/IVKKT20186108.5721","url":null,"abstract":"Air and soil quality assessment at the Rodniki town, Ivanovo Region, was performed using physical chemical analysis and biomonitoring techniques: soil and snow analysis, moss biomonitoring, fluctuating asymmetry (IFA) for the silver birch (Betula pendula Roth.). Elemental content in moss, soil and snow samples was determined by neutron activation analysis (NAA) and atomic absorption spectrometry (AAS). A total of 40 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Zr, Mo, Ag, In, Sb, I, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb, Lu, Hf, Ta, W) was determined by NAA. To determine concentrations of Pb, Cd, and Cu AAS technique was used. To reveal potential sources of element-pollutants the descriptive statistics and factor analysis were applied in OriginPro 8 and SPSS 17.0 software packages for Windows. To evaluate the contribution to the metal content in moss from anthropogenic sources, enrichment factors (EF) were calculated. Distribution maps were prepared to point out areas most affected by pollution and to characterize the main deposition patterns of pollutants. To create GIS maps QGIS software was used. The complex assessment of the air and soil quality of the Rodniki town and its vicinity showed an acceptable level of the contamination. It was established that the main source of pollution is the machine-building plant situated in the north of the town. This plant causes soil contamination by Zn, As, Fe, and Co. The IFA values successfully confirm the obtained concentration data. Besides, it was established that the soil contamination has a bigger influence on IFA than atmospheric pollution. Measures for nature conservation are suggested.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41606216","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 : 2018-08-21DOI: 10.6060/IVKKT201861008.5755
D. Gurulev, L. Palatkina, A. Yudina, V. I. Porkhun
To date, it is considered established that quinones with lower energy state, under the action of light tear away a hydrogen atom from a hydrocarbon or an electron donor from inorganic anion-radicals, which have a high reduction potential. However, even for the simplest quinones (1,4-benzoquinone, 1,4-naphthoquinones, 9,10-anthraquinone and their derivatives) there is no consensus in the science literature about the nature of the initial event in photoreaction with compounds which are potential donors of hydrogen atom and electron. The first step in many photochemical reactions is the formation of complexes between donors and acceptors of electrons in the excited state (exiplexes). Photoreactive quinones as elementary acts include the transfer of electron (or) hydrogen atom. The mechanism depends on the presence and strength of donor-acceptor complexes (DAC) of the quinones with the reagents. Studies of triplet exiplexes allow you to set the details of the elementary reaction acts. Only short-lived intermediate product was registered upon photoexcitation of the studied quinone Q in low-polarity solvents. The kinetic of decay of the first order with rate constant of about 2∙106 s-1 in toluene and dibutylphthalate and the introduction of oxygen leads to a decrease in the lifetime of the product in the triplet state. With the introduction of solutions of amines quenching of triplet state (QT) with rate constant close to diffusion was observed. Rate constants of quenching by dissolving in benzene and by dissolving in dibutyl phthalate were determined. It is established that formation of intermediate products is carried out from triplet state (QT). Excited complexes with charge transfer in acetonitrile were not observed. It is concluded that with decrease in electron affinity of the acceptors, when the connection of the molecules in the complex becomes weaker, the lifetime of TE increases significantly.
{"title":"PROPERTIES OF EXCITED MOLECULES IN PHOTOLYSIS OF 2,6-DIPHENYL-1,4-BENZOQUINONE WITH AMINES","authors":"D. Gurulev, L. Palatkina, A. Yudina, V. I. Porkhun","doi":"10.6060/IVKKT201861008.5755","DOIUrl":"https://doi.org/10.6060/IVKKT201861008.5755","url":null,"abstract":"To date, it is considered established that quinones with lower energy state, under the action of light tear away a hydrogen atom from a hydrocarbon or an electron donor from inorganic anion-radicals, which have a high reduction potential. However, even for the simplest quinones (1,4-benzoquinone, 1,4-naphthoquinones, 9,10-anthraquinone and their derivatives) there is no consensus in the science literature about the nature of the initial event in photoreaction with compounds which are potential donors of hydrogen atom and electron. The first step in many photochemical reactions is the formation of complexes between donors and acceptors of electrons in the excited state (exiplexes). Photoreactive quinones as elementary acts include the transfer of electron (or) hydrogen atom. The mechanism depends on the presence and strength of donor-acceptor complexes (DAC) of the quinones with the reagents. Studies of triplet exiplexes allow you to set the details of the elementary reaction acts. Only short-lived intermediate product was registered upon photoexcitation of the studied quinone Q in low-polarity solvents. The kinetic of decay of the first order with rate constant of about 2∙106 s-1 in toluene and dibutylphthalate and the introduction of oxygen leads to a decrease in the lifetime of the product in the triplet state. With the introduction of solutions of amines quenching of triplet state (QT) with rate constant close to diffusion was observed. Rate constants of quenching by dissolving in benzene and by dissolving in dibutyl phthalate were determined. It is established that formation of intermediate products is carried out from triplet state (QT). Excited complexes with charge transfer in acetonitrile were not observed. It is concluded that with decrease in electron affinity of the acceptors, when the connection of the molecules in the complex becomes weaker, the lifetime of TE increases significantly.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46078288","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 : 2018-08-21DOI: 10.6060/IVKKT20186108.5707
M. Akhmedov, S. Khidirov, Madina Yu. Kaparova
In this paper the electrochemical oxidation of dimethyl sulfone (DMSO2) on a platinum electrode in an alkaline medium has been studied by cyclic voltammetry. It is shown that during the electrochemical oxidation of dimethylsulfone in an alkaline medium on a smooth platinum electrode, a significant suppression of the oxygen evolution (O2) occurs in the potential range of E = 1.3-2.0 V. By scanning electron microscopy methods, Raman scattering and infrared spectrometry it is shown that the main substance is the dimethyl disulfone (DMDSO2) during the anodic oxidation of DMSO2 on a platinum electrode. By the preparative electrolysis of aqueous solutions of various concentrations of DMSO2 in 0.1 M NaOH solution at controlled potentials E = 1.6 and 1.8 V it is established that the current yield of the base material is not more than 84%. Based on the data of the physicochemical analysis of the final products of preparative electrolysis, a mechanism is proposed for the formation of dimethyl disulfone in an alkaline medium. It has been shown that the oxidation of dimethyl sulfone proceeds in the oxygen region by breaking C-S bonds in the DMSO2 molecule to form methyl (CH3•) and methylsulfonic (CH3S•(O)2) radicals. It is assumed that the methylsulfone radicals readily dimerize with the formation of stable DMDSO2 molecules and are desorbed in the bulk of the solution, and the methyl radicals bind to the HO radicals to form methanol molecules. The latter is well chemisorbed on the surface of platinum with the formation of adsorbed COH particles that are oxidized on a platinum electrode with the formation and evolution of carbon dioxide (CO2) from the volume of the anolyte solution. The formation of molecules of methanol was identified by the method of chromato-mass -spectrometry, and the emission of carbon dioxide by the gravimetry.
{"title":"ELECTROCHEMICAL OXIDATION OF DIMETHYL SULFONE IN ALKALINE MEDIUM","authors":"M. Akhmedov, S. Khidirov, Madina Yu. Kaparova","doi":"10.6060/IVKKT20186108.5707","DOIUrl":"https://doi.org/10.6060/IVKKT20186108.5707","url":null,"abstract":"In this paper the electrochemical oxidation of dimethyl sulfone (DMSO2) on a platinum electrode in an alkaline medium has been studied by cyclic voltammetry. It is shown that during the electrochemical oxidation of dimethylsulfone in an alkaline medium on a smooth platinum electrode, a significant suppression of the oxygen evolution (O2) occurs in the potential range of E = 1.3-2.0 V. By scanning electron microscopy methods, Raman scattering and infrared spectrometry it is shown that the main substance is the dimethyl disulfone (DMDSO2) during the anodic oxidation of DMSO2 on a platinum electrode. By the preparative electrolysis of aqueous solutions of various concentrations of DMSO2 in 0.1 M NaOH solution at controlled potentials E = 1.6 and 1.8 V it is established that the current yield of the base material is not more than 84%. Based on the data of the physicochemical analysis of the final products of preparative electrolysis, a mechanism is proposed for the formation of dimethyl disulfone in an alkaline medium. It has been shown that the oxidation of dimethyl sulfone proceeds in the oxygen region by breaking C-S bonds in the DMSO2 molecule to form methyl (CH3•) and methylsulfonic (CH3S•(O)2) radicals. It is assumed that the methylsulfone radicals readily dimerize with the formation of stable DMDSO2 molecules and are desorbed in the bulk of the solution, and the methyl radicals bind to the HO radicals to form methanol molecules. The latter is well chemisorbed on the surface of platinum with the formation of adsorbed COH particles that are oxidized on a platinum electrode with the formation and evolution of carbon dioxide (CO2) from the volume of the anolyte solution. The formation of molecules of methanol was identified by the method of chromato-mass -spectrometry, and the emission of carbon dioxide by the gravimetry.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44945704","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 : 2018-08-21DOI: 10.6060/ivkkt201861008.5759
I. S. Spiridonov, M. S. Illarionova, N. F. Ushmarin, S. I. Sandalov, N. I. Kol’tsov
Rubber-technical products, which are used in the oil and gas industry, must have high thermal and aggressive strength. Rubbers based on butadiene-nitrile caoutchoucs are usually used for these purposes, since they have good operational properties. However, under the influence of elevated temperatures, the resistance of such rubbers to the action of petroleum products is reduced, as a result of which the physico-mechanical characteristics decrease. To improve the operational properties of rubber-technical products, various technological additives are introduced into the rubber mixtures. Such additives can be copolymers of ethylene with vinyl acetate(EVA), which increase the resistance of rubbers to action of high temperatures and aggressive media. This is due to the fact that these copolymers are well combined with butadiene-nitrile caoutchoucs, forming coordination bonds with rubber molecules, which contributes thereby increasing in the elastic-strength and performance properties of rubber. In this connection, the influence of EVA (sevillenes 11104-030, 11808-340 and MarPol 1802), differing in the content of vinyl acetate units, on the rheometric, physico-mechanical and operational properties of the rubber mixture based on butadiene-nitrile rubber in this paper was investigated. The study was carried out to improve the thermo-resistance of rubber used for the manufacture of oil and petrol resistant rubber-technical products for the oil and gas industry. The rubber mixture was prepared on laboratory rolls and standard samples were vulcanized in an electrically heated press. The study of rheometric properties has shown that EVA affect the characteristics of the vulcanization process of a rubber mixture. For vulcanizates, the influence of the content of EVA in a rubber mixture on the physical and mechanical properties was studied: the conditional tensile strength, elongation at break, tear resistance, rebound elasticity, Shore A hardness, relative compression deformation. The effect of the standard liquid ZHR-1 on the change in these properties, as well as the degree of swelling of the vulcanizates after their daily soaking in the standard liquid SZHR-1 and a mixture of isooctane + toluene, was studied. It has been established that vulcanizate of a rubber mixture containing sevilene 11808-340 is characterized by the best physico-mechanical and operational properties.
{"title":"THE INFLUENCE OF ETHYLENE COPOLYMERS WITH VINYL ACETATE ON PROPERTIES OF RUBBER BASED OF BUTADIENE-NITRILE CAOUTCHOUC","authors":"I. S. Spiridonov, M. S. Illarionova, N. F. Ushmarin, S. I. Sandalov, N. I. Kol’tsov","doi":"10.6060/ivkkt201861008.5759","DOIUrl":"https://doi.org/10.6060/ivkkt201861008.5759","url":null,"abstract":"Rubber-technical products, which are used in the oil and gas industry, must have high thermal and aggressive strength. Rubbers based on butadiene-nitrile caoutchoucs are usually used for these purposes, since they have good operational properties. However, under the influence of elevated temperatures, the resistance of such rubbers to the action of petroleum products is reduced, as a result of which the physico-mechanical characteristics decrease. To improve the operational properties of rubber-technical products, various technological additives are introduced into the rubber mixtures. Such additives can be copolymers of ethylene with vinyl acetate(EVA), which increase the resistance of rubbers to action of high temperatures and aggressive media. This is due to the fact that these copolymers are well combined with butadiene-nitrile caoutchoucs, forming coordination bonds with rubber molecules, which contributes thereby increasing in the elastic-strength and performance properties of rubber. In this connection, the influence of EVA (sevillenes 11104-030, 11808-340 and MarPol 1802), differing in the content of vinyl acetate units, on the rheometric, physico-mechanical and operational properties of the rubber mixture based on butadiene-nitrile rubber in this paper was investigated. The study was carried out to improve the thermo-resistance of rubber used for the manufacture of oil and petrol resistant rubber-technical products for the oil and gas industry. The rubber mixture was prepared on laboratory rolls and standard samples were vulcanized in an electrically heated press. The study of rheometric properties has shown that EVA affect the characteristics of the vulcanization process of a rubber mixture. For vulcanizates, the influence of the content of EVA in a rubber mixture on the physical and mechanical properties was studied: the conditional tensile strength, elongation at break, tear resistance, rebound elasticity, Shore A hardness, relative compression deformation. The effect of the standard liquid ZHR-1 on the change in these properties, as well as the degree of swelling of the vulcanizates after their daily soaking in the standard liquid SZHR-1 and a mixture of isooctane + toluene, was studied. It has been established that vulcanizate of a rubber mixture containing sevilene 11808-340 is characterized by the best physico-mechanical and operational properties.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42806423","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 : 2018-07-17DOI: 10.6060/tcct.20165908.34y
M. Shavelkina, R. Amirov, T. Borodina, V. Kiselev, T. Shatalova, K. Rabadanov
Thermal plasma processing of carbon sources using a plasma jet with high heat capacity is one of the most promising methods for the synthesis of new materials. This paper describes the low-temperature deposition of carbon nanomaterials by remote plasma-enhanced chemical vapor deposition (PECVD) in the absence of catalysts. The remote PECVD process differs from conventional and direct PECVD process in two ways: (a) only a subset of the process reactants and/or diluents are directly plasma excited; and (b) thin film deposition takes place on a substrate that is outside of the plasma glow region. In conventional CVD methods, carbon is produced from the decomposition of carbon sources such as hydrocarbons, carbon monoxide, alcohols, and so on, over a metal catalyst. The unavoidable metal species remaining in carbon nanomaterials would lead to obvious disadvantages for property characterization and application exploration. Despite sustained efforts, it is still an intractable problem to remove metal catalysts completely from carbon nanomaterials samples without introducing defects and contaminations. Good reactor design allowed to overcome problems of chemical and structural purity, and poor process robustness in terms of phase composition of product from run to run. For the synthesis of graphene materials, carbon black, carbon nanotubes, nanowires we used the thermal plasma generator which is a high current divergent anode-channel DC plasma torch. The experiment involved a simultaneous input of hydrocarbons (methane, propane, butane, acetylene) with the plasma forming gas (helium, argon, nitrogen) into the plasma torch, wherein heating and decompositions occurred in the plasma jet and in the region of the arc discharge, followed by condensation of the synthesis product on metallic surfaces. The deposition rate was varied with distance from the plasma. Consumption of carbon source, plasma forming gas and plasma torch power were changed independently from each other. For the experimental conditions the electric power of plasma torch was set up to 40 kW. Regularities of formation of carbon thread-like nanostructures and graphene in the course of hydrocarbons pyrolysis in thermal plasma without participation of catalytic particles were studied by means of electron microscopy, X-ray diffraction, IR-spectrometry and thermogravimetry. Depending on the pyrolytic synthesis parameters, different proportions of crystal carbon and soot may be obtained. It has been demonstrated that the phase composition is varied by hydrocarbons flow rate, plasma forming gas pressure and dc plasma torch power. It has been established through the experiments that carbon nucleation is volumetric and proceeds according to the model of explosive soot formation.
{"title":"FORMATION OF NANO STRUCTURES IN RESULT OF HOMOGENOUS NUCLEATION OF CARBON OBTAINED IN THERMAL PLASMA UNDER ATMOSPHERIC PRESSURE","authors":"M. Shavelkina, R. Amirov, T. Borodina, V. Kiselev, T. Shatalova, K. Rabadanov","doi":"10.6060/tcct.20165908.34y","DOIUrl":"https://doi.org/10.6060/tcct.20165908.34y","url":null,"abstract":"Thermal plasma processing of carbon sources using a plasma jet with high heat capacity is one of the most promising methods for the synthesis of new materials. This paper describes the low-temperature deposition of carbon nanomaterials by remote plasma-enhanced chemical vapor deposition (PECVD) in the absence of catalysts. The remote PECVD process differs from conventional and direct PECVD process in two ways: (a) only a subset of the process reactants and/or diluents are directly plasma excited; and (b) thin film deposition takes place on a substrate that is outside of the plasma glow region. In conventional CVD methods, carbon is produced from the decomposition of carbon sources such as hydrocarbons, carbon monoxide, alcohols, and so on, over a metal catalyst. The unavoidable metal species remaining in carbon nanomaterials would lead to obvious disadvantages for property characterization and application exploration. Despite sustained efforts, it is still an intractable problem to remove metal catalysts completely from carbon nanomaterials samples without introducing defects and contaminations. Good reactor design allowed to overcome problems of chemical and structural purity, and poor process robustness in terms of phase composition of product from run to run. For the synthesis of graphene materials, carbon black, carbon nanotubes, nanowires we used the thermal plasma generator which is a high current divergent anode-channel DC plasma torch. The experiment involved a simultaneous input of hydrocarbons (methane, propane, butane, acetylene) with the plasma forming gas (helium, argon, nitrogen) into the plasma torch, wherein heating and decompositions occurred in the plasma jet and in the region of the arc discharge, followed by condensation of the synthesis product on metallic surfaces. The deposition rate was varied with distance from the plasma. Consumption of carbon source, plasma forming gas and plasma torch power were changed independently from each other. For the experimental conditions the electric power of plasma torch was set up to 40 kW. Regularities of formation of carbon thread-like nanostructures and graphene in the course of hydrocarbons pyrolysis in thermal plasma without participation of catalytic particles were studied by means of electron microscopy, X-ray diffraction, IR-spectrometry and thermogravimetry. Depending on the pyrolytic synthesis parameters, different proportions of crystal carbon and soot may be obtained. It has been demonstrated that the phase composition is varied by hydrocarbons flow rate, plasma forming gas pressure and dc plasma torch power. It has been established through the experiments that carbon nucleation is volumetric and proceeds according to the model of explosive soot formation.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48185399","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 : 2018-07-17DOI: 10.6060/TCCT.20165907.5391
S. Niftaliev, Y. Peregudov, O. Kozaderova, Kseniya B. Kim
Ion-exchange membranes are widely used for extraction, separation and concentration of aqueous nitrogen-containing solutions. In the study the heterogeneous ion-exchange membranes of cationic type- MK-40, Ralex CM (H) -PP, MK-41 – and anionic type - MA-41, Ralex AM (H) -PP and also their granular analogues – cation exchanger KУ-2·8 and anion exchanger AB-17·8 were used. Sorption of nitrate ions and ammonium ions was conducted from the ammonium nitrate solution with concentration of 0.012 mole / dm³. To determine sorption thermochemical characteristics of the studied ions the calorimetric method was used. It was found that for all the studied types of membranes and ion exchangers the processes were accompanied by heat evolution. From the calorimetric measurements the thermokinetic interaction curves of cation-exchange membranes and KУ-2×8 with the ammonium nitrate solution and anion-exchange membranes and AB-17×8 with the solution of the same salt were obtained. According to the curves the power of heat evolution and time of the process were determined. It was shown that the ion exchangers KУ-2·8 and AB-17·8 are characterized by a longer time to achieve the maximum of heat evolution and process time than for the similar membranes. This fact is explained by the different number and accessibility of the functional groups in the membranes and ion exchangers. From the thermo-kinetic curves the enthalpies of interaction were calculated. The process of the interaction between the granular ion exchangers and ions is characterized by higher values of the enthalpy than for the membranes which large steric effects are common for. Saline concentration, nature of exchangeable ions and type of functional groups of the ion exchanger and also its moisture content influence the enthalpy value. Experimental calorimetric data indicated that the energy costs connected with the effects of dehydration and conformational changes in the sorbent polymer chains do not overlap the exothermic sorption effect. The calorimetric method is informative to determine the nature and mechanism of sorption.
{"title":"ENTHALPY OF INTERACTION OF ION-EXCHANGE HETEROGENEOUS MEMBRANES AND THEIR GRANULAR ANALOGUES WITH AMMONIUM NITRATE SOLUTION","authors":"S. Niftaliev, Y. Peregudov, O. Kozaderova, Kseniya B. Kim","doi":"10.6060/TCCT.20165907.5391","DOIUrl":"https://doi.org/10.6060/TCCT.20165907.5391","url":null,"abstract":"Ion-exchange membranes are widely used for extraction, separation and concentration of aqueous nitrogen-containing solutions. In the study the heterogeneous ion-exchange membranes of cationic type- MK-40, Ralex CM (H) -PP, MK-41 – and anionic type - MA-41, Ralex AM (H) -PP and also their granular analogues – cation exchanger KУ-2·8 and anion exchanger AB-17·8 were used. Sorption of nitrate ions and ammonium ions was conducted from the ammonium nitrate solution with concentration of 0.012 mole / dm³. To determine sorption thermochemical characteristics of the studied ions the calorimetric method was used. It was found that for all the studied types of membranes and ion exchangers the processes were accompanied by heat evolution. From the calorimetric measurements the thermokinetic interaction curves of cation-exchange membranes and KУ-2×8 with the ammonium nitrate solution and anion-exchange membranes and AB-17×8 with the solution of the same salt were obtained. According to the curves the power of heat evolution and time of the process were determined. It was shown that the ion exchangers KУ-2·8 and AB-17·8 are characterized by a longer time to achieve the maximum of heat evolution and process time than for the similar membranes. This fact is explained by the different number and accessibility of the functional groups in the membranes and ion exchangers. From the thermo-kinetic curves the enthalpies of interaction were calculated. The process of the interaction between the granular ion exchangers and ions is characterized by higher values of the enthalpy than for the membranes which large steric effects are common for. Saline concentration, nature of exchangeable ions and type of functional groups of the ion exchanger and also its moisture content influence the enthalpy value. Experimental calorimetric data indicated that the energy costs connected with the effects of dehydration and conformational changes in the sorbent polymer chains do not overlap the exothermic sorption effect. The calorimetric method is informative to determine the nature and mechanism of sorption.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49195809","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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