Кислотно-основна взаємодія та сульфоокиснення при хе-мосорбції оксиду сульфуру (IV) водними розчинами алкіламінів
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2020
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Дисертація на здобуття наукового ступеня доктора хімічних наук за спе-ціальністю 02.00.01 – неорганічна хімія. – Інститут загальної та неорганічної хімії ім. В.І. Вернадського НАН України, Київ, 2019.
Дисертацію присвячено вивченню фізико-хімічних процесів при взаємодії оксиду сульфуру (IV) з алкіламінами та їх похідними у водних розчинах залежно від будови органічної основи, температури і присутності кисню.
Вперше синтезовано 20 амонієвих солей сульфурвмісних оксианіонів і три вандерваальсових клатрати. Проведено рентгеноструктурний аналіз та встановлено структуру 23 сполук. Вперше виявлено кореляцію між фізико-хімічними властивостями амінів (AM) і складом виділених продуктів взаємодії в 35 системах SO2 – AM – H2O – O2. Розроблено новий метод синтезу сульфамінової кислоти.
Вперше отримано несуперечливу і об’єктивну інформацію про склад сполук, що утворюються у 23 системах SO2 – AM – H2O. Зазначена взаємодія су-проводжується утворенням у розчинах сульфітів, гідросульфітів, піросульфітів та сульфіто-гідросульфітів відповідних амонієвих катіонів.
Запропоновано та запатентовано нові методи синтезу амінометансульфонової кислоти (AMSA) та її N-алкілованих похідних. За оригінальним методом синтезовано 5 нових N-алкілованих похідних AMSA, які володіють противірусними і протистафілококовими властивостями і можуть використовуватись як компоненти буферних розчинів. Розроблені та запатентовані імпортозаміщуючі імпрегновані волокнисті хемосорбенти респіраторного призначення впроваджено на практиці.
Диссертация на соискание ученой степени доктора химических наук по специальности 02.00.01 – неорганическая химия. – Институт общей и неорганической химии им. В.И. Вернадского НАН Украины, Киев, 2019. Диссертация посвящена изучению физико-химических процессов при взаимодействии оксида серы (IV) с алкиламинами и их производными в водных растворах в зависимости от строения органического основания, температуры и присутствия кислорода. Впервые синтезировано 20 аммониевых солей серосодержащих оксианионов и три ван-дерваальсовых клатрата. Проведен рентгеноструктурный анализ и установлена структура 23 соединений. Впервые выявлена корреляция между физико-химическими свойствами аминов (AM) и составом выделен-ных продуктов взаимодействия в 35 системах SO2 – AM – H2O – O2. Разработан новый метод синтеза сульфаминовой кислоты. Впервые получена непротиворечивая и объективная информация о составе соединений, образующихся в 23 системах SO2 – AM – H2O. Указанное взаимодействие сопровождается образованием в растворах аммониевых сульфитов, гидросульфитов, пиросульфитов и сульфито-гидросульфитов. Предложены и запатентованы новые методы синтеза аминометансульфоновой кислоты (AMSA) и ее N-алкилированных производных. По оригинальной методике синтезировано 5 новых N-алкилированных производных AMSA – перспективных фармацевтических препаратов, компонентов буферных растворов для биологических и биохимических исследований. Разработанные импортозамещающие импрегнированные волокнистые хемосорбенты респираторного назначения внедрены на практике.
Thesis for a scientific degree of the Doctor of Chemistry in the specialty 02.00.01 – Inorganic Chemistry. – V.I. Vernadskii Institute of General and Inor-ganic Chemistry of the National Academy of Sciences of Ukraine, Kyiv, 2019. The dissertation is devoted to the study of physico-chemical processes in the interaction of sulfur dioxide with alkylamines and their derivatives in aqueous so-lutions, depending on organic base structure, temperature and the presence of O2. Methylamine, n-propylamine, n-butylamine, tert-butylamine, n-heptylamine, n-octylamine, benzylamines (benzylamine, α-phenylethylamine, N,N-dimethyl-benzylamine, dibenzylamine, tribenzylamine), ethanolamines (monoethanolamine, diethanolamine, triethanolamine, N-methylmonoethanolamine, N-methyldiethanol-amine, N,N-diethylmonoethanolamine, N,N-dimethylmonoethanolamine, N-(3-aminopropyl)monoethanolamine, N-(2-hydroxyethyl)ethylenediamine, tris(hydro-xymethyl)aminomethane), diamines (ethylenediamine, N,N,N',N'-tetra-methyl-ethylenediamine, piperazine, 1,4-diazobicyclo[2.2.2]octane, hexamethylenedia-mine), polyamines (diethylenetriamine, hexamethylenetetramine, polyethylenepol-yamine), morpholine, amides (acetamide, propionamide, acrylamide, 2-imid-azolidinone, caprolactam, malonamide, N,N'-dimethylmalonamide, biuret), thio-amides (thiourea, thioacetamide) and N-aminoguanidine were investigated as al-kylamines. 20 ammonium sulfur-containing oxyanions salts and three van der Waals clath-rates were synthesized for the first time. X-ray diffraction analysis was performed and the structure of 23 compounds were established. The correlation between the amines (AM) physico-chemical properties (basicity and lipophilicity) and the composition of the isolated oxysulfur-containing products in 35 SO2 – AM – H2O – O2 systems was revealed for the first time. A new method for the sulfamic acid synthesis has been developed. New methods for aminomethanesulfonic acid (AMSA) and its N-alkylated de-rivatives synthesis have been offered. 5 new N-alkylated AMSA derivatives were synthesized by the original method. It was established for the first time the interaction in SO2 – AM – H2O – O2 systems to accompany by the formation of sulfur-containing oxyanions salts in the case of AM with such basicity constants: aniline (pKa = 4.63), ethanolamines (7.76 pKa 9.85), benzylamines (8.52 pKa 9.84), alkylamines (10.60 pKa 10.77), aminoguanidine (pKa = 11.04). Since the products of interaction with low-basic dipyridyl (pKa = 4.34) and tribenzylamine (pKa = 3.63) are van der Waals clathrates, the value pKa = 4.63 can be regarded as a first approximation as the lower bound of ligand basicity for salt formation realization in the studied reaction systems. Ethanolamines (with the exception of Tris) completely inhibit the sulfur (IV) autoxidation, because they, according to literature data, are free radicals traps; rep-resentatives of ethylenediamine N-derivatives partially inhibit – the process stops at the formation of ammonium dithionates stage; in the case of alkylamines, ben-zylamines, ammonium sulfates are formed. An increase in the number of aminogroups by introducing an additional aminoethylene fragment in the ethylenediamine molecules instead of amine H (to form diethylenetriamine) also causes partial inhibition of these processes. The polyethylenepolyamines of the general formula NH2(CH2CH2NH)n-H (n = 4-6) bind sulfur dioxide to ammonium sulfites that do not respond to the oxidation of air O2. It is shown the sulfate salts relative thermal stability to decrease with the decrease in the basicity and lipophilicity function (pKa + lgPow) in the series of ammonium cations n-C8H17NH 3 n-C7H15NH 3 > n-C4H9NH 3 > n-C3H7NH 3 > C6H5NH 3 . The synthesized benzylammonium sulfates relative stability decreases simbatically with the pKa of the corresponding ammonium cation and antibactically with the lipophilicity of AM indicating the bond between the reagents strengthening, with an increase in the basicity and hydrophilicity of AM. The reaction of “soft” oxidation of S (IV) to S (VI) can be used to obtain highly concentrated SO3 resulting of the formed ammonium sulfates thermolysis. The latter is typical for these salts, in which the melting temperature (destruction) of amines, formed them, is above 260 0С (H2SO4 decomposition temperatures). For the first time, consistent and objective information about the composition of ammonium compounds formed in 23 SO2 – AM – H2O systems was obtained. It was shown this interaction was accompanied by the corresponding ammonium cations formation in the solutions of sulfites, hydrosulfites, pyrosulfites and mixed salts (sulfite-hydrosulfite). It was established that the relationship between the stability of ammonium sulfite and hydrosulfite with pKa values of ethanolamines had symbate character. For the first time, the contributions of the chemical and physical components to the total solubility of sulfur dioxide in aqueous solutions of ethanolamines have been revealed. It was shown with a decrease in the basicity of ethanolamine and an increase of its hydration degree in the series of methylmono-, mono-, di- and triethanolamine, the salting in constant in the equation for physical sorption of SO2 to decrease. The revealed for the first time correlations can be useful in the development sanitary air purification from SO2 methods, immobilized chemical sorbents for gas and ion-exchange chromatography, regeneration of chemical sorbents and utilization of sorption products. The developed import-substituting SO2 impregnated fibrous chemical sorbents are introduced in practice and are used for the manufacture of gas-mask elements of lightweight gas-dust respirators. The new reactions simplify the methods of known compounds synthesis and allow to obtain new components of buffer solutions for biological and biochemical studies, and prospective pharmaceuticals.
Диссертация на соискание ученой степени доктора химических наук по специальности 02.00.01 – неорганическая химия. – Институт общей и неорганической химии им. В.И. Вернадского НАН Украины, Киев, 2019. Диссертация посвящена изучению физико-химических процессов при взаимодействии оксида серы (IV) с алкиламинами и их производными в водных растворах в зависимости от строения органического основания, температуры и присутствия кислорода. Впервые синтезировано 20 аммониевых солей серосодержащих оксианионов и три ван-дерваальсовых клатрата. Проведен рентгеноструктурный анализ и установлена структура 23 соединений. Впервые выявлена корреляция между физико-химическими свойствами аминов (AM) и составом выделен-ных продуктов взаимодействия в 35 системах SO2 – AM – H2O – O2. Разработан новый метод синтеза сульфаминовой кислоты. Впервые получена непротиворечивая и объективная информация о составе соединений, образующихся в 23 системах SO2 – AM – H2O. Указанное взаимодействие сопровождается образованием в растворах аммониевых сульфитов, гидросульфитов, пиросульфитов и сульфито-гидросульфитов. Предложены и запатентованы новые методы синтеза аминометансульфоновой кислоты (AMSA) и ее N-алкилированных производных. По оригинальной методике синтезировано 5 новых N-алкилированных производных AMSA – перспективных фармацевтических препаратов, компонентов буферных растворов для биологических и биохимических исследований. Разработанные импортозамещающие импрегнированные волокнистые хемосорбенты респираторного назначения внедрены на практике.
Thesis for a scientific degree of the Doctor of Chemistry in the specialty 02.00.01 – Inorganic Chemistry. – V.I. Vernadskii Institute of General and Inor-ganic Chemistry of the National Academy of Sciences of Ukraine, Kyiv, 2019. The dissertation is devoted to the study of physico-chemical processes in the interaction of sulfur dioxide with alkylamines and their derivatives in aqueous so-lutions, depending on organic base structure, temperature and the presence of O2. Methylamine, n-propylamine, n-butylamine, tert-butylamine, n-heptylamine, n-octylamine, benzylamines (benzylamine, α-phenylethylamine, N,N-dimethyl-benzylamine, dibenzylamine, tribenzylamine), ethanolamines (monoethanolamine, diethanolamine, triethanolamine, N-methylmonoethanolamine, N-methyldiethanol-amine, N,N-diethylmonoethanolamine, N,N-dimethylmonoethanolamine, N-(3-aminopropyl)monoethanolamine, N-(2-hydroxyethyl)ethylenediamine, tris(hydro-xymethyl)aminomethane), diamines (ethylenediamine, N,N,N',N'-tetra-methyl-ethylenediamine, piperazine, 1,4-diazobicyclo[2.2.2]octane, hexamethylenedia-mine), polyamines (diethylenetriamine, hexamethylenetetramine, polyethylenepol-yamine), morpholine, amides (acetamide, propionamide, acrylamide, 2-imid-azolidinone, caprolactam, malonamide, N,N'-dimethylmalonamide, biuret), thio-amides (thiourea, thioacetamide) and N-aminoguanidine were investigated as al-kylamines. 20 ammonium sulfur-containing oxyanions salts and three van der Waals clath-rates were synthesized for the first time. X-ray diffraction analysis was performed and the structure of 23 compounds were established. The correlation between the amines (AM) physico-chemical properties (basicity and lipophilicity) and the composition of the isolated oxysulfur-containing products in 35 SO2 – AM – H2O – O2 systems was revealed for the first time. A new method for the sulfamic acid synthesis has been developed. New methods for aminomethanesulfonic acid (AMSA) and its N-alkylated de-rivatives synthesis have been offered. 5 new N-alkylated AMSA derivatives were synthesized by the original method. It was established for the first time the interaction in SO2 – AM – H2O – O2 systems to accompany by the formation of sulfur-containing oxyanions salts in the case of AM with such basicity constants: aniline (pKa = 4.63), ethanolamines (7.76 pKa 9.85), benzylamines (8.52 pKa 9.84), alkylamines (10.60 pKa 10.77), aminoguanidine (pKa = 11.04). Since the products of interaction with low-basic dipyridyl (pKa = 4.34) and tribenzylamine (pKa = 3.63) are van der Waals clathrates, the value pKa = 4.63 can be regarded as a first approximation as the lower bound of ligand basicity for salt formation realization in the studied reaction systems. Ethanolamines (with the exception of Tris) completely inhibit the sulfur (IV) autoxidation, because they, according to literature data, are free radicals traps; rep-resentatives of ethylenediamine N-derivatives partially inhibit – the process stops at the formation of ammonium dithionates stage; in the case of alkylamines, ben-zylamines, ammonium sulfates are formed. An increase in the number of aminogroups by introducing an additional aminoethylene fragment in the ethylenediamine molecules instead of amine H (to form diethylenetriamine) also causes partial inhibition of these processes. The polyethylenepolyamines of the general formula NH2(CH2CH2NH)n-H (n = 4-6) bind sulfur dioxide to ammonium sulfites that do not respond to the oxidation of air O2. It is shown the sulfate salts relative thermal stability to decrease with the decrease in the basicity and lipophilicity function (pKa + lgPow) in the series of ammonium cations n-C8H17NH 3 n-C7H15NH 3 > n-C4H9NH 3 > n-C3H7NH 3 > C6H5NH 3 . The synthesized benzylammonium sulfates relative stability decreases simbatically with the pKa of the corresponding ammonium cation and antibactically with the lipophilicity of AM indicating the bond between the reagents strengthening, with an increase in the basicity and hydrophilicity of AM. The reaction of “soft” oxidation of S (IV) to S (VI) can be used to obtain highly concentrated SO3 resulting of the formed ammonium sulfates thermolysis. The latter is typical for these salts, in which the melting temperature (destruction) of amines, formed them, is above 260 0С (H2SO4 decomposition temperatures). For the first time, consistent and objective information about the composition of ammonium compounds formed in 23 SO2 – AM – H2O systems was obtained. It was shown this interaction was accompanied by the corresponding ammonium cations formation in the solutions of sulfites, hydrosulfites, pyrosulfites and mixed salts (sulfite-hydrosulfite). It was established that the relationship between the stability of ammonium sulfite and hydrosulfite with pKa values of ethanolamines had symbate character. For the first time, the contributions of the chemical and physical components to the total solubility of sulfur dioxide in aqueous solutions of ethanolamines have been revealed. It was shown with a decrease in the basicity of ethanolamine and an increase of its hydration degree in the series of methylmono-, mono-, di- and triethanolamine, the salting in constant in the equation for physical sorption of SO2 to decrease. The revealed for the first time correlations can be useful in the development sanitary air purification from SO2 methods, immobilized chemical sorbents for gas and ion-exchange chromatography, regeneration of chemical sorbents and utilization of sorption products. The developed import-substituting SO2 impregnated fibrous chemical sorbents are introduced in practice and are used for the manufacture of gas-mask elements of lightweight gas-dust respirators. The new reactions simplify the methods of known compounds synthesis and allow to obtain new components of buffer solutions for biological and biochemical studies, and prospective pharmaceuticals.
Опис
Ключові слова
оксид сульфуру (IV), алкіламіни, водні розчини, хемосорбція, кислотно-основна взаємодія, сульфоокиснення, оксид серы (IV), алкиламины, водные растворы, хемосорбция, кислотно-основное взаимодействие, сульфоокисление, sulfur dioxide, alkylamines, aqueous solutions, chemosorption, acid- base interaction, sulfooxidation
Бібліографічний опис
Хома Р. Є. Кислотно-основна взаємодія та сульфоокиснення при хе-мосорбції оксиду сульфуру (IV) водними розчинами алкіламінів : автореф. дис. … док. хіміч. наук : спец.: 02.00.01 – неорганічна хімія/ Р. Є. Хома. – Київ, 2019. – 53 с.