Herald of Technological University Herald of Technological University ВЕСТНИК ТЕХНОЛОГИЧЕСКОГО УНИВЕРСИТЕТА 3034-4689 60224 СТРУКТУРА ВЕЩЕСТВА И ТЕОРИЯ ХИМИЧЕСКИХ ПРОЦЕССОВ СТРУКТУРА ВЕЩЕСТВА И ТЕОРИЯ ХИМИЧЕСКИХ ПРОЦЕССОВ КВАНТОВО-ХИМИЧЕСКОЕ ИССЛЕДОВАНИЕ КАТАЛИТИЧЕСКОГО ВЛИЯНИЯ КАРБОНАТ-ИОНА НА ОКИСЛЕНИЕ АРСЕНИТА ГИДРОКСИЛ-РАДИКАЛАМИ КВАНТОВО-ХИМИЧЕСКОЕ ИССЛЕДОВАНИЕ КАТАЛИТИЧЕСКОГО ВЛИЯНИЯ КАРБОНАТ-ИОНА НА ОКИСЛЕНИЕ АРСЕНИТА ГИДРОКСИЛ-РАДИКАЛАМИ Твердов И Д Твердов И Д Гришаева Т Н Гришаева Т Н Маслий А Н Маслий А Н masliy@kstu.ru Кузнецов Ан М Кузнецов Ан М am_kuznetsov@kstu.ru Коршин Г В Коршин Г В korshin@uw.edu КНИТУ ru КНИТУ ru КНИТУ ru КНИТУ ru КНИТУ ru КНИТУ ru КНИТУ ru КНИТУ ru Department of Civil and Environmental Engineering, Box 352700, University of Washington, Seattle, WA 98195-2700, United States ru Department of Civil and Environmental Engineering, Box 352700, University of Washington, Seattle, WA 98195-2700, United States ru 01 08 2025 01 08 2025 16 4 58 63 19 04 2023 https://vestniktu.ru/en/nauka/article/60224/view

В рамках теории функционала плотности исследован механизм окисления арсенита гидроксил-радикалами, рассчитаны термодинамические и структурные характеристики исходных частиц, переходных состояний, а также пред- и постреакционных комплексов, которые формируются в этом процессе. Оценена энергия активации процесса окисления и показана каталитическая роль карбонат-ионов в окислении арсенита.

The mechanism of oxidation of arsenite by hydroxil radicals was examined via quantum-chemical simulations that employed the density functional theory. Structural and thermodynamic characteristics of reactants, transition states, pre- and post-reaction complexes which are formed in this process were determined as well. The activation energy of the oxidation process was estimated and a catalytic role of the carbonate ions in oxidation of arsenite was shown.

теория функционала плотности PCM арсенит карбонта-ионы механизм окисления density functional theory PCM arsenite carbonate ions oxidation mechanism теория функционала плотности PCM арсенит карбонта-ионы механизм окисления density functional theory PCM arsenite carbonate ions oxidation mechanism

Smedley, P. L A review of the source, behavior and distribution of arsenic in natural waters. / Smedley, P. L.; Kinniburgh, D. G. // Appl. Geochem. - 2002, -Vol. 17. -P. 517-568. Smedley, P. L A review of the source, behavior and distribution of arsenic in natural waters. / Smedley, P. L.; Kinniburgh, D. G. // Appl. Geochem. - 2002, -Vol. 17. -P. 517-568. Rahman, A Arsenic Exposure and Risk of Spontaneous Abortion, Stillbirth, and Infant Mortality./ Rahman, A.; Persson, L.A.; Nermell, B.; El Arifeen, S.; Ekstrom, E.C.; Smith, A.H.; Vahter, M. // Epidemiology. -2010, -Vol. 21. - P. 797-804. Rahman, A Arsenic Exposure and Risk of Spontaneous Abortion, Stillbirth, and Infant Mortality./ Rahman, A.; Persson, L.A.; Nermell, B.; El Arifeen, S.; Ekstrom, E.C.; Smith, A.H.; Vahter, M. // Epidemiology. -2010, -Vol. 21. - P. 797-804. Berg M. Arsenic contamination of groundwater and drinking water in Vietnam: a human health threat. / Berg M.; Tran, H. C.; Nguyen, T. C.; Pham H. V.; Schertenleib, R.; Giger,W. // Environ. Sci. Technol. 2001, 35 (13), 2621-2626. Berg M. Arsenic contamination of groundwater and drinking water in Vietnam: a human health threat. / Berg M.; Tran, H. C.; Nguyen, T. C.; Pham H. V.; Schertenleib, R.; Giger,W. // Environ. Sci. Technol. 2001, 35 (13), 2621-2626. Mao, G.Y. Prevalence of disability in an arsenic exposure area in Inner Mongolia, China. / Mao, G.Y.; Guo, X.J.; Kang, R.Y.; Ren, C.S.; Yang, Z.P.; Sun, Y.S.; Zhang, C.W.; Zhang, X.J.; Zhang, H.T.; Yang, W. // Chemosphere. -2010, -Vol. 80. -P. 978-981. Mao, G.Y. Prevalence of disability in an arsenic exposure area in Inner Mongolia, China. / Mao, G.Y.; Guo, X.J.; Kang, R.Y.; Ren, C.S.; Yang, Z.P.; Sun, Y.S.; Zhang, C.W.; Zhang, X.J.; Zhang, H.T.; Yang, W. // Chemosphere. -2010, -Vol. 80. -P. 978-981. Kumar, M. Arsenic enrichment in groundwater in the middle Gangetic Plain of Ghazipur District in Uttar Pradesh, India. / Kumar, M.; Kumar, P.; Ramanathan, A.L.; Bhattacharya, P.; Thunvik, R.; Singh, U.K.; Tsujimura, M.; Sracek, O. // J. Geochemical Exploration. -2010. -Vol. 105. -P. 83-94. Kumar, M. Arsenic enrichment in groundwater in the middle Gangetic Plain of Ghazipur District in Uttar Pradesh, India. / Kumar, M.; Kumar, P.; Ramanathan, A.L.; Bhattacharya, P.; Thunvik, R.; Singh, U.K.; Tsujimura, M.; Sracek, O. // J. Geochemical Exploration. -2010. -Vol. 105. -P. 83-94. Le, X. C. Determination of monomethyl arsonous acid, a key arsenic methylation intermediate, in human urine. / Le, X. C.; Ma, M.; Lu, X.; Cullen, W. R.; Aposhian, V.; Zheng, B. // Environ. Health Perspect. -2000. -Vol. 108. -P. 1015-1018. Le, X. C. Determination of monomethyl arsonous acid, a key arsenic methylation intermediate, in human urine. / Le, X. C.; Ma, M.; Lu, X.; Cullen, W. R.; Aposhian, V.; Zheng, B. // Environ. Health Perspect. -2000. -Vol. 108. -P. 1015-1018. Le, X. C. Speciation of key arsenic metabolic intermediates in human urine. / Le, X. C.; Lu, X.; Ma, M.; Cullen, W. R.; Aposhian, H. V.; Zheng, B. // Anal. Chem. -2000. -Vol. 72. -P. 5172-5177. Le, X. C. Speciation of key arsenic metabolic intermediates in human urine. / Le, X. C.; Lu, X.; Ma, M.; Cullen, W. R.; Aposhian, H. V.; Zheng, B. // Anal. Chem. -2000. -Vol. 72. -P. 5172-5177. Benjamin, M.M. Water Chemistry // McGraw Hill. -2002. Benjamin, M.M. Water Chemistry // McGraw Hill. -2002. Bissen, M. Arsenic-A Review. Part II. Oxidation of arsenic and its removal in water treatment. / Bissen, M.; Frimmel, F. H.// Acta Hydrochim.Hydrobiol. -2003. -Vol. 31. -P. 97-107. Bissen, M. Arsenic-A Review. Part II. Oxidation of arsenic and its removal in water treatment. / Bissen, M.; Frimmel, F. H.// Acta Hydrochim.Hydrobiol. -2003. -Vol. 31. -P. 97-107. Deschamps, E. Removal of As(III) and As(V) from water using a natural Fe and Mn enriched sample. / Deschamps, E.; Ciminelli, V.S.T. ; Holl, W.H. // Water Res. -2005. -Vol. 39. -P. 5212-5220. Deschamps, E. Removal of As(III) and As(V) from water using a natural Fe and Mn enriched sample. / Deschamps, E.; Ciminelli, V.S.T. ; Holl, W.H. // Water Res. -2005. -Vol. 39. -P. 5212-5220. Zhang, G.S. Preparation and evaluation of a novel Fe-Mn binary oxide adsorbent for effective arsenite removal. / , G.S.; Qu, J.H.; Liu, H.J.; Liu, R.P.; Wu, R.C. // Water Res. -2007. -Vol. 41. -P. 1921-1928. Zhang, G.S. Preparation and evaluation of a novel Fe-Mn binary oxide adsorbent for effective arsenite removal. / , G.S.; Qu, J.H.; Liu, H.J.; Liu, R.P.; Wu, R.C. // Water Res. -2007. -Vol. 41. -P. 1921-1928. Chen, W.F. Arsenic removal by iron-modified activated carbon. / Chen, W.F.; Parette, R.; Zou, J.Y.; Cannon, F.S. ; Dempsey, B.A. // Water Res. -2007. -Vol. 41. -P. 1851-1858. Chen, W.F. Arsenic removal by iron-modified activated carbon. / Chen, W.F.; Parette, R.; Zou, J.Y.; Cannon, F.S. ; Dempsey, B.A. // Water Res. -2007. -Vol. 41. -P. 1851-1858. Zhang, G.S. Removal mechanism of As(III) by a novel Fe-Mn binary oxide adsorbent: Oxidation and sorption. / , G.S.; Qu, J.H.; Liu, H.J.; Liu, R.P.; Li, G.T. // Env. Sci. Technol. 2007,41 (13), 4613-4619. Zhang, G.S. Removal mechanism of As(III) by a novel Fe-Mn binary oxide adsorbent: Oxidation and sorption. / , G.S.; Qu, J.H.; Liu, H.J.; Liu, R.P.; Li, G.T. // Env. Sci. Technol. 2007,41 (13), 4613-4619. Korshin, G. V. Development of an Electrochemical System for Arsenite Oxidation in Drinking Water; / Korshin, G. V.; Kim, J.; Velichenko, A. B. // Awwa Research Foundation: Denver, CO. -2004. Korshin, G. V. Development of an Electrochemical System for Arsenite Oxidation in Drinking Water; / Korshin, G. V.; Kim, J.; Velichenko, A. B. // Awwa Research Foundation: Denver, CO. -2004. Zhou, W. Mesoporous TiO2/alpha-Fe2O3: Bifunctional Composites for Effective Elimination of Arsenite Contamination through Simultaneous Photocatalytic Oxidation and Adsorption. / Zhou, W.; Fu, H.G.; Pan, K.; Tian, C.G.; Qu, Y.; Lu, P.P.; Sun, C.C. // J. Phys. Chem. A. -2008. -Vol. 112. -P. 19584-19589. Zhou, W. Mesoporous TiO2/alpha-Fe2O3: Bifunctional Composites for Effective Elimination of Arsenite Contamination through Simultaneous Photocatalytic Oxidation and Adsorption. / Zhou, W.; Fu, H.G.; Pan, K.; Tian, C.G.; Qu, Y.; Lu, P.P.; Sun, C.C. // J. Phys. Chem. A. -2008. -Vol. 112. -P. 19584-19589. Moore, K.W. Arsenic removal using oxidative media and nanofiltration. / Moore, K.W.; Huck, P.M.; Siverns, S. // J. American Water Works Assoc. -2008. -Vol. 100. -P. 74-83. Moore, K.W. Arsenic removal using oxidative media and nanofiltration. / Moore, K.W.; Huck, P.M.; Siverns, S. // J. American Water Works Assoc. -2008. -Vol. 100. -P. 74-83. Korshin, G.V. Electrochemical and XAFS study of effects of carbonate in oxidation of arsenite. / Korshin, G.V., Kim, J.; Velichenko, A.B.; Frenkel, A.I.// Env. Sci. Technol. -2006. -Vol. 40. -P. 228-234. Korshin, G.V. Electrochemical and XAFS study of effects of carbonate in oxidation of arsenite. / Korshin, G.V., Kim, J.; Velichenko, A.B.; Frenkel, A.I.// Env. Sci. Technol. -2006. -Vol. 40. -P. 228-234. Neuberger, C.S. Arsenic(III) carbonate complexing. / Neuberger, C.S.; Helz, G.R // Applied Geochemistry. -2005. -Vol. 20. -P. 1218-1225. Neuberger, C.S. Arsenic(III) carbonate complexing. / Neuberger, C.S.; Helz, G.R // Applied Geochemistry. -2005. -Vol. 20. -P. 1218-1225. Klaning, U.K. Arsenic (IV) - a pulse radiolysis study. / Klaning, U.K.; Bielski, B.H.J.; Sehested, K.// Inorg. Chem. -1989. -Vol. 28. -P. 2717-2724. Klaning, U.K. Arsenic (IV) - a pulse radiolysis study. / Klaning, U.K.; Bielski, B.H.J.; Sehested, K.// Inorg. Chem. -1989. -Vol. 28. -P. 2717-2724. Mustafa, I.A. Some specific features of the electrochemical behavior of arsenite ions at a rotating platinum electrode studied by cyclic voltammetry. / Mustafa, I.A.; Igumnov, M.S.; Rysev, A.P. // J. Anal. Chem. -1997. -Vol. 52. -P. 987-991. Mustafa, I.A. Some specific features of the electrochemical behavior of arsenite ions at a rotating platinum electrode studied by cyclic voltammetry. / Mustafa, I.A.; Igumnov, M.S.; Rysev, A.P. // J. Anal. Chem. -1997. -Vol. 52. -P. 987-991. Tossell, J.A. Theoretical studies on arsenic oxide and hydroxide species in minerals and in aqueous solution. / Tossell, J.A// Geochim. Cosmochim. Acta. -1997. -Vol. 61. -P. 1613-1623. Tossell, J.A. Theoretical studies on arsenic oxide and hydroxide species in minerals and in aqueous solution. / Tossell, J.A// Geochim. Cosmochim. Acta. -1997. -Vol. 61. -P. 1613-1623. Tossell, J.A. Calculation of the visible-UV absorption spectra of hydrogen sulfide, bisulfide, polysulfides, and As and Sb sulfides, in aqueous solution. / Tossell, J.A. // Geochem. Transactions. -2003. -Vol. 4. -P. 28-33. Tossell, J.A. Calculation of the visible-UV absorption spectra of hydrogen sulfide, bisulfide, polysulfides, and As and Sb sulfides, in aqueous solution. / Tossell, J.A. // Geochem. Transactions. -2003. -Vol. 4. -P. 28-33. Ramirez-Solis, A. Experimental and theoretical characterization of arsenite in water: Insights into the coordination environment of As-O. / Ramirez-Solis, A.; Mukopadhyay, R.; Rosen, B.P.; Stemmler, T.L. // Inorg. Chem. -2004. -Vol. 43. -P. 2954-2959. Ramirez-Solis, A. Experimental and theoretical characterization of arsenite in water: Insights into the coordination environment of As-O. / Ramirez-Solis, A.; Mukopadhyay, R.; Rosen, B.P.; Stemmler, T.L. // Inorg. Chem. -2004. -Vol. 43. -P. 2954-2959. Dombrowski, P.M. Thermodynamic analysis of arsenic methylation. / Dombrowski, P.M.; Long W., Farley, K.J.; Mahony, J.D.; Capitani J.F.; Di Toro, D.M.// Env. Sci. Technol. -2005. -Vol. 39. -P. 2169-2176 Dombrowski, P.M. Thermodynamic analysis of arsenic methylation. / Dombrowski, P.M.; Long W., Farley, K.J.; Mahony, J.D.; Capitani J.F.; Di Toro, D.M.// Env. Sci. Technol. -2005. -Vol. 39. -P. 2169-2176 Tossel, J.A. Calculations of interactions of bicarbonate with arsenites in aqueous solution and with the surfaces of Al hydroxide minerals./ Tossel, J.A.// In: Advances in Arsenic Research. American Chemical Society of Symposium Series. -2005. ACS, Washington, DC. Chapter 9. -P.118-128. Tossel, J.A. Calculations of interactions of bicarbonate with arsenites in aqueous solution and with the surfaces of Al hydroxide minerals./ Tossel, J.A.// In: Advances in Arsenic Research. American Chemical Society of Symposium Series. -2005. ACS, Washington, DC. Chapter 9. -P.118-128. Kubicki, J.D. Surface complex structures modelled with quantum chemical calculations: carbonate, phosphate, sulphate, arsenate and arsenite. / Kubicki, J.D.; Kwon, K.D.; Paul, K.W.; Sparks, D.L.// European J. Soil Science. -2007. -Vol. 58. -P. 932-944. Kubicki, J.D. Surface complex structures modelled with quantum chemical calculations: carbonate, phosphate, sulphate, arsenate and arsenite. / Kubicki, J.D.; Kwon, K.D.; Paul, K.W.; Sparks, D.L.// European J. Soil Science. -2007. -Vol. 58. -P. 932-944. Helz, G. R. Thermodynamic model for arsenic speciation in sulfidic waters: A novel use of ab initio computations. / Helz, G. R., Tossell, J. A. // Geochim. Cosmochim. Acta. -2008. -Vol. 72. -P. 4457-4468. Helz, G. R. Thermodynamic model for arsenic speciation in sulfidic waters: A novel use of ab initio computations. / Helz, G. R., Tossell, J. A. // Geochim. Cosmochim. Acta. -2008. -Vol. 72. -P. 4457-4468. Tossell, J. A. Calculation of the structures, stabilities, and vibrational spectra of arsenites, thioarsenites and thioarsenates in aqueous solution. / Tossell, J. A., Zimmermann, M. D. // Geochim. Cosmochim. Acta. -2008. -Vol. 72. -P. 5232-5242. Tossell, J. A. Calculation of the structures, stabilities, and vibrational spectra of arsenites, thioarsenites and thioarsenates in aqueous solution. / Tossell, J. A., Zimmermann, M. D. // Geochim. Cosmochim. Acta. -2008. -Vol. 72. -P. 5232-5242. Zimmermann, M.D. Acidities of Arsenic (III) and Arsenic (V) Thio- and Oxyacids in Aqueous Solution using the CBS-QB3/CPCM Method. / Zimmermann, M.D.; Tossell, J.A. // J. Phys. Chem. -2009. -Vol. 113. -P. 5105-5111. Zimmermann, M.D. Acidities of Arsenic (III) and Arsenic (V) Thio- and Oxyacids in Aqueous Solution using the CBS-QB3/CPCM Method. / Zimmermann, M.D.; Tossell, J.A. // J. Phys. Chem. -2009. -Vol. 113. -P. 5105-5111. Zhu, M.Q. Quantum Chemical Study of Arsenic (III, V) Adsorption on Mn-Oxides: Implications for Arsenic (III) Oxidation. / Zhu, M.Q.; Paul, K.W.; Kubicki, J.D.; Sparks, D.L.// Env. Sci. Technol. -2009. -Vol. 43. -P. 6655-6661 Zhu, M.Q. Quantum Chemical Study of Arsenic (III, V) Adsorption on Mn-Oxides: Implications for Arsenic (III) Oxidation. / Zhu, M.Q.; Paul, K.W.; Kubicki, J.D.; Sparks, D.L.// Env. Sci. Technol. -2009. -Vol. 43. -P. 6655-6661 Hernandez-Cobos, J. Aqueous solvation of As(OH)3: A Monte Carlo study with flexible polarizable classical interaction potentials. / Hernandez-Cobos, J; Vargas, MC; Ramirez-Solis, A; Ortega-Blake, I. // J. Chem. Phys. -2010. -Vol. 133. -P. 114501. Hernandez-Cobos, J. Aqueous solvation of As(OH)3: A Monte Carlo study with flexible polarizable classical interaction potentials. / Hernandez-Cobos, J; Vargas, MC; Ramirez-Solis, A; Ortega-Blake, I. // J. Chem. Phys. -2010. -Vol. 133. -P. 114501. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, ... W. Chen, M.W. Wong, J.L. Andres, C. Gonzalez, M. Head-Gordon, E.S. Replogle, and J.A. Pople, Gaussian 98, Revision A.11.2, Gaussian, Inc., Pittsburgh PA, 2001 M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, ... W. Chen, M.W. Wong, J.L. Andres, C. Gonzalez, M. Head-Gordon, E.S. Replogle, and J.A. Pople, Gaussian 98, Revision A.11.2, Gaussian, Inc., Pittsburgh PA, 2001 Becke, A.D. Density-functional thermochemistry. III. The role of exact exchange. / Becke, A.D. // J. Chem. Phys. -1993. -Vol. 98. -P. 5648-5652 Becke, A.D. Density-functional thermochemistry. III. The role of exact exchange. / Becke, A.D. // J. Chem. Phys. -1993. -Vol. 98. -P. 5648-5652 Lee, C. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density / Lee, C.; Yang, W.; Parr, R.G.// Phys. Rev. B. -1988. -Vol. 37. -P. 785-789. Lee, C. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density / Lee, C.; Yang, W.; Parr, R.G.// Phys. Rev. B. -1988. -Vol. 37. -P. 785-789. Chai, J.-D. Systematic optimization of long-range corrected hybrid density functionals. / J.-D. Chai and M. Head-Gordon // J. Chem. Phys. -2008. -Vol. 128. -P. 84-106 Chai, J.-D. Systematic optimization of long-range corrected hybrid density functionals. / J.-D. Chai and M. Head-Gordon // J. Chem. Phys. -2008. -Vol. 128. -P. 84-106 Chai, J.-D. Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. / J.-D. Chai and M. Head-Gordon // Phys. Chem. Chem. Phys. -2008. -Vol. 10. -P. 6615-6620. Chai, J.-D. Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. / J.-D. Chai and M. Head-Gordon // Phys. Chem. Chem. Phys. -2008. -Vol. 10. -P. 6615-6620. Dunning Jr., T. H. Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen. / T. H. Dunning Jr. // J. Chem. Phys. -1989. -Vol. 90. -P. 1007-1023. Dunning Jr., T. H. Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen. / T. H. Dunning Jr. // J. Chem. Phys. -1989. -Vol. 90. -P. 1007-1023. Barone, V. Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model / Barone, V.; Cossi, M. // J. Phys. Chem. A. -1998. -Vol. 102. -P. 1995-2001. Barone, V. Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model / Barone, V.; Cossi, M. // J. Phys. Chem. A. -1998. -Vol. 102. -P. 1995-2001. Маслий, А.Н. Квантово-химическое исследование комплексообразования в системе H3AsO3-CO32-/HCO3--H2O / А.Н. Маслий, Ан.М. Кузнецов, Г.В.Коршин // Вестник Казанск. Технол. Унив. -2012. -T.15, -N.15, -C.7-11. Masliy, A.N. Kvantovo-himicheskoe issledovanie kompleksoobrazovaniya v sisteme H3AsO3-CO32-/HCO3--H2O / A.N. Masliy, An.M. Kuznecov, G.V.Korshin // Vestnik Kazansk. Tehnol. Univ. -2012. -T.15, -N.15, -C.7-11. Бусыгина, А.А. Квантово-химическое исследование механизма окисления арсенита гидроксил-радикалами / А.А. Бусыгина, Т.Н. Гришаева, А.Н. Маслий, Ан.М. Кузнецов, Г.В.Коршин // Вестник Казанск. Технол. Унив. -2012. -T.15, -N.22, -C.22-27. Busygina, A.A. Kvantovo-himicheskoe issledovanie mehanizma okisleniya arsenita gidroksil-radikalami / A.A. Busygina, T.N. Grishaeva, A.N. Masliy, An.M. Kuznecov, G.V.Korshin // Vestnik Kazansk. Tehnol. Univ. -2012. -T.15, -N.22, -C.22-27.