vuzbiochemiИзвестия вузов. Прикладная химия и биотехнологияProceedings of Universities. Applied Chemistry and Biotechnology2227-29252500-1558ИРНИТУ10.21285/2227-2925-2019-9-2-170-175vuzbiochemi-187Research ArticleХИМИЧЕСКИЕ НАУКИCHEMICAL SCIENCESКонцентрации нейтральных и заряженных комплексов и кластеров воды, тионилхлорида и продуктов его гидролиза в газовой фазеConcentrations of water and thionyl chloride complexes and clusters: hydrolysis products in the gas phaseЗасовскаяМ. А.ZasovskayaM. A.

к.х.н., доцент, заведующая кафедрой химии,

г. Ухта, Республика Коми

Ph.D. (Chemistry), Associate Professor, Head of the Department of Chemistry,

Ukhta, Komi Republic

aspect51@yandex.ruУхтинский государственный технический университетРоссияUkhta State Technical UniversityRussian Federation20192709201992170175Copyright © Засовская М.А., 20192019Засовская М.А.Zasovskaya M.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vuzbiochemi.elpub.ru/jour/article/view/187

Участие в реакциях гидролиза и гидратации комплексов и кластеров воды предполагает протекание сложных многостадийных реакций по различным механизмам. Концентрация нейтральных и заряженных комплексов и кластеров в реакционной смеси влияет на скорость и механизм гидролиза. Поэтому целью данной работы является расчет концентраций комплексов и кластеров участвующих в газофазном гидролизе тионилхлорида и установление наиболее вероятных каналов реакции. На основе термодинамических данных, полученных методами квантово-химического моделирования B3LYP/6–311++G(2d,2р), MP2/aug-cc-pVTZ и G4 были рассчитаны концентрации комплексов и кластеров воды, тионилхлорида, а также продуктов его гидролиза в газовой фазе. Оптимизированы структуры комплексов воды состава (H2O)n, n=1–5,8. Найдены ациклические структуры комплексов (H2O)4 и (H2O)5 в газовой фазе, рассчитаны их концентрации, которые отличны от концентраций циклических комплексов. Рассчитанные концентрации заряженных комплексов и кластеров (H+)∙(H2O)n и (H2O)n·(OH-) Cl–(H2O)n, SOCl+ (H2O)n, (SOCl2(H2O)n) – несущественны, поэтому предположение о гидролизе ионных частиц, образующихся или существующих в газовой фазе внутри кластеров воды может быть исключено. Концентрации нейтральных кластеров SOCl2(H2O)n и HCl(H2O)n составляют от 1014 до 101 молекул/см3 , в зависимости от числа молекул воды в кластере, наибольшей концентрацией обладают SOCl2(H2O) и HCl(H2O). Расчет концентраций кластеров SOCl2(H2O)n проводился в предположении, что концентрация тионилхлорида равна концентрациям насыщенного пара воды, что вполне возможно вблизи промышленных объектов по производству высокоёмких источников тока. Наиболее вероятными каналами гидролиза являются реакции с комплексами и кластерами, концентрации которых являются самыми высокими, это реакции нейтральных кластеров (H2O)n и SOCl2(H2O)n, что совпадает с результатами предыдущей работы. 

The presence of water complexes and clusters in hydrolysis and hydration reactions implies complex multi-step processes involving various mechanisms. The concentration of neutral and charged complexes and clusters in the reaction mixture affects the rate and mechanism of hydrolysis. Therefore, the aim of this work was to calculate the concentrations of the complexes and clusters involved in gas -phase hydrolysis of thionyl chloride, as well as to establish the most probable reaction channels. Based on the thermodynamic data obtained by the B3LYP/6–311++G(2d,2p), MP2/aug-cc-pVTZ and G4 methods of quantum chemical modelling, the gas-phase concentrations of the complexes and clusters of water and thionyl chloride, as well as the hydrolysis products of the latter, were calculated. The structures of water complexes of composition (H2O)n (n = 1-5.8) were identified and optimised. Acyclic structures of the (H2O)4 and (H2O)5 complexes were identified in the gas phase having concentrations different from those calculated in cyclic complexes. Calculated concentrations of charged complexes and clusters (H+ )∙(H2O)n and (H2O)n·(OH-) Cl-(H2O)n, SOCl+(H2O)n, (SOCl2(H2O)n) - are negligible. Therefore, the assumption concerning the hydrolysis of formed or existing ionic particles in the gas phase inside water clusters can be excluded. Concentrations of SOCl2(H2O)n and HCl (H2O)n neutral clusters range from 1014 to 101 molecules/cm3 , depending on the number of water molecules in a cluster. SOCl2(H2O) and HCl(H2O) are characterised by the highest concentration. A calculation of SOCl2(H2O)n cluster concentrations was performed under the assumption that the concentration of thionyl chloride is equal to the concentration of saturated water vapour, which is quite possible near industrial facilities for the production of high-capacity current sources. The most probable channels for hydrolysis are presented by reactions of complexes and clusters having the highest concentrations. These reactions of (H2O)n and SOCl2(H2O)n neutral clusters are in a good agreement with the results of previous work. 

концентрации кластеров водытионилхлоридгазофазный гидролизconcentration of water clustersthionyl chloridegas-phase hydrolysisReferencesSzczesniak M.M., Scheiner S., Bouteiller Y. Theoretical study of H2O-HF and H2O-HCl: Comparison with experiment // The Journal of Chemical Physics. 1984. Vol. 81. No. 11. P. 5024–5030.Szczesniak M.M., Scheiner S., Bouteiller Y. Theoretical study of H2O-HF and H2O-HCl: Comparison with experiment. Journal of Chemical Physics. 1984, vol. 81, no. 11, pp. 5024–5030.Chaban G.M., Gerber R.B., Janda K.C. The transition from hydrogen bonding to ionization in (HCl)n(NH3)n and (HCl)n(H2O)n clusters: consequences for anharmonic vibrational spectroscopy // J. Phys. Chem. A. 2001. Vol. 105. P. 8323–8332.Chaban G.M., Gerber R.B., Janda K.C. The transition from hydrogen bonding to ionization in (HCl)n(NH3)n and (HCl)n(H2O)n clusters: consequences for anharmonic vibrational spectroscopy. Journal of Physical Chemistry. A. 2001, vol. 105, pp. 8323–8332.Ignatov S.K., Sennikov P.G., Ault B.S., Bagatur’yants A.A., Simdyanov I.V., Razuvaev A.G., Klimov E.Ju., Gropen O. Water Complexes and Hydrolysis of Silicon Tetrafluoride in the Gas Phase: An ab InitioStudy // The Journal of Physical Chemistry A. 1999. Vol. 103. No. 41. P. 8328–8336.Ignatov S.K., Sennikov P.G., Ault B.S., Bagatur’yants A.A., Simdyanov I.V., Razuvaev A.G., Klimov E.Ju., Gropen O. Water Complexes and Hydrolysis of Silicon Tetrafluoride in the Gas Phase: An ab InitioStudy. Journal of Physical Chemistry. A. 1999, vol. 103, no. 41, pp. 8328–8336.Yeung C.S., Ng P.S., Guan X., Phillips D.L. Water-Assisted Dehalogenation of Thionyl Chloride in the Presence of Water Molecules // The Journal of Physical Chemistry A. 2010. Vol. 114. P. 4123–4130.Yeung C.S., Ng P.S., Guan X., Phillips D.L. Water-Assisted Dehalogenation of Thionyl Chloride in the Presence of Water Molecules. Journal of Physical Chemistry. A. 2010, vol. 114, pp. 4123–4130.Johnson T.J., Disselkamp R.S., Su Y.-F.,Fel lows R.J., Alexander M.L., Driver C.J. Gas-phase Hydrolysis of SOCl2 // J. Phys. Chem. A. 2003. Vol. 107. No. 32. P. 6183–6190. DOI: 10.1021/jp022090vJohnson T.J., Disselkamp R.S., Su Y.-F., Fellows R.J., Alexander M.L., Driver C.J. Gas-phase Hydrolysis of SOCl2. Journal of Physical Chemistry. A. 2003, vol. 107, no. 32, pp. 6183–6190. DOI: 10.1021/jp022090vDriver C.J., Johnson T.J., Su Y.-F., Alexander M.L., Fellows R.J., Magnuson J., Disselkamp R.S., Roberts B.A. The Impact of Humidity, Temperature and Ultraviolet Light on the Near-Field Environmental Fate of Pinacolyl Alcohol, Methyl Iodide, Methylphosphonic Dichloride (DCMP) and Thionyl Chloride Using an Environmental Wind Tunnel. Humidity. Waschington: PNNL-14172, 2003. 70 p.Driver C.J., Johnson T.J., Su Y.-F., Alexander M.L., Fellows R.J., Magnuson J., Disselkamp R.S., Roberts B.A. The Impact of Humidity, Temperature and Ultraviolet Light on the Near-Field Environmental Fate of Pinacolyl Alcohol, Methyl Iodide, Methylphosphonic Dichloride (DCMP) and Thionyl Chloride Using an Environmental Wind Tunnel. Humidity. Waschington: PNNL-14172, 2003, 70 p.Ignatov S.K., Sennikov P.G., Razuvaev A.G., Schrems O. Ab-initio and DFT Study of the Molecular Mechanisms of SO3 and SOCl2 Reactions with water in the Gas Phase // J. Phys. Chem. A. 2004. Vol. 108. P. 3642–3649.Ignatov S.K., Sennikov P.G., Razuvaev A.G., Schrems O. Ab-initio and DFT Study of the Molecular Mechanisms of SO3 and SOCl2 Reactions with water in the Gas Phase. Journal of Physical Chemistry. A. 2004, vol. 108, pp. 3642–3649.Zasovskaya M.A., Ignatov S.K., Molecular pathways of SOCl2 hydrolysis within mono- and diaqua complexes. A quantum chemical study // Computational and Theoretical Chemistry. 2015. Vol. 1069. P. 56–65.Zasovskaya M.A., Ignatov S.K., Molecular pathways of SOCl2 hydrolysis within mono- and diaqua complexes. A quantum chemical study. Computational and Theoretical Chemistry. 2015, vol. 1069, pp. 56–65.Засовская М.А., Игнатов С.К. Поверхность потенциальной энергии системы SOCl2+2H2 // Известия Коми научного центра Уральского отделения РАН. 2015. N 2 (22). С. 12–18.Zasovskaya M.A., Ignatov S.K. Potential energy surface of the SOCl2+2H2O system. Izvestiya Komi nauchnogo tsentra Ural'skogo otdeleniya RAN. 2015, no. 2 (22), pp. 12–18. (In Russian)Засовская М.А., Игнатов С.К. Комплексы и кластеры воды, тионилхлорида и продуктов его гидролиза в газовой фазе. Термодинамические характеристики // Известия вузов. Прикладная химия и биотехнология. 2017. Т. 7. N 1. С. 40–49. DOI: 10.21285/2227-2925-2017-7-1-40-49.Zasovskaya M.A., Ignatov S.K. Complexes and clusters of water, thionil chloride and products of its hydrolysis in a gas phase. Thermodynamic characteristics. Izvestiya vuzov. Prikladnaya khimiya i Biotekhnologiya. 2017, vol. 7, no. 1, pp. 40–49. (In Russian) DOI: 10.21285/2227-2925-2017-7-1-40-49.Dunn M.E., Pokon E.K., Shields G.C. Thermodynamics of Forming Water Clusters at Various Temperatures and Pressures by Gaussian2, Gaussian-3,Complete Basis Set-QB3, and Complete Basis Set-APNO Model Chemistries; Implications for Atmospheric Chemistry // J. Am. Chem. Soc. 2003. Vol. 126. P. 2647–2653.Dunn M.E., Pokon E.K., Shields G.C. Thermodynamics of Forming Water Clusters at Various Temperatures and Pressures by Gaussian-2, Gaussian-3,Complete Basis Set-QB3, and Complete Basis Set-APNO Model Chemistries; Implications for Atmospheric Chemistry. J. Am. Chem. Soc. 2003, vol. 126, pp. 2647–2653.Kathmann Sh.M., SchenterG.K., Garrett B.C. Understanding the sensitivity of nucleation kinetics: A case study on water // The Journal of Chemical Physics. 2002. Vol. 116. P. 5046–5057.Kathmann Sh.M., Schenter G.K., Garrett B.C. Understanding the sensitivity of nucleation kinetics: A case study on water. Journal of Chemical Physics. 2002, vol. 116, pp. 5046–5057.Domnguez A., Niehaus T.A., Frauenheim T. Accurate Hydrogen Bond Energies within the Density Functional Tight Binding Method // The Journal of Physical Chemistry. A. 2015. Vol. 119. P. 3535−3544.Domnguez A., Niehaus T.A., Frauenheim T. Accurate Hydrogen Bond Energies within the Density Functional Tight Binding Method. Journal of Physical Chemistry. A. 2015, vol. 119, pp. 3535−3544.Yoskioki S.J. Application of the independent molecule model to the calculation of free energy and rigid-body motions of water hexamers // Journal of Molecular Graphics and Modelling. 2003. Vol. 21. No. 6. P. 487–498.Yoskioki S.J. Application of the independent molecule model to the calculation of free energy and rigid-body motions of water hexamers. Journal of Molecular Graphics and Modelling. 2003, vol. 21, no. 6, pp. 487–498.Saykally R.J., Wales D.J. Pinning Down the Water Hexamer // Science. 2012. Vol. 336: P. 814–815.Saykally R.J., Wales D.J. Pinning Down the Water Hexamer. Science. 2012, vol. 336, pp. 814–815.Bartolotti L.J., Rai D., Kulkarni A.D., Gejji S.P., Pathak R.K. Water clusters (H2O)n [n = 9–20] in external electric fields: exotic OH stretching frequencies near breakdown // Computational and Theoretical Chemistry. 2014. Vol. 1044. P. 66–73.Bartolotti L.J., Rai D., Kulkarni A.D., Gejji S.P., Pathak R.K. Water clusters (H2O)n [n = 9–20] in external electric fields: exotic OH stretching frequencies near breakdown. Computational and Theoretical Chemistry. 2014, vol. 1044, pp. 66–73.

The authors declare that there are no conflicts of interest present.