Concentrations of water and thionyl chloride complexes and clusters: hydrolysis products in the gas phase
https://doi.org/10.21285/2227-2925-2019-9-2-170-175
Abstract
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.
About the Author
M. A. Zasovskaya
Ukhta State Technical University
Russian Federation
Russian Federation
Ph.D. (Chemistry), Associate Professor, Head of the Department of Chemistry,
Ukhta, Komi Republic
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For citations:
Zasovskaya M.A. Concentrations of water and thionyl chloride complexes and clusters: hydrolysis products in the gas phase. Proceedings of Universities. Applied Chemistry and Biotechnology. 2019;9(2):170-175. https://doi.org/10.21285/2227-2925-2019-9-2-170-175
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