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H3O -2 ions with a strong quasi-symmetrical H-bond and their hydration in aqueous solutions of NaOH and KOH

  • Kinetics and Mechanism of Chemical Reactions. Catalysis
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Abstract

Ion-molecular interactions in aqueous solutions of NaOH (0–47.8%) and KOH (0–51.95%) are studied by multiple frustrated total internal reflection IR spectroscopy. Interpretation of the spectra and analysis of the spectral data are performed based on the results of DFT calculations (B3LYP/6-31++G(d, p)) of the characteristics of the free and double hydrated H3O -2 ion. It is established that the changes in the IR spectra of NaOH and KOH aqueous solutions caused by increasing alkali concentration are due to the formation of H3O -2 ions with a strong quasi-symmetrical hydrogen bond and their subsequent hydration by one or two water molecules. The influence of the cation nature on the degree of hydration of H3O -2 ions is demonstrated. The equilibrium concentrations of monohydrate (H3O -2 ∙ H2O) and dihydrate (H3O -2 ∙ 2H2O) are calculated and their IR continuous absorption spectra are isolated.

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Authors and Affiliations

  1. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

    V. D. Maiorov, G. I. Voloshenko & I. S. Kislina

  2. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia

    E. G. Tarakanova & G. V. Yukhnevich

Authors
  1. V. D. Maiorov
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  2. G. I. Voloshenko
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  3. I. S. Kislina
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  4. E. G. Tarakanova
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  5. G. V. Yukhnevich
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Correspondence to V. D. Maiorov or E. G. Tarakanova.

Additional information

Original Russian Text © V.D. Maiorov, G.I. Voloshenko, I.S. Kislina, E.G. Tarakanova, G.V. Yukhnevich, 2016, published in Khimicheskaya Fizika, 2016, Vol. 35, No. 5, pp. 36–46.

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Maiorov, V.D., Voloshenko, G.I., Kislina, I.S. et al. H3O -2 ions with a strong quasi-symmetrical H-bond and their hydration in aqueous solutions of NaOH and KOH. Russ. J. Phys. Chem. B 10, 407–416 (2016). https://doi.org/10.1134/S1990793116030040

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  • DOI: https://doi.org/10.1134/S1990793116030040

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