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Hydrate-Anion Complex of Proton [H(H2O)n]+А− as the Basis of the Complex Acidity Function Н0w of Aqueous Solutions of Strong Mineral Acids in Excess of Water

  • Selected articles originally published in Russian in Rossiiskii Khimicheskii Zhurnal (Russian Chemistry Journal)
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Abstract

Based on the concept of the proton hydrate-anion complex [H(H2O)n]+A−, equations are proposed that characterize the catalytic activity of the proton in aqueous solutions of three acids: sulfuric, hydrochloric, and chloric. The equations are based on the linear dependence of the value of “excessive acidity” on the logarithm of the relative stoichiometric concentration of water Х = f(log C*w) in acid solutions with a predominance of water (Н2О/НА > 1). Using the directly proportional dependence of the Hammett function (–H0) on the sum of parameters (log C*H+ + mX), two-parameter equations were obtained for calculating the complex function of acidity –Hw0 = log C*H+ + Blog C*w (standard state—pure water, C0w). The equations make it possible to calculate the function Hw0 at a given acid concentration, having only data on the concentrations of the proton CH+ and water Hw0, i.e. avoiding the use of the ratio of the activity coefficients of the components included in parameter X. The function Hw0 collectively reflects the participation of proton and water in the acidity of the medium, practically reproduces the experimental values of H0 obtained by different authors in the concentration range from pure water to 68 wt % (H2SO4), 40% (HCl), 70% (HClO4), combines the pH and H0 scales. It is concluded that the Blog Hw0 contribution, which characterizes the participation of water in the hydration shells of ions, is determined by their nature and plays no less important role in characterizing the acidity of the medium than the proton itself. The final tables of the concentration dependence of the values Hw0 for each of the acids are given. The paper represents a methodological review, since it is based on a critical analysis of experimental literature data.

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Notes

  1. Cw—stoichiometric water concentration (analytical concentration of H2O in a two-component H2O/HA system, expressed in mol/L and reduced to normal conditions).

  2. The state of pure solvent (water) at 298.15 K is taken as the standard state of water (C0w = 1000 cm3·0.99705 g/cm3/ 18.01153 g/mol = 55.34462mol; log C0w = 1.74308).

  3. The activity of water is the result of its corrected concentration on the activity coefficient, which takes into account a decrease in the vapor pressure of water over an acid solution compared with the vapor pressure over clean water and, in turn, an supposed decrease in its real concentration due to the formation of H-bonds with an excess proton and other ions of the medium.

  4. In the case of sulfuric acid, parameter B reflects the total effect of the anions: HSO4– and the doubly charged anion SO42–, which reaches a maximum concentration of 56% H2SO4.

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  121. Cw—stoichiometric water concentration (analytical concentration of H2O in a two-component H2O/HA system, expressed in mol/L and reduced to normal conditions).

  122. The state of pure solvent (water) at 298.15 K is taken as the standard state of water (C0w = 1000 cm3·0.99705 g/cm3/ 18.01153 g/mol = 55.34462mol; log C0w = 1.74308).

  123. The activity of water is the result of its corrected concentration on the activity coefficient, which takes into account a decrease in the vapor pressure of water over an acid solution compared with the vapor pressure over clean water and, in turn, an supposed decrease in its real concentration due to the formation of H-bonds with an excess proton and other ions of the medium.

  124. In the case of sulfuric acid, parameter B reflects the total effect of the anions: HSO4– and the doubly charged anion SO42–, which reaches a maximum concentration of 56% H2SO4.

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  1. Ivanovo State University, 153025, Ivanovo, Russia

    S. N. Ivanov & D. F. Pyreu

  2. Ivanovo State University of Chemistry and Technology, 153000, Ivanovo, Russia

    V. A. Kozlov, T. E. Nikiforova & O. I. Koifman

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Ivanov, S.N., Kozlov, V.A., Nikiforova, T.E. et al. Hydrate-Anion Complex of Proton [H(H2O)n]+А− as the Basis of the Complex Acidity Function Н0w of Aqueous Solutions of Strong Mineral Acids in Excess of Water. Russ J Gen Chem 93, 3207–3223 (2023). https://doi.org/10.1134/S1070363223120216

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