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DOI: 10.1039/A803473G (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 2535-2540

The problem of acidity in concentrated aqueous solutions of sulfuric acid

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Nunziata C. Marziano, Alberto Tomasin, Claudio Tortato and Paolo Isandelli

Abstract

Concentrated aqueous sulfuric acid mixtures, which ionize according to the equilibria (a) and (b) [(a) HSO4– ⇄ SO42– + H+; (b) H2SO4 ⇄ HSO4– + H+], have been analysed and the corresponding activity coefficient functions [Mc(s)] of the solvent [Mc(HSO4–) = –log ([hair space][hair space]fSO42– fH+/[hair space]fHSO4–[hair space]); Mc(H2SO4) = –log ([hair space][hair space]fHSO4– fH+/fH2SO4)] have been determined by using the concentrations of the species SO42–, HSO4–, H2SO4. The Mc(s) have been compared with the Mc(i) function [Mc(i) = –log ([hair space][hair space]fB[hair space][hair space] fH+/fBH+)], the latter one being determined by the protonation equilibria of weak bases (B) (B + H+ ⇄ BH+). The results show that the interactions of solute and solvent can be linearly related [i.e.Mc(i) = nisMc*(s) and Mc*(s) = Mc(HSO4–) + Mc(H2SO4)] in the range 0.1–100 wt% H2SO4 provided that both equilibria of sulfuric acid, correctly normalized, are taken into account.

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