Activity coefficients of hydrochloric acid in hydrogen chloride-metal perchlorate-water systems.

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In the HCl–LiClO4–H2O, HCl–NaClO4–H2O, HCl–Mg(ClO4)2–H2O, HCl–Ba(ClO4)2–H2O, HCl–LiClO4–NaClO4–H2O, HCl–NaClO4–Ba(ClO4)2–H2O, and HCl–LiClO4–NaClO4–Ba(ClO4)2–H2O systems, the mean activity coefficients of hydrochloric acid, γ±HCl have been obtained at 25 °C by emf measuremts of the cell: H2(Pt)⁄HCl,MClO4,M′(ClO4)2,···⁄AgCl,Ag(M=Li,Na;M′=Mg,Ba) Moreover, the following relation has been examined with the experimental results: logγ±HCl=logγ°±HCl+\underseti∑ai(HCl)mi (i\neweqH,Cl) where γ°±HCl is the mean activity coefficient of hydrochloric acid in a solution containing only hydrochloric acid at the same ionic strength as the mixture; mi is the molality of the i ion, and ai(HCl) is the parameter assigned to the three-ion system of hydrogen, chloride, and i ions, but is independent of the ionic strength. The results of the examination with aM(HCl) determined in our previous paper showed that aClO4(HCl) may be about zero regardless of the kind of metal ion coexisting in the solution. The activity coefficients calculated by the above relationship with the determined parameters agree, with deviation of only about 5%, with the experimental results for all the systems.
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