Abstract
The aqueous mixed (sodium chloride + sodium hydroxide) system has been studied using e.m.f. measurements at T=298.15 K of the combined cells Pt|Na–Hg|NaCl( m 1)+NaOH( m 2)|HgO|Hg|Pt and Pt|Tl–Hg|TlCl|NaCl( m 1)+NaOH( m 2)|HgO|Hg|Pt at constant total molalities ( m 1+ m 2) of (1, 2, 3, 4, 5, 6, 7, 9, and 11) mol·kg −1. The mean molal activity coefficients γ of each single component have been determined as a function of the respective molalities. For both components, the behaviour can, with reasonable approximation, be represented by Harned’s rule (linear dependence of lgγ on m), although a quadratic dependence is more appropriate. In terms of the mixing fraction X= m 2/ m TOT, the lgγ against X curves for NaCl and NaOH have slopes in opposite directions, contrary to (KCl+KOH) aq and most other (MX+MY) aq. The respective trace activity coefficients are unequal, and both of them are lower than the corresponding pure-component activity coefficients.
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