Volume 63, 1967

Apparent molal volumes and expansibilities of electrolytes in dilute aqueous solution

Abstract

A magnetic float technique has been developed for the measurement of densities of dilute aqueous solutions to within ±1 part in 106. Apparent molal volumes ϕv at 5 and 25° are presented for alkali chlorides and tetra-alkylammonium bromides in the molar concentration range 0.002 < c < 0.1. The results are discussed in terms of deviations from the Debye-Hückel limiting law, and it is shown that for the salts R4NBr, the concentration dependence of ϕv does not conform to the trends normally observed for univalent electrolytes. The ϕv(c½) behaviour is interpreted in terms of cation-cation interactions, induced by co-operative ion-water interactions. Mean apparent molal expansibilities ϕE at 15° are presented, and the ϕE(c½) plots for NaCl and KCl show good agreement with predicted limiting law behaviour. For the series R4NBr (except where R = Me) increasingly large positive excess expansibilities are observed.

Article information

Article type
Paper

Trans. Faraday Soc., 1967,63, 2586-2598

Apparent molal volumes and expansibilities of electrolytes in dilute aqueous solution

F. Franks and H. T. Smith, Trans. Faraday Soc., 1967, 63, 2586 DOI: 10.1039/TF9676302586

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