Density of nafion exchanged with transition metal complexes and tetramethyl ammonium, ferrous, and hydrogen ions: commercial and recast films.

The densities of commercial Nafion 117 and cast Nafion 1100 films were determined by the hydrostatic weighing method for films fully exchanged with hexaammineruthenium(III), tris(2,2' bipyridyl)ruthenium(II), tetramethylammonium, ferrous, and hydrogen ions. Films were pretreated in either water or concentrated nitric acid prior to cation exchange. All densities ranged between 1.65 and 2.19 g/cm3. Excluding the proton-exchanged films, the average density is 1.90 +/- 0.14 g/cm3, well in excess of the 1.58 g/cm3 commonly employed for Nafion. The density of acid-pretreated Nafion 1100 was constant at 1.95 +/- 0.03 g/cm3 for all cations except the proton. A simple, empirical model based on the Coulombic interaction between the intercalated cation and the sulfonate sites of the Nafion characterizes density for the commercial Nafion 117 films. A modified version of the model is appropriate for water-treated Nafion 1100. Water content of the films and implications for characterizing modified electrodes are discussed.