Abstract
Isobaric volumetric heat capacities of aqueous solutions of K4Fe(CN)6, K3Fe(CN)6, K3Co(CN)6, K2Ni(CN)4, and KAg(CN)2 have been measured at 298.15 K over the approximate concentration range 0.02 to 0.4 mol·kg–1 using a Picker flow calorimeter. These data were combined with measured densities to calculate the corresponding apparent molar isobaric heat capacities, Cpϕ. The values so obtained were fitted as a function of concentration using an extended Redlich–Rosenfeld–Meyer-type equation to provide the standard state (infinite dilution) quantities, Cpϕo, for each salt. The Cpϕ values for all the salts studied showed similar dependences on concentration, with a slight upward curvature at higher molalities, possibly due to anion aggregation. Values of Cpϕo for the aquated cyanometallate anions were estimated using the tetraphenylphosphonium tetraphenylborate extrathermodynamic assumption and were little affected by ion size but were strongly dependent on ionic charge, ranging from −191 J·K–1·mol–1 for [Fe(CN)...
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