Apparent Molal Heat Capacities and Volumes of Tetrabutylammonium Carboxylates and Related Solutes in Water at 25 °C

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Abstract
The apparent molal volumes and heat capacities were measured in water at 25 °C with a flow digital densimeter and a flow microcalorimeter for the following salts: tetrabutylammonium octanoate, tetrabutylammonium butanoate, tetrabutylammonium bromide, ammonium acetate, ammonium chloride, ammonium bromide, sodium octanoate, and sodium acetate. The tetrabutylammonium octanoate and butanoate and sodium octanoate form micelles at 0.13, 0.6, and 0.35 M, respectively. The concentration dependence of the apparent molal volumes of the carboxylate salts is similar to that of typical hydrophobic or hydrophilic electrolytes. On the other hand, in the submicellar region, the concentration dependence of their apparent molal heat capacities is abnormal when compared with model electrolytes. It seems that the heat capacities may be reflecting interactions involving a hydrogen bonding of the carboxylate group with water.

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