Phase equilibrium (temperature−composition) relations of tetra-n-butylphosphonium formate (TBP-For), acetate (TBP-Ace), and lactate (TBP-Lac) semiclathrate hydrate systems have been measured. The highest equilibrium temperatures of TBP-For, TBP-Ace, and TBP-Lac semiclathrate hydrates were 280.9, 284.6, and 283.8 K at the atmospheric pressure, respectively, where the composition of tetran-butylphosphonium carboxylate was approximately 0.035 ± 0.001 (mole fraction) in every system. The dissociation enthalpies of tetra-nbutylphosphonium carboxylate semiclathrate hydrates were measured by differential scanning calorimetry. The dissociation enthalpies of TBP-For, TBP-Ace, and TBP-Lac semiclathrate hydrates were (187 ± 3), (193 ± 3), and (177 ± 3) J•g −1 , respectively.

Semiclathrate hydrate (SCH) is one of the phase change materials suitable for cold energy storage. Thermodynamic properties of SCHs, such as an equilibrium temperature and the dissociation enthalpy, depend on the size and shape of the guest substances. In the present study, to reveal the effects of steric conformations of the guest anions on the thermodynamic properties of SCHs, tetra-n-butylphosphonium dicarboxylate (TBP-DC) SCHs, where the anion was oxalate (TBP-Oxa), malonate (TBP-Mal), succinate (TBP-Suc), glutarate (TBP-Glu), maleate (TBP-Male), or fumarate (TBP-Fum), were investigated. TBP-Oxa, -Mal, -Suc, and -Fum SCHs had similar equilibrium temperatures, whereas the equilibrium temperatures of TBP-Glu and -Male SCHs were higher. This suggests that the size and conformation of glutarate and maleate anions are appropriate for the cage structures of SCHs. Moreover, we compared the equilibrium temperatures of TBP-Suc, -Male, and -Fum SCHs because TBP-Suc, -Male, and -Fum have similar anion structures. The equilibrium temperature of TBP-Suc SCH was similar to that of TBP-Fum SCH, whereas TBP-Male SCH showed a higher equilibrium temperature. This result implies that the succinate anion is accommodated in the trans conformation, similar to the fumarate anion, in the hydrate cages.