Peritectic phase behavior of tetra-n-butylphosphonium trifluoroacetate semiclathrate hydrate

Abstract

Phase equilibrium (temperature–composition) relations of the tetra-n-butylphosphonium trifluoroacetate (TBP-TFA) + water binary system including solid (semiclathrate hydrate, SCH)-liquid equilibria and liquid-liquid equilibria were investigated. Phase diagram of TBP-TFA SCH exhibited peritectic behavior. The maximum decomposition temperature (peritectic temperature) of TBP-TFA SCH at atmospheric pressure were 275.9 ± 0.1 K. The stoichiometric composition of TBP-TFA SCH was located at the mole fraction of 0.027 ± 0.002. The decomposition enthalpy of TBP-TFA SCH was 199 ± 2 J/g. At temperatures above the lower critical solution temperature (LCST), the liquid-liquid phase separation appeared. Interestingly, the composition at the LCST was 0.026 ± 0.002, which is very similar to the stoichiometric composition of TBP-TFA SCH. It implies that both cluster-based solution structures are similar.