Effect of introducing a cyclobutylmethyl group into an onium cation on the thermodynamic properties of ionic clathrate hydrates

Abstract

Ionic clathrate hydrates (ICHs) have been applied to thermal storage materials, which can be utilized as unusual thermal energy sources. In the present study, we developed a novel ICH including tri-n-butyl(cyclobutylmethyl)phosphonium bromide (P444(1c4)-Br) as an unprecedented guest species. The highest equilibrium temperature and the dissociation enthalpy of P444(1c4)-Br ICH were 279.5 ± 0.1 K and 202 ± 2 J g⁻¹, respectively, at the mole fraction of 0.0255 ± 0.0008. The highest equilibrium temperature of P444(1c4)-Br ICH was slightly lower than that of the tetra-n-butylphosphonium bromide (P4444-Br) ICH. The dissociation enthalpy of P444(1c4)-Br ICH was larger than that of other ICHs with similar highest equilibrium temperatures. Cyclic hydrocarbon groups, together with normal, branched, saturated, and unsaturated hydrocarbon chains, can be one of the options for tuning the equilibrium temperature of ICHs.