A comparative study of ammonia solubility in imidazolium-based ionic liquids with different structural compositions

Four imidazolium-based ionic liquids (ILs) with two cations 1-pentyl-3-butylimidazolium [PBIM](+) and 1-benzyl-3-butylimidazolium tetrafluoroborate [BzBIM](+), and two anions tetrafluoroborate (BF4) and trifluoromethanesulfonate (OTf) were synthesized for NH3 solubility enhancement. The structural, thermal, and electrochemical stabilities, ionic conductivity, and viscosity of the four ILs, namely, [PBIM]BF4, [BzBIM]BF4, [PBIM]OTf, and [BzBIM]OTf, were investigated. Due to the intermolecular interaction of the benzyl group attached to the imidazolium ring, [BzBIM](+)-based ILs exhibited higher thermal stability but lower ionic conductivity compared to [PBIM](+)-based ILs. Further, the NH3 solubility in all ILs was measured using a custom-made setup at temperatures ranging from 293.15 to 323.15 K and pressures ranging from 1 to 5 bar. The effects of the cation and anion structures of ILs, as well as pressure and temperature, on the NH3 solubility in the ILs were also investigated. [PBIM]BF4 showed the best solubility because of its high free volume and low viscosity. Density functional calculations validated the superior NH3 solubility in [PBIM]BF4, attributable to the minimal reorganization of the [cation]anion complex geometry during the solvation process, yielding a low solvation free energy. The findings of this study suggest that ILs exhibit a high NH3 solubility capacity and cation and anion structures considerably affect the NH3 solubility in ILs.