Thermodynamic validation of 1‐alkyl‐3‐methylimidazolium carboxylates as task‐specific ionic liquids for H₂S absorption

Abstract

Solubilities of H 2 S in five 1‐alkyl‐3‐methylimidazolium carboxylates ionic liquids (ILs) have been measured at temperatures from 293.15 to 333.15 K and pressures up to 350 kPa. It is shown that these ILs have significantly larger absorption capacities for H 2 S than those common ILs reported in the literature. The solubility is found to increase dramatically with the increasing alkalinity of the anions and slightly with the increasing length of the alkyl chains on the cations. It is further demonstrated that the absorption isotherms are typically nonideal. With the assumption of complex formation between H 2 S and ILs, a reaction equilibrium thermodynamic model is developed to correlate the experimental solubilities. The model favors a reaction mechanism of AB 2 type that two IL molecules interact with one H 2 S molecule. Thermodynamic parameters such as Henry's law constants, reaction equilibrium constants, and heat of complex formation are also calculated to evaluate the absorption process of H 2 S in these ILs. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2227–2235, 2013