Determination of pH Value and Acid-base Property of Ionic Liquid Aqueous Solutions

Abstract

The ionic liquids (ILs) and their aqueous solutions have been considered as a new generation of absorption working substances for applications in gas separation and absorption refrigeration processes. It is important to understand the physicochemical properties of ionic liquids in aqueous solutions, such as chemical potential and acid-base properties before any industry application. In this study, we focused on the acid-base properties of the IL aqueous solutions by testing the pH values of the aqueous solutions of two ionic liquids, 1-ethyl-3-methylimidazolium acetate ([EMIM]Ac) and 1-hexyl-3-methylimidazolium chloride ([HMIM]Cl). All the tests were carried out at 25 and in a well controlled dry air ℃ surrounding. There were 16 water mass fractions for each of [EMIM]Ac and [HMIM]Cl aqueous solutions tested in range of 0.04 to 0.95 and 0.01 to 0.96, respectively. There, two methods, the sophisticated pH paper and the pH meter, were applied for the tests and the differences between the two test methods were detected. The test data from the two test methods and their differences were then evaluated with an aggregation film model and the activity theory for the film and aqueous solution phases. The results show that the difference of the pH values tested by the two methods is significant. The pH data from the sophisticated pH paper test present the bulk acid-base property of the IL aqueous solutions, while the pH meter can only reflect the hydrogen ion concentration in the IL aggregation film which was formed on the surface of the electrode of the pH meter. With analysis of acid-base reaction in the IL aqueous solution, a calculation model for the pH value of the bulk solution region was developed, and the data of the sophisticated pH paper test were correlated and the solution acid-base values were obtained. Based on analysis of the water species equilibrium in the IL aggregation film and the bulk aqueous solution phases and its effect on the concentration of hydrogen ions in the aggregation film, a method for calculation of the difference of pH values between the aggregation film and the bulk solution was proposed and the data from the pH meter were then fitted with the proposed calculation method. The results provide experimental data and a quantitative method for analysis of the acid-base property of IL aqueous solution systems.