Author:
Al-Salih Hilal,Abu-Lebdeh Yaser
Abstract
AbstractThe relationship between phase diagram features around the solid–liquid equilibrium region and ionic conductivity in aqueous solutions is not well understood over the whole concentration range as is the case for acidic aqueous solutions. In this work, we have studied the ionic conductivity (κ) as a function of molar fraction (x) and temperature (T) for four acid/water solutions namely, monoprotic hydrochloric acid (HCl) and nitric acid (HNO3), diprotic sulfuric acid (H2SO4) and triprotic phosphoric acid (H3PO4) along with their binary phase diagrams. The connection between the main features of the phase diagrams and the trends in the ionic conductivity isotherms is established with a new insight on the two pertinent dominant conductivity mechanisms (hopping and vehicular). Ionic conductivity at different temperatures were collected from literature and fitted to reported isothermal (κ vs. x) and iso-compositional (κ vs. T) equations along with a novel semi-empirical equation (κ = f (x, T)) for diprotic and triprotic acids. This equation not only has the best fit for acids with different valency; but also contains four parameters, less than any other similar equation in literature. This work is one of few that advances the understanding of the intricate relationship between structure and ionic transport in various acidic aqueous solutions.
Publisher
Springer Science and Business Media LLC
Reference30 articles.
1. Aurbach, D. Nonaqueous Electrochemistry (CRC Press, 1999).
2. Barthel, J., Krienke, H. & Kunz, W. Physical chemistry of electrolyte solutions: Modern aspects. (1998).
3. Angell, C. A. & Bressel, R. D. Fluidity and conductance in aqueous electrolyte solutions. An approach from the glassy state and high-concentration limit. I. Ca(NO3)2 solutions. J. Phys. Chem. 76, 3244–3253 (1972).
4. Izutsu, K. Electrochemistry in Nonaqueous Solutions (John Wiley & Sons, 2009).
5. Smedley, S. The Interpretation of Ionic Conductivity in Liquids (Springer Science & Business Media, 2012).