Structure and Hydrogen Bonding in Liquid and Supercritical Aqueous NaCl Solutions at a Pressure of 1000 bar and Temperatures up to 500 °C: A Comprehensive Experimental and Computational Study

Abstract

The behavior of aqueous 1.1 M NaCl solution at a constant pressure of 1000 bar in the temperature range 25-500 degrees C has been studied with the use of IR absorption, Raman scattering, X-ray diffraction, and molecular dynamics (MD) simulations. The results are compared with the data for pure water under identical external conditions. The main purpose of the experimental and theoretical studies was to understand in what way an electrolyte dissolved in water influences the hydrogen bonding and structural features of water. As was found, the vibrational spectra show no essential difference between the properties of solution and pure water. However, the experimental pair correlation functions and the results of MD simulations present an evidence for very different nature of these substances. A characteristic feature of the structure of NaCl solution is a considerable contribution of strong O-H...Cl- bonds. As the temperature increases, the number of such bonds decreases partially due to a phenomenon of ion pairing, so that at high temperatures the properties of the solution become closer to the properties of water.