In situ Raman and X-ray scattering of a single supersaturated aqueous Mg(NO3)2 droplet ultrasonically levitated

Anal Sci. 2023 Jun;39(6):977-987. doi: 10.1007/s44211-023-00306-8. Epub 2023 Mar 1.

Abstract

A single liquid droplet in the air generated by ultrasonic levitation provides such analytical advantages as a small sample volume (~ μL) for expensive proteins, container-free condition for deeply supercooling and supersaturation, time-dependent observation, and homogeneous rapid mixing. The investigation of the properties and structure of a droplet at a molecular level is highly needed for understanding the physicochemical behaviors of a droplet and an underlying mechanism of processes in the droplet. We develop in situ Raman and synchrotron X-ray scattering methods of a single liquid droplet of ~ 1 mm size ultrasonically levitated. The composition of a supersaturated Mg(NO3)2 droplet and speciation in the droplet are determined by analyzing the nitrate N-O and the water O-H stretching vibrational Raman bands. The X-ray interference function of an supersaturated Mg(NO3)2 droplet is subjected to an empirical potential structure refinement modeling to reveal the ion solvation, association, and solvent water structure. Furthermore, crystallization of Mg(NO3)2⋅nH2O from a saturated droplet is observed and identified.

Keywords: Crystallization; Ion solvation; Liquid droplet; Raman scattering; Structure; X-ray scattering.