title: Raman Spectroscopic Observations of the Ion Association between Mg(2+) and SO4(2-) in MgSO4-Saturated Droplets at Temperatures of ≤380 °C.
abstract: Liquid–liquid phase separation was observed in aqueous MgSO4 solutions with excess H2SO4 at elevated temperatures; the aqueous MgSO4/H2SO4 solutions separated into MgSO4-rich droplets (fluid F1) and a MgSO4-poor phase (fluid F2) during heating. The phase separation temperature increases with SO4(2–)/Mg2+ ratio at a constant MgSO4 concentration. At a MgSO4/H2SO4 ratio of 5, the liquid–liquid phase separation temperature decreases with an increase in MgSO4 concentration up to ∼1.0 mol/kg and then increases at higher concentrations, showing a typical macroscale property of polymer solutions with a lower critical solution temperature (LCST) of ∼271.4 °C. In situ Raman spectroscopic analyses show that the MgSO4 concentration in fluid F1 increases with an increase in temperature, whereas that in fluid F2 decreases with an increase in temperature. In addition, HSO4(–), which does not readily form complexes with Mg(2+), tends to accumulate in fluid F2. Analyses of the v1(SO4(2–)) bands confirmed the presence of four-sulfate species of unassociated SO4(2–) (∼980 cm(–1)), contact ion pairs (CIPs; ∼995 cm(–1)), and triple ion pairs (TIPs; ∼1005 cm(–1)) in aqueous solution, and more complex ion pair chain structure (∼1020 cm(–1)) in fluid F1. Comparison of the sulfate species in fluids F1 and F2 at 280 °C suggests that SO4(2–) in fluid F2 is less associated with Mg(2+). On the basis of in situ visual and Raman spectroscopic observations, we suggest that the formation of the complex Mg(2+)–SO4(2–) ion association might be responsible for the liquid–liquid phase separation. In addition, Raman spectroscopic analyses of the OH stretching bands indicate that the hydrogen bonding in fluid F1 is stronger than that in fluid F2, which might be ascribed to the increasing probability of collision of H2O with Mg(2+) and SO4(2–) in fluid F1.
authors.forename: Ye
authors.initials: Y
authors.lastname: Wan
authors.forename: Xiaolin
authors.initials: X
authors.lastname: Wang
authors.forename: Wenxuan
authors.initials: W
authors.lastname: Hu
authors.forename: I-Ming
authors.initials: IM
authors.lastname: Chou
mesh_terms: D006860:Hydrogen Bonding; D059625:Liquid-Liquid Extraction; D008278:Magnesium Sulfate / Q000737:chemistry* / Q000302:isolation & purification; D013059:Spectrum Analysis, Raman; D013696:Temperature
chemical_list: D008278:Magnesium Sulfate