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Room-temperature NaI/H2O compression icing: solute-solute interactions.

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Concentration and solute type uniquely influence high-pressure ice phase transitions in sodium iodide/water solutions. Anion-anion repulsion affects hydrogen bonds differently under compression versus salt solvation.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Geophysics

Background:

  • High-pressure phases of water (ice) are crucial for understanding planetary interiors.
  • The influence of solutes on water's phase behavior under pressure is complex and not fully understood.
  • Sodium iodide (NaI) in water exhibits unique phase transitions influenced by concentration and temperature.

Purpose of the Study:

  • To investigate the phase transitions of concentrated NaI/H2O solutions under pressure at 298 K.
  • To differentiate the effects of solute concentration versus solute type on ice phase transitions.
  • To elucidate the molecular mechanisms governing these pressure-induced phase changes.

Main Methods:

  • In situ Raman spectroscopy was employed to monitor phase transitions.
  • Solutions of varying NaI concentrations were subjected to increasing pressure.
  • Phase transition pressures (Pc1 and Pc2) were precisely determined.

Main Results:

  • Phase transitions to ice VI and then ice VII were observed, with pathways differing from solute-type driven transitions.
  • Increasing NaI concentration raised the liquid-VI transition pressure (Pc1) but minimally affected the VI-VII transition pressure (Pc2).
  • Anion-anion repulsion in hydration shells and its impact on hydrogen bond dynamics were identified as key factors.

Conclusions:

  • The Hofmeister series order governs the VI-VII transition under specific concentration conditions.
  • Compression's effect on hydrogen bonds contrasts with salt solvation, with compression recovering polarization-deformed bonds first.
  • Anion-anion interactions play a critical role in distinguishing concentration effects from solute-type effects on phase transitions.