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Related Experiment Videos

Hydrogen Bond Donor/Acceptor Cosolvent-Modified Choline Chloride-Based Deep Eutectic Solvents.

Ashish Pandey1, Bhawna1, Divya Dhingra1

  • 1Department of Chemistry, Indian Institute of Technology Delhi , Hauz Khas, New Delhi 110016, India.

The Journal of Physical Chemistry. B
|April 8, 2017
PubMed
Summary

Deep eutectic solvents (DESs) modified with hydrogen bond (HB) donors or acceptors like TFE and HMPA show altered properties. Their interactions depend on the specific DES and cosolvent, influencing cybotactic region dipolarity and system equilibria.

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Area of Science:

  • Physical Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Deep eutectic solvents (DESs) are emerging as sustainable alternatives to traditional organic solvents and ionic liquids.
  • DESs are typically formed by combining hydrogen bond (HB) donors and acceptors, such as ammonium salts and polyols.
  • Modifying DESs with cosolvents can tune their properties and expand their applications.

Purpose of the Study:

  • To investigate the effects of hydrogen bond donating (TFE) and accepting (HMPA) cosolvents on the properties of two distinct DESs: reline and glyceline.
  • To understand the interactions between DESs and cosolvents at a molecular level using spectroscopic and physical property measurements.
  • To explore how cosolvent addition influences the local environment (cybotactic region) and overall system behavior.

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Main Methods:

  • Preparation and mixing of DESs (reline, glyceline) with varying mole fractions of cosolvents (TFE, HMPA).
  • Solvatochromic measurements using absorbance and fluorescence probes to assess local dipolarity.
  • Fourier transform infrared (FTIR) absorbance and Raman spectroscopy to analyze structural changes and interactions.
  • Measurement of excess molar volumes and excess logarithmic viscosities to characterize mixture behavior.

Main Results:

  • TFE was miscible up to 0.25 mole fraction with both reline and glyceline, while HMPA showed limited miscibility with glyceline and immiscibility with reline.
  • Cybotactic region dipolarity was found to be solute-dependent in TFE/HMPA-added DESs.
  • Spectroscopic analysis revealed minor spectral broadening but no major shifts, suggesting subtle interactions.
  • Physical property measurements indicated TFE interacts differently with reline (interstitial accommodation) and glyceline (H-bonding), while HMPA addition to glyceline increased repulsive interactions.

Conclusions:

  • The addition of HB donor/acceptor cosolvents significantly impacts DES properties by perturbing the intricate salt-HB donor equilibria.
  • The miscibility and interaction behavior are highly dependent on the specific DES components and the nature of the cosolvent.
  • Understanding these interactions is crucial for designing tailored DES systems for specific applications.