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Study on hydrogen bonding network in aqueous methanol solution by Raman spectroscopy.

Bo Yang1, Xianwen Cao1, Hongzhi Lang1

  • 1Coherent Light and Atomic and Molecular Spectroscopy Laboratory, College of Physics, Jilin University, Changchun 130012, China.

Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy
|October 27, 2019
PubMed
Summary

Raman spectra reveal a phase transition in methanol-water solutions at a methanol volume fraction of 0.4. This transition, driven by hydrogen bonding changes, affects molecular vibrations and the methanol-water complex structure.

Keywords:
Hydrogen bondMethanol-water binary solutionMolecular associationPhase transitionRaman spectroscopy

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Area of Science:

  • Physical Chemistry
  • Spectroscopy
  • Solution Chemistry

Background:

  • Methanol-water mixtures are common binary solutions.
  • Understanding hydrogen bonding is crucial for characterizing solution properties.
  • Phase transitions in such systems influence their physical and chemical behavior.

Purpose of the Study:

  • To investigate the structural and hydrogen bonding changes in methanol-water solutions.
  • To identify phase transition points using Raman spectroscopy.
  • To elucidate the role of hydrogen bonds in the observed spectral shifts.

Main Methods:

  • Raman spectroscopy was employed to analyze aqueous methanol solutions.
  • Measurements were conducted at room temperature and atmospheric pressure.
  • Varying concentrations (volume fraction of methanol, Vm) were studied.

Main Results:

  • A significant blue shift in the CO stretching vibration mode of methanol was observed for Vm > 0.4.
  • CH symmetric and asymmetric stretching vibration modes showed a red shift under the same conditions.
  • The frequency shift of C-H bonds was correlated with the C-O…H-O hydrogen bond.

Conclusions:

  • A phase transition in the methanol-water complex occurs at Vm = 0.4, indicated by spectral shifts.
  • The red shift of CH modes suggests no direct hydrogen bonding involving the CH3 group.
  • Theoretical analysis supports the phase transition mechanism driven by hydrogen bond variations.