Glasslike behavior in aqueous electrolyte solutions

D.A. Turton, J. Hunger, G. Hefter, R. Buchner, K. Wynne

Research output: Contribution to journalArticle

79 Citations (Scopus)

Abstract

When salts are added to water, generally the viscosity increases, suggesting that the ions increase the strength of the water's hydrogen-bond network. However, infrared pump-probe measurements on electrolyte solutions have found that ions have no influence on the rotational dynamics of water molecules, implying no enhancement or breakdown of the hydrogen-bond network. Here, we report optical Kerr effect and dielectric relaxation spectroscopic measurements, which have enabled us to separate the effects of rotational and transitional motions of the water molecules. These data show that electrolyte solutions behave like a supercooled liquid approaching a glass transition in which rotational and translational molecular motions are decoupled. It is now possible to understand previously conflicting viscosity data, nuclear magnetic resonance relaxation, and ultrafast infrared spectroscopy in a single unified picture.
LanguageEnglish
Pages161102-1
Number of pages161101
JournalJournal of Chemical Physics
Volume128
Issue number16
DOIs
Publication statusPublished - 28 Apr 2008

Fingerprint

Electrolytes
electrolytes
Water
water
Hydrogen bonds
Viscosity
Ions
viscosity
Optical Kerr effect
hydrogen bonds
Molecules
Dielectric relaxation
Kerr effects
molecules
Glass transition
Infrared spectroscopy
ions
Salts
breakdown
infrared spectroscopy

Keywords

  • dielectric relaxation
  • electrolytes
  • glass transition
  • high-speed optical techniques
  • hydrogen bonds
  • infrared spectra
  • nuclear magnetic resonance
  • optical Kerr effect
  • viscosity
  • water

Cite this

Turton, D. A., Hunger, J., Hefter, G., Buchner, R., & Wynne, K. (2008). Glasslike behavior in aqueous electrolyte solutions. Journal of Chemical Physics, 128(16), 161102-1. https://doi.org/10.1063/1.2906132
Turton, D.A. ; Hunger, J. ; Hefter, G. ; Buchner, R. ; Wynne, K. / Glasslike behavior in aqueous electrolyte solutions. In: Journal of Chemical Physics. 2008 ; Vol. 128, No. 16. pp. 161102-1.
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Turton, DA, Hunger, J, Hefter, G, Buchner, R & Wynne, K 2008, 'Glasslike behavior in aqueous electrolyte solutions' Journal of Chemical Physics, vol. 128, no. 16, pp. 161102-1. https://doi.org/10.1063/1.2906132

Glasslike behavior in aqueous electrolyte solutions. / Turton, D.A.; Hunger, J.; Hefter, G.; Buchner, R.; Wynne, K.

In: Journal of Chemical Physics, Vol. 128, No. 16, 28.04.2008, p. 161102-1.

Research output: Contribution to journalArticle

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T1 - Glasslike behavior in aqueous electrolyte solutions

AU - Turton, D.A.

AU - Hunger, J.

AU - Hefter, G.

AU - Buchner, R.

AU - Wynne, K.

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AB - When salts are added to water, generally the viscosity increases, suggesting that the ions increase the strength of the water's hydrogen-bond network. However, infrared pump-probe measurements on electrolyte solutions have found that ions have no influence on the rotational dynamics of water molecules, implying no enhancement or breakdown of the hydrogen-bond network. Here, we report optical Kerr effect and dielectric relaxation spectroscopic measurements, which have enabled us to separate the effects of rotational and transitional motions of the water molecules. These data show that electrolyte solutions behave like a supercooled liquid approaching a glass transition in which rotational and translational molecular motions are decoupled. It is now possible to understand previously conflicting viscosity data, nuclear magnetic resonance relaxation, and ultrafast infrared spectroscopy in a single unified picture.

KW - dielectric relaxation

KW - electrolytes

KW - glass transition

KW - high-speed optical techniques

KW - hydrogen bonds

KW - infrared spectra

KW - nuclear magnetic resonance

KW - optical Kerr effect

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KW - water

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Turton DA, Hunger J, Hefter G, Buchner R, Wynne K. Glasslike behavior in aqueous electrolyte solutions. Journal of Chemical Physics. 2008 Apr 28;128(16):161102-1. https://doi.org/10.1063/1.2906132