Jump to main content
Jump to site search


Thermodynamic and kinetic isotope effects on the order–disorder transition of ice XIV to ice XII

Author affiliations

Abstract

Isotope effects accompanying the order–disorder transition of ice XIV to ice XII are studied using calorimetry, X-ray diffraction, and dielectric spectroscopy. Particular emphasis is placed on the impact of the cooling rate applied during high-pressure production and during ambient-pressure recooling on the degree of hydrogen order in the low-temperature ice XIV phase. For specimens from D2O, ordering is harder to achieve in the sense that despite smaller cooling rates, the degree of order is less than in crystals produced from H2O. The degree of ordering can be quantified in terms of the Pauling entropy using calorimetry and manifests itself in structural and dynamical features that were examined using X-ray diffraction and dielectric spectroscopy, respectively. In hydrogen chloride doped samples, H/D substitution was found to slow down the dipolar dynamics up to about 30-fold and shifts the order–disorder transition by 4–6 K. By contrast to earlier assumptions it is possible to reach a high degree of ordering also at ambient pressure, provided the cooling rate is small enough. That is, at ambient pressure, orthorhombic stress slows down the dipolar reorientation near the ordering transition by a factor of 300–2000 for H2O and 30–100 for D2O samples. Furthermore, by long-term storage of our samples at 77 K we have reached surprisingly large increases in degree of order. For the D2O samples we observed an unprecedented high order, corresponding to more than 45% of the Pauling entropy.

Graphical abstract: Thermodynamic and kinetic isotope effects on the order–disorder transition of ice XIV to ice XII

Back to tab navigation

Publication details

The article was received on 14 Jun 2018, accepted on 23 Jul 2018 and first published on 13 Aug 2018


Article type: Paper
DOI: 10.1039/C8CP03786H
Citation: Phys. Chem. Chem. Phys., 2018, Advance Article
  • Open access: Creative Commons BY license
  •   Request permissions

    Thermodynamic and kinetic isotope effects on the order–disorder transition of ice XIV to ice XII

    V. Fuentes-Landete, K. W. Köster, R. Böhmer and T. Loerting, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C8CP03786H

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements