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World desk2 min

What a Study Found About Hydrogen Ordering in Ice V and Ice XIII

Researchers reported a stable, partially ordered β state between ice V and ice XIII. The finding complicates a simple disorder-to-order picture but does not disprove hydrogen ordering in ice.
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A 2024 study found that hydrogen ordering in the ice V–ice XIII system is not a simple change between a disordered phase and a fully ordered one. At ambient pressure, the researchers reported a thermodynamically stable, partially ordered intermediate—called β—in experiments spanning about 113–120 K. Its detailed structure remains unresolved, and the finding does not disprove hydrogen ordering in ice generally.

What the study found

Keishiro Yamashita and Thomas Loerting examined the relationship between ice V and ice XIII, a pair useful for studying hydrogen ordering because ice XIII has a definable fully ordered configuration and the transition can be reversible at ambient pressure. They reported three temperature regions: ice XIII was dominant below about 113 K, a partially ordered β intermediate appeared from about 113 to 120 K, and ice V was dominant above about 120 K. These are the approximate ranges reported for their experiments, not universal boundaries for every sample or condition. The 2024 paper

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The β state was distinguished from ice V and ice XIII by its enthalpy and ordering kinetics. The authors interpreted those differences as evidence for a separate, thermodynamically stable partially ordered phase—not merely a short-lived transition on the way between two phases.

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Why the result matters

Ice phases can differ in both the arrangement of their oxygen atoms and the orientations of their water molecules. Hydrogen ordering concerns the development of orientational order; it does not necessarily mean that the oxygen framework changes. A phase can therefore be partially ordered rather than fitting neatly into a fully disordered or fully ordered category.

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The broader significance is specific: for this ice V–ice XIII pair, the transition picture includes an intermediate state. The study does not establish that partially ordered equilibrium phases occur in every ice polymorph pair, nor does it overturn hydrogen ordering as a general feature of ice physics.

How the researchers distinguished a stable phase from a transient

A central challenge is that molecular reorientation slows at low temperatures. Ice can become kinetically stuck in an orientationally disordered or partly ordered state, making a frozen, non-equilibrium sample resemble a stable phase. To address that ambiguity, the authors used isothermal annealing and differential scanning calorimetry, focusing on how the sample behaved over time and at equilibrated limits.

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They prepared ice V from ice Ih containing 0.01 M HCl by heating under pressure at approximately 0.5 GPa, then quenched it and studied ordering at ambient pressure. Distinct enthalpy plateaus and different fitted kinetic behavior across the temperature ranges supported their interpretation of β as a separate stable state. The authors also reported that long annealing around 110–113 K could yield better-ordered ice XIII than earlier slow-cooling protocols.

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What remains unknown

The study established thermodynamic and kinetic distinctions for the β intermediate but did not provide a detailed structural characterization. Its exact molecular arrangement is therefore not resolved by this work. The authors identify computation and further experimental approaches, including vibrational spectroscopy and neutron diffraction, as ways to investigate the structure.

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The paper’s introduction notes 20 experimentally accessible ice polymorphs, a figure attributed to the authors’ 2024 publication rather than a current, independently verified count. The study’s own result concerns the ice V–ice XIII system at ambient pressure.

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