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Clouds over the Himalayas

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Stacking disordered ice; Ice Isd

Stacking-disordered ice is proposed to be the real structure of cubic ice

 

link Cubic ice

link Hexagonal ice

 

The solid form of water that forms in high clouds has been found to consist of mixed crystals of cubic ice and stacking disordered ice. Stacking disordered ice is a metastable form of ice intermediate between cubic and hexagonal ice. Many early studies on cubic ice were actually subsequently proven to contain substantial amounts of stacking disordered ice. Crystals of ice formed on homogeneous ice nucleation in deeply supercooled water nanodrops (r ≈ 10 nm) at ∼225 K were only 78 % cubic ice with 22% hexagonal ice; effectively 44% stacking-disordered ice [3032].

 

Shown below is the interesting structure consisting of alternating sheets of hexagonal ice and cubic ice, which was first described on this website in 2000. This structure is now thought to play a significant part in cubic ice structures, with randomly mixed hexagonal and cubic ice planes are often found [1236] and the ice is called stacking disordered ice Isd. It is found in several cloud types including upper tropospheric cirrus clouds and contrails formed by aircraft [2304]. It is metastable with respect to hexagonal ice having a higher vapor pressure, stability being: ice Ih > ice Isd > Ice Ic.

 

Alternating ice Ih/Ic unit; two Ih sheets followed by an Ic sheet

Alternating ice Ih/1c unit; two Ih sheets followed by an Ic sheet

 

 

 

Alternative ice Ih/1c lattice

 

Alternative ice Ih/1c lattice

Note that in all these structural diagrams, the hydrogen bonding is ordered whereas, if the structure were to exist, the hydrogen bonding would in all likelihood be random  (obeying the 'ice rules': two hydrogen atoms near each oxygen, one hydrogen atom on each O····O bond). Also, the stacking disorder would be more random than alternate. The (perfectly ordered) crystal structure appears to be hexagonal with unit cell (8 molecules) dimensions 4.48 Å (a,b) and 14.62 Å (c). It has trigonal P3m1 space group with threefold rotational symmetry.

 

      Trigonal snowflake,

      from SnowCrystals.com

                     trigonal snowflake, from SnowCrystals.com

Stacking disordered ice gives rise to trigonal snowflakes (see above left, from SnowCrystals.com) [2304].

 

X-ray diffraction; comparison of the low-pressure ices; from [2349]

X-ray diffraction; comparison of the low pressure ices; redrawn from [2349]

Hexagonal, cubic and stacking disordered ices are indistinguishable using vibrational spectroscopy but can be easily told apart using X-ray diffraction [2349]. The calculated X-ray diffractograms of cubic and hexagonal ices are shown right with their Miller indices (lattice planes) together with the powder X-ray diffractogram of a stacking disordered ice [2349].

 

Ice crystals giving miller indices

(x,y,z) of faces; from [2304]

 

ice crystals giving miller indices (x,y,z) of faces; from [2304]

 

 

 

 

 

 

 

 

The (001) plane of ice Ih and the (111) plane of ice Ic are identical to the (001) plane of ice Isd allowing alternating cubic and hexagonal layers to stack. Ice Isd does not necessarily consist of alternate single sheets of hexagonal ice and cubic ice but may usually be found with one or several sheets of hexagonal ice followed by one or several sheets of cubic ice in an apparently random sequence dependent on the freezing history of the ice [1236e]. The difference in energy between ice Isd and ice Ih of the crystals has been estimated variously as 13 to 160 J mol-1 [2559] depending mostly on the degree of cubicity of the ice Isd .

 

Interactive structures are given (Jmol).

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This page was established in 2001 and last updated by Martin Chaplin on 8 November, 2017


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