How and Why Does Helium Permeate Nonporous Arsenolite Under High Pressure?. Issue 7 (13th February 2018)

• Record Type: Journal Article
• Authors: Guńka, Piotr A.; Hapka, Michał; Hanfland, Michael; Dranka, Maciej; Chałasiński, Grzegorz; Zachara, Janusz
• Is Part Of: Chemphyschem. Volume 19:Issue 7(2018)
• Page Start: 857
• Page End: 864
• Publication Date: 2018-02-13
• Subjects: arsenic -- helium -- high-pressure chemistry -- inclusion compounds -- X-ray diffraction; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.201701156
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: Investigations into the helium permeation of arsenolite, the cubic, molecular arsenic(III) oxide polymorph As4 O6, were carried out to understand how and why arsenolite helium clathrate As4 O6 ⋅ 2 He is formed. High‐pressure synchrotron X‐ray diffraction experiments on arsenolite single crystals revealed that the permeation of helium into nonporous arsenolite depends on the time for which the crystal is subjected to high pressure and on the crystal history. The single crystal was totally transformed into As4 O6 ⋅ 2 He within 45 h under 5 GPa. After release of the pressure, arsenolite was recovered and a repeated increase in pressure up to 3 GPa led to practically instant As4 O6 ⋅ 2 He formation. However, when a pristine arsenolite single crystal was quickly subjected to a pressure of 13 GPa, no helium permeation was observed at all. No neon permeation was observed in analogous experiments. Quantum mechanical computations indicate that there are no specific attractive interactions between He atoms and As4 O6 molecules at the distances observed in the As4 O6 ⋅ 2 He crystal structure. Detailed analysis of As4 O6 molecular structure changes has shown that the introduction of He into the arsenolite crystal lattice significantly reduces molecular deformations by decreasing the anisotropy of stress exerted on the As4 O6 molecules. This effect and the p Δ V term, rather than any specific As⋅⋅⋅He binding, are the driving forces for the formation As4 O6 ⋅ 2 He. Abstract : A nonporous puzzle : A joint experimental and theoretical study sheds more light on the recently discovered permeation of arsenolite by helium under high pressure. It is found that the phenomenon depends on the time given for permeation to take place and on the crystal history, and the thermodynamic driving force for it is also elucidated.