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Acoustic cavitation generates molecular mercury(ii) hydroxide, Hg(OH)2, from biphasic water/mercury mixtures.

ABSTRACT: Emulsification of elemental mercury in aqueous solution in the form of grey particles occurs upon exposure to intense sound fields. We show the concomitant formation of molecular Hg(OH)2 in the solution phase reaching a saturation limit of 0.24 mM at 25 °C. The formation of Hg(OH)2 is consistent with the 'hot spot' model which suggests the formation of OH? as a result of acoustic cavitation; such radicals are proposed to combine with Hg to form the Hg(OH)2 species here characterised using voltammetry.

SUBMITTER: Yang M

PROVIDER: S-EPMC7472659 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Acoustic cavitation generates molecular mercury(ii) hydroxide, Hg(OH)2, from biphasic water/mercury mixtures.

Yang Minjun M Rasche Bertold B Compton Richard G RG

Chemical science 20191122 2

Emulsification of elemental mercury in aqueous solution in the form of grey particles occurs upon exposure to intense sound fields. We show the concomitant formation of molecular Hg(OH)2 in the solution phase reaching a saturation limit of 0.24 mM at 25 °C. The formation of Hg(OH)2 is consistent with the 'hot spot' model which suggests the formation of OH˙ as a result of acoustic cavitation; such radicals are proposed to combine with Hg to form the Hg(OH)2 specie ...[more]

PMID: 32953005

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Project description:The cobalt carbonate hydroxide Co2CO3(OH)2 is a technologically important solid which is used as a precursor for the synthesis of cobalt oxides in a wide range of applications. It also has relevance as a potential immobilizer of the toxic element cobalt in the natural environment, but its detailed crystal structure is so far unknown. The structure of Co2CO3(OH)2 has now been investigated using density functional theory (DFT) simulations and powder X-ray diffraction (PXRD) measurements on samples synthesized via deposition from aqueous solution. Two possible monoclinic phases are considered, with closely related but symmetrically different crystal structures, based on those of the minerals malachite [Cu2CO3(OH)2] and rosasite [Cu1.5Zn0.5CO3(OH)2], as well as an orthorhombic phase that can be seen as a common parent structure for the two monoclinic phases, and a triclinic phase with the structure of the mineral kolwezite [Cu1.34Co0.66CO3(OH)2]. The DFT simulations predict that the rosasite-like and malachite-like phases are two different local minima of the potential energy landscape for Co2CO3(OH)2 and are practically degenerate in energy, while the orthorhombic and triclinic structures are unstable and experience barrierless transformations to the malachite phase upon relaxation. The best fit to the PXRD data is obtained using a rosasite model [monoclinic with space group P1121/n and cell parameters a = 3.1408 (4) Å, b = 12.2914 (17) Å, c = 9.3311 (16) Å and γ = 82.299 (16)°]. However, some features of the PXRD pattern are still not well accounted for by this refinement and the residual parameters are relatively poor. The relationship between the rosasite and malachite phases of Co2CO3(OH)2 is discussed and it is shown that they can be seen as polytypes. Based on the similar calculated stabilities of these two polytypes, it is speculated that some level of stacking disorder could account for the poor fit of the PXRD data. The possibility that Co2CO3(OH)2 could crystallize, under different growth conditions, as either rosasite or malachite, or even as a stacking-disordered phase intermediate between the two, requires further investigation.

Dataset Information

Acoustic cavitation generates molecular mercury(ii) hydroxide, Hg(OH)2, from biphasic water/mercury mixtures.

Publications

Acoustic cavitation generates molecular mercury(ii) hydroxide, Hg(OH)<sub>2</sub>, from biphasic water/mercury mixtures.

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