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Carbonic acid monohydrate

  • Evan H. Abramson EMAIL logo , Olivier Bollengier , J. Michael Brown , Baptiste Journaux , Werner Kaminsky and Anna Pakhomova
Published/Copyright: August 28, 2018
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American Mineralogist
From the journal American Mineralogist Volume 103 Issue 9

Abstract

In the water-carbon dioxide system, above a pressure of 4.4 GPa, a crystalline phase consisting of an adduct of the two substances can be observed to exist in equilibrium with the aqueous fluid. The phase had been found to be triclinic, and its unit-cell parameters determined, but the full crystalline and even molecular structure remained undetermined. Here, we report new diamond-anvil cell, X-ray diffraction data of a quality sufficient to allow us to propose a full structure. The crystal exists in the P1̅ space group. Unit-cell parameters (at 6.5 GPa and 140 °C) are a = 5.8508(14), b = 6.557(5), c = 6.9513(6) Å, α = 88.59(2)°, β = 79.597(13)°, and γ = 67.69(4)°. Direct solution for the heavy atoms (carbon and oxygen) revealed CO3 units, with co-planar, but isolated, O units. Construction of a hydrogen network, in accordance with the requirements of hydrogen bonding and with minimum allowed distances between non-bonded atoms, indicates that the phase consists of a monohydrate of carbonic acid (H2CO3·H2O) with the carbonic acid molecule in the cis-trans configuration. This is the first experimental determination of the crystalline structure of a H2CO3 compound. The structure serves as a guide for ab initio calculations that have until now explored only anhydrous H2CO3 solids, while validating calculations that indicated that high pressures should stabilize H2CO3 in the solid state. If 4.4 GPa is the lowest pressure at which the phase is thermodynamically stable, this probably precludes its existence in our solar system, although it may exist on larger, volatile-rich exoplanets. If, however, its range of stability extends to lower pressures at lower temperatures (which possibility has not yet been adequately explored), then it might have been be a stable form of CO2 within the water-rich moons and dwarf planets prior to differentiation and might still exist on an undifferentiated Callisto.

Keywords: Carbonic acid; CO2; hydrate; high pressure; single-crystal X-ray diffraction; exoplanets

Acknowledgments

This work was partially funded by NASA Solar System Workings grant 80NSSC17K0775 and by the Icy Worlds node of NASA’s Astrobiology Institute (08-NAI5-0021). Single-crystal X-ray diffraction data were acquired at the ID15B beamline of the European Synchrotron Radiation Facility, Grenoble, France. B. Journaux is being supported by the NASA Postdoctoral Program and the NASA Astrobiology Institute. The authors thank S. Petitgirard, I. Collings, and M. Hanfland for their scientific and technical support during the ID15b synchrotron beam time.

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Received: 2018-03-15
Accepted: 2018-05-15
Published Online: 2018-08-28
Published in Print: 2018-09-25

© 2018 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.2138/am-2018-6554
Keywords for this article
Carbonic acid; CO2; hydrate; high pressure; single-crystal X-ray diffraction; exoplanets

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. The tales of disequilibrium and equilibrium crystallization of rare metal minerals: Data from new experiments
  3. Pressure, temperature, water content, and oxygen fugacity dependence of the Mg grain-boundary diffusion coefficient in forsterite
  4. Questioning the biogenicity of Neoproterozoic superheavy pyrite by SIMS
  5. The effect of disequilibrium crystallization on Nb-Ta fractionation in pegmatites: Constraints from crystallization experiments of tantalite-tapiolite
  6. Titanite major and trace element compositions as petrogenetic and metallogenic indicators of Mo ore deposits: Examples from four granite plutons in the southern Yidun arc, SW China
  7. Kuliginite, a new hydroxychloride mineral from the Udachnaya kimberlite pipe, Yakutia: Implications for low-temperature hydrothermal alteration of the kimberlites
  8. Electron microprobe technique for the determination of iron oxidation state in silicate glasses
  9. Experimental investigation of F and Cl partitioning between apatite and Fe-rich basaltic melt at 0 GPa and 950–1050 °C: Evidence for steric controls on apatite-melt exchange equilibria in OH-poor apatite
  10. Carbonic acid monohydrate
  11. High spatial resolution analysis of the iron oxidation state in silicate glasses using the electron probe
  12. Disturbance of the Sm-Nd isotopic system by metasomatic alteration: A case study of fluorapatite from the Sin Quyen Cu-LREE-Au deposit, Vietnam
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  16. Letter
  17. Making tissintite: Mimicking meteorites in the multi-anvil
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