Reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate
International audience The mechanisms involved in the formation/dissociation of methane hydrate confined at the nanometer scale are unraveled using advanced molecular modeling techniques combined with a mesoscale thermodynamic approach. Using atom-scale simulations probing coexistence upon confineme...
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ftccsdartic:oai:HAL:hal-03357589v1 2023-05-15T17:11:41+02:00 Reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate Jin, Dongliang Coasne, Benoit Laboratoire Interdisciplinaire de Physique Saint Martin d’Hères (LIPhy ) Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA) 2021-04-13 https://hal.archives-ouvertes.fr/hal-03357589 https://hal.archives-ouvertes.fr/hal-03357589/document https://hal.archives-ouvertes.fr/hal-03357589/file/djin_PNAS_2021Mar_0.pdf https://doi.org/10.1073/pnas.2024025118 en eng HAL CCSD National Academy of Sciences info:eu-repo/semantics/altIdentifier/doi/10.1073/pnas.2024025118 hal-03357589 https://hal.archives-ouvertes.fr/hal-03357589 https://hal.archives-ouvertes.fr/hal-03357589/document https://hal.archives-ouvertes.fr/hal-03357589/file/djin_PNAS_2021Mar_0.pdf doi:10.1073/pnas.2024025118 info:eu-repo/semantics/OpenAccess ISSN: 0027-8424 EISSN: 1091-6490 Proceedings of the National Academy of Sciences of the United States of America https://hal.archives-ouvertes.fr/hal-03357589 Proceedings of the National Academy of Sciences of the United States of America , National Academy of Sciences, 2021, 118 (16), pp.e2024025118. ⟨10.1073/pnas.2024025118⟩ [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat] [CHIM.MATE]Chemical Sciences/Material chemistry info:eu-repo/semantics/article Journal articles 2021 ftccsdartic https://doi.org/10.1073/pnas.2024025118 2021-10-23T22:39:56Z International audience The mechanisms involved in the formation/dissociation of methane hydrate confined at the nanometer scale are unraveled using advanced molecular modeling techniques combined with a mesoscale thermodynamic approach. Using atom-scale simulations probing coexistence upon confinement and free energy calculations, phase stability of confined methane hydrate is shown to be restricted to a narrower temperature and pressure domain than its bulk counterpart. The melting point depression at a given pressure, which is consistent with available experimental data, is shown to be quantitatively described using the Gibbs–Thomson formalism if used with accurate estimates for the pore/liquid and pore/hydrate interfacial tensions. The metastability barrier upon hydrate formation and dissociation is found to decrease upon confinement, therefore providing a molecular-scale picture for the faster kinetics observed in experiments on confined gas hydrates. By considering different formation mechanisms—bulk homogeneous nucleation, external surface nucleation, and confined nucleation within the porosity—we identify a cross-over in the nucleation process; the critical nucleus formed in the pore corresponds either to a hemispherical cap or to a bridge nucleus depending on temperature, contact angle, and pore size. Using the classical nucleation theory, for both mechanisms, the typical induction time is shown to scale with the pore volume to surface ratio and hence the pore size. These findings for the critical nucleus and nucleation rate associated with such complex transitions provide a means to rationalize and predict methane hydrate formation in any porous media from simple thermodynamic data. Article in Journal/Newspaper Methane hydrate Archive ouverte HAL (Hyper Article en Ligne, CCSD - Centre pour la Communication Scientifique Directe) Proceedings of the National Academy of Sciences 118 16 e2024025118 |
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Open Polar |
collection |
Archive ouverte HAL (Hyper Article en Ligne, CCSD - Centre pour la Communication Scientifique Directe) |
op_collection_id |
ftccsdartic |
language |
English |
topic |
[PHYS.COND]Physics [physics]/Condensed Matter [cond-mat] [CHIM.MATE]Chemical Sciences/Material chemistry |
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[PHYS.COND]Physics [physics]/Condensed Matter [cond-mat] [CHIM.MATE]Chemical Sciences/Material chemistry Jin, Dongliang Coasne, Benoit Reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate |
topic_facet |
[PHYS.COND]Physics [physics]/Condensed Matter [cond-mat] [CHIM.MATE]Chemical Sciences/Material chemistry |
description |
International audience The mechanisms involved in the formation/dissociation of methane hydrate confined at the nanometer scale are unraveled using advanced molecular modeling techniques combined with a mesoscale thermodynamic approach. Using atom-scale simulations probing coexistence upon confinement and free energy calculations, phase stability of confined methane hydrate is shown to be restricted to a narrower temperature and pressure domain than its bulk counterpart. The melting point depression at a given pressure, which is consistent with available experimental data, is shown to be quantitatively described using the Gibbs–Thomson formalism if used with accurate estimates for the pore/liquid and pore/hydrate interfacial tensions. The metastability barrier upon hydrate formation and dissociation is found to decrease upon confinement, therefore providing a molecular-scale picture for the faster kinetics observed in experiments on confined gas hydrates. By considering different formation mechanisms—bulk homogeneous nucleation, external surface nucleation, and confined nucleation within the porosity—we identify a cross-over in the nucleation process; the critical nucleus formed in the pore corresponds either to a hemispherical cap or to a bridge nucleus depending on temperature, contact angle, and pore size. Using the classical nucleation theory, for both mechanisms, the typical induction time is shown to scale with the pore volume to surface ratio and hence the pore size. These findings for the critical nucleus and nucleation rate associated with such complex transitions provide a means to rationalize and predict methane hydrate formation in any porous media from simple thermodynamic data. |
author2 |
Laboratoire Interdisciplinaire de Physique Saint Martin d’Hères (LIPhy ) Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA) |
format |
Article in Journal/Newspaper |
author |
Jin, Dongliang Coasne, Benoit |
author_facet |
Jin, Dongliang Coasne, Benoit |
author_sort |
Jin, Dongliang |
title |
Reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate |
title_short |
Reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate |
title_full |
Reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate |
title_fullStr |
Reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate |
title_full_unstemmed |
Reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate |
title_sort |
reduced phase stability and faster formation/dissociation kinetics in confined methane hydrate |
publisher |
HAL CCSD |
publishDate |
2021 |
url |
https://hal.archives-ouvertes.fr/hal-03357589 https://hal.archives-ouvertes.fr/hal-03357589/document https://hal.archives-ouvertes.fr/hal-03357589/file/djin_PNAS_2021Mar_0.pdf https://doi.org/10.1073/pnas.2024025118 |
genre |
Methane hydrate |
genre_facet |
Methane hydrate |
op_source |
ISSN: 0027-8424 EISSN: 1091-6490 Proceedings of the National Academy of Sciences of the United States of America https://hal.archives-ouvertes.fr/hal-03357589 Proceedings of the National Academy of Sciences of the United States of America , National Academy of Sciences, 2021, 118 (16), pp.e2024025118. ⟨10.1073/pnas.2024025118⟩ |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1073/pnas.2024025118 hal-03357589 https://hal.archives-ouvertes.fr/hal-03357589 https://hal.archives-ouvertes.fr/hal-03357589/document https://hal.archives-ouvertes.fr/hal-03357589/file/djin_PNAS_2021Mar_0.pdf doi:10.1073/pnas.2024025118 |
op_rights |
info:eu-repo/semantics/OpenAccess |
op_doi |
https://doi.org/10.1073/pnas.2024025118 |
container_title |
Proceedings of the National Academy of Sciences |
container_volume |
118 |
container_issue |
16 |
container_start_page |
e2024025118 |
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1766068468234321920 |