CO2 and C2H2 in cold nanodroplets of oxygenated organic molecules and water

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dc.contributor.authorDevlin, J. Paul
dc.contributor.authorBalci, F. Mine
dc.contributor.authorMaslakci, Zafer
dc.contributor.authorUras-Aytemiz, Nevin
dc.date.accessioned2024-09-29T16:01:10Z
dc.date.available2024-09-29T16:01:10Z
dc.date.issued2014
dc.departmentKarabük Üniversitesien_US
dc.description.abstractRecent demonstrations of subsecond and microsecond timescales for formation of clathrate hydrate nanocrystals hint at future methods of control of environmental and industrial gases such as CO2 and methane. Combined results from cold-chamber and supersonic-nozzle [A. S. Bhabhe, Experimental study of condensation and freezing in a supersonic nozzle, Ph.D. thesis (Ohio State University, 2012), Chap. 7] experiments indicate extremely rapid encagement of components of all-vapor pre-mixtures. The extreme rates are derived from (a) the all-vapor premixing of the gas-hydrate components and (b) catalytic activity of certain oxygenated organic large-cage guests. Premixing presents no obvious barrier to large-scale conditions of formation. Further, from sequential efforts of the groups of Trout and Buch, a credible defect-based model of the catalysis mechanism exists for guidance. Since the catalyst-generated defects are both mobile and abundant, it is often unnecessary for a high percentage of the cages to be occupied by a molecular catalyst. Droplets represent the liquid phase that bridges the premixed vapor and clathrate hydrate phases but few data exist for the droplets themselves. Here we describe a focused computational and FTIR spectroscopic effort to characterize the aerosol droplets of the all-vapor cold-chamber methodology. Computational data for CO2 and C2H2, hetero-dimerized with each of the organic catalysts and water, closely match spectroscopic redshift patterns in both magnitude and direction. Though vibrational frequency shifts are an order of magnitude greater for the acetylene stretch mode, both CO2 and C2H2 experience redshift values that increase from that for an 80% water-methanol solvent through the solvent series to approximately doubled values for tetrahydrofuran and trimethylene oxide (TMO) droplets. The TMO solvent properties extend to a 50 mol.% solution of CO2, more than an order of magnitude greater than for the water-methanol solvent mixture. The impressive agreement between heterodimer and experimental shift values throughout the two series encourages speculation concerning local droplet structures while the stable shift patterns appear to be useful indicators of the gas solubilities. (C) 2014 AIP Publishing LLC.en_US
dc.description.sponsorshipNational Science Foundation (NSF) [CHE-1213732]; Karabuk University [KBU-BAP-13/2-DR-001]; Direct For Mathematical & Physical Scien; Division Of Chemistry [1213732] Funding Source: National Science Foundationen_US
dc.description.sponsorshipSupport of this research by the National Science Foundation (NSF) through Grant No. CHE-1213732 is gratefully acknowledged. N.U.-A. is appreciative of partial support for this project by Karabuk University (Project No. KBU-BAP-13/2-DR-001).en_US
dc.identifier.doi10.1063/1.4895549
dc.identifier.issn0021-9606
dc.identifier.issn1089-7690
dc.identifier.issue18en_US
dc.identifier.pmid25399171en_US
dc.identifier.scopus2-s2.0-84907168964en_US
dc.identifier.scopusqualityQ1en_US
dc.identifier.urihttps://doi.org/10.1063/1.4895549
dc.identifier.urihttps://hdl.handle.net/20.500.14619/5555
dc.identifier.volume141en_US
dc.identifier.wosWOS:000344847600050en_US
dc.identifier.wosqualityQ1en_US
dc.indekslendigikaynakWeb of Scienceen_US
dc.indekslendigikaynakScopusen_US
dc.indekslendigikaynakPubMeden_US
dc.language.isoenen_US
dc.publisherAip Publishingen_US
dc.relation.ispartofJournal of Chemical Physicsen_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subjectCarbon-Dioxideen_US
dc.subjectAb-Initioen_US
dc.subjectSpectroscopic Evidenceen_US
dc.subjectClathrate Hydrateen_US
dc.subjectComplexen_US
dc.subjectAcetyleneen_US
dc.subjectEtheren_US
dc.subjectIceen_US
dc.subjectTransitionen_US
dc.subjectConversionen_US
dc.titleCO2 and C2H2 in cold nanodroplets of oxygenated organic molecules and wateren_US
dc.typeArticleen_US

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