File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Insights into unexpected photoisomerization from photooxidation of tribromoacetic acid in aqueous environment using ultrafast spectroscopy

TitleInsights into unexpected photoisomerization from photooxidation of tribromoacetic acid in aqueous environment using ultrafast spectroscopy
Authors
KeywordsSolvent-assisted dehalogenation
Disinfection byproducts
Haloacetic acid
Ultrafast transient absorption spectroscopy
Density functional theory
Issue Date2021
PublisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/jhazmat
Citation
Journal of Hazardous Materials, 2021, v. 418, p. article no. 126214 How to Cite?
AbstractHaloacetic acids are carcinogenic disinfection by-products (DPBs) and their photo-decomposition pathways, especially for those containing bromine and iodine, are not fully understood. In this study, femtosecond transient absorption (fs-TA) spectroscopy experiments were introduced for the first time to investigate the photochemistry of tribromoacetic acid. The fs-TA experiments showed that a photoisomerization intermediate species HOOCCBr2−Br (iso-TBAA) was formed within several picoseconds after the excitation of TBAA. The absorption wavelength of the iso-TBAA was supported by time-dependent density calculations. With the Second-order Møller-Plesset perturbation theory, the structures and thermodynamics of the OH-insertion reactions of iso-TBAA were elucidated when water molecules were involved in the reaction complex. The calculations also revealed that the isomer species were able to react with water with its reaction dynamics dramatically catalyzed by the hydrogen bonding network. The proposed water catalyzed OH-insertion/HBr elimination mechanism predicted three major photoproducts, namely, HBr, CO and CO2, which was consistent with the photolysis experiments with firstly reported CO formation rate and mass conversion yield as 0.096 min-1 and 0.75 ± 0.1 respectively. The spectroscopic technique, numerical tool and disclosed mechanisms provided insights on photodecomposition and subsequent reactions of polyhalo-DPBs contain heavy atom(s) (e.g., Br, I) with water, aliphatic alcohols or other nucleophiles.
Persistent Identifierhttp://hdl.handle.net/10722/300913
ISSN
2023 Impact Factor: 12.2
2023 SCImago Journal Rankings: 2.950
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorYeung, CS-
dc.contributor.authorTse, HY-
dc.contributor.authorLau, CY-
dc.contributor.authorGuan, J-
dc.contributor.authorHuang, J-
dc.contributor.authorPhillips, DL-
dc.contributor.authorLeu, SY-
dc.date.accessioned2021-07-06T03:11:57Z-
dc.date.available2021-07-06T03:11:57Z-
dc.date.issued2021-
dc.identifier.citationJournal of Hazardous Materials, 2021, v. 418, p. article no. 126214-
dc.identifier.issn0304-3894-
dc.identifier.urihttp://hdl.handle.net/10722/300913-
dc.description.abstractHaloacetic acids are carcinogenic disinfection by-products (DPBs) and their photo-decomposition pathways, especially for those containing bromine and iodine, are not fully understood. In this study, femtosecond transient absorption (fs-TA) spectroscopy experiments were introduced for the first time to investigate the photochemistry of tribromoacetic acid. The fs-TA experiments showed that a photoisomerization intermediate species HOOCCBr2−Br (iso-TBAA) was formed within several picoseconds after the excitation of TBAA. The absorption wavelength of the iso-TBAA was supported by time-dependent density calculations. With the Second-order Møller-Plesset perturbation theory, the structures and thermodynamics of the OH-insertion reactions of iso-TBAA were elucidated when water molecules were involved in the reaction complex. The calculations also revealed that the isomer species were able to react with water with its reaction dynamics dramatically catalyzed by the hydrogen bonding network. The proposed water catalyzed OH-insertion/HBr elimination mechanism predicted three major photoproducts, namely, HBr, CO and CO2, which was consistent with the photolysis experiments with firstly reported CO formation rate and mass conversion yield as 0.096 min-1 and 0.75 ± 0.1 respectively. The spectroscopic technique, numerical tool and disclosed mechanisms provided insights on photodecomposition and subsequent reactions of polyhalo-DPBs contain heavy atom(s) (e.g., Br, I) with water, aliphatic alcohols or other nucleophiles.-
dc.languageeng-
dc.publisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/jhazmat-
dc.relation.ispartofJournal of Hazardous Materials-
dc.subjectSolvent-assisted dehalogenation-
dc.subjectDisinfection byproducts-
dc.subjectHaloacetic acid-
dc.subjectUltrafast transient absorption spectroscopy-
dc.subjectDensity functional theory-
dc.titleInsights into unexpected photoisomerization from photooxidation of tribromoacetic acid in aqueous environment using ultrafast spectroscopy-
dc.typeArticle-
dc.identifier.emailPhillips, DL: phillips@hku.hk-
dc.identifier.authorityPhillips, DL=rp00770-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1016/j.jhazmat.2021.126214-
dc.identifier.pmid34102359-
dc.identifier.scopuseid_2-s2.0-85107651619-
dc.identifier.hkuros323185-
dc.identifier.volume418-
dc.identifier.spagearticle no. 126214-
dc.identifier.epagearticle no. 126214-
dc.identifier.isiWOS:000689377500005-
dc.publisher.placeNetherlands-

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats