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Article: A theoretical study of the mechanism of the water-catalyzed HCl elimination reactions of CHXCl(OH) (X = H, Cl) and HClCO in the gas phase and in aqueous solution

TitleA theoretical study of the mechanism of the water-catalyzed HCl elimination reactions of CHXCl(OH) (X = H, Cl) and HClCO in the gas phase and in aqueous solution
Authors
Issue Date2005
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpca
Citation
Journal Of Physical Chemistry A, 2005, v. 109 n. 42, p. 9653-9673 How to Cite?
AbstractA systematic ab initio investigation of the water-assisted decomposition of chloromethanol, dichloromethanol, and formyl chloride as a function of the number of water molecules (up to six) building up the solvation shell is presented. The decomposition reactions of the chlorinated methanols and formyl chloride are accelerated substantially as the reaction system involves additional explicit coordination of water molecules. Rate constants for the decomposition of chlorinated methanols and formyl chloride were found to be in reasonable agreement with previous experimental observations of aqueous phase decomposition reactions of dichloromethanol [CHCl 2-(OH)] and formyl chloride. For example, using the calculated activation free energies in conjunction with the stabilization free energies from the ab initio calculations, the rate constant was predicted to be 1.2-1.5 × 10 4 s -1 for the decomposition of formyl chloride in aqueous solution. This is in good agreement with the experimental rate constant of about 10 4 s -1 reported in the literature. The mechanism for the water catalysis of the decomposition reactions as well as probable implications for the decomposition of these chlorinated methanol compounds and formaldehydes in the natural environment and as intermediates in advanced oxidation processes are briefly discussed. © 2005 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167967
ISSN
2015 Impact Factor: 2.883
2015 SCImago Journal Rankings: 1.231
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorPhillips, DLen_US
dc.contributor.authorZhao, Cen_US
dc.contributor.authorWang, Den_US
dc.date.accessioned2012-10-08T03:13:32Z-
dc.date.available2012-10-08T03:13:32Z-
dc.date.issued2005en_US
dc.identifier.citationJournal Of Physical Chemistry A, 2005, v. 109 n. 42, p. 9653-9673en_US
dc.identifier.issn1089-5639en_US
dc.identifier.urihttp://hdl.handle.net/10722/167967-
dc.description.abstractA systematic ab initio investigation of the water-assisted decomposition of chloromethanol, dichloromethanol, and formyl chloride as a function of the number of water molecules (up to six) building up the solvation shell is presented. The decomposition reactions of the chlorinated methanols and formyl chloride are accelerated substantially as the reaction system involves additional explicit coordination of water molecules. Rate constants for the decomposition of chlorinated methanols and formyl chloride were found to be in reasonable agreement with previous experimental observations of aqueous phase decomposition reactions of dichloromethanol [CHCl 2-(OH)] and formyl chloride. For example, using the calculated activation free energies in conjunction with the stabilization free energies from the ab initio calculations, the rate constant was predicted to be 1.2-1.5 × 10 4 s -1 for the decomposition of formyl chloride in aqueous solution. This is in good agreement with the experimental rate constant of about 10 4 s -1 reported in the literature. The mechanism for the water catalysis of the decomposition reactions as well as probable implications for the decomposition of these chlorinated methanol compounds and formaldehydes in the natural environment and as intermediates in advanced oxidation processes are briefly discussed. © 2005 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpcaen_US
dc.relation.ispartofJournal of Physical Chemistry Aen_US
dc.titleA theoretical study of the mechanism of the water-catalyzed HCl elimination reactions of CHXCl(OH) (X = H, Cl) and HClCO in the gas phase and in aqueous solutionen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL:phillips@hku.hken_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jp053015yen_US
dc.identifier.pmid16866419-
dc.identifier.scopuseid_2-s2.0-27744537957en_US
dc.identifier.hkuros116999-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-27744537957&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume109en_US
dc.identifier.issue42en_US
dc.identifier.spage9653en_US
dc.identifier.epage9673en_US
dc.identifier.isiWOS:000232857300036-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US
dc.identifier.scopusauthoridZhao, C=7403563836en_US
dc.identifier.scopusauthoridWang, D=7407071795en_US

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