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Kinetics of hydrolysis of 4-methoxyphenyl-2,2-dichloroethanoate in binary water-cosolvent mixtures; the role of solvent activity and solute-solute interactions
Nederländerna.ORCID iD: 0000-0002-3200-9945
2005 (English)In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 3, no 4, p. 597-602Article in journal (Refereed) Published
Abstract [en]

Rate constants are reported for the pH-independent hydrolysis of 4-methoxyphenyl-2,2-dichloroethanoate in aqueous solution as a function of the concentration of added cyanomethane ( acetonitrile), polyethylene glycol ( PEG 400) and tetrahydrofuran ( THF). The concentration of water was varied between ca. 25 and 55.5 M. It was found that the variation in water activity yields only a minor contribution to the observed variation in rate constants. Interestingly, for both cyanomethane and PEG 400 log(k) varies approximately linearly with the molar concentration of water. Medium effects in highly aqueous solutions ( [ H2O] > 50 M) of ethanol, 1-propanol, 2-propanol, 1-butanol and 2-methyl-2-propanol have also been determined. Unexpectedly, in this concentration range the alcohols induce significantly smaller effects per unit volume than cyanomethane. The present results are discussed in terms of pairwise interaction parameters. Isobaric activation parameters have been determined and reveal remarkable differences in the nature of the induced medium effects.

Place, publisher, year, edition, pages
Univ Groningen, Phys Organ Chem Unit, Strating Inst, NL-9747 AG Groningen, Netherlands.: ROYAL SOC CHEMISTRY , 2005. Vol. 3, no 4, p. 597-602
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:hkr:diva-21750DOI: 10.1039/b414593cISI: 000226876800009PubMedID: 15703794OAI: oai:DiVA.org:hkr-21750DiVA, id: diva2:1539761
Available from: 2021-03-25 Created: 2021-03-25 Last updated: 2021-03-26Bibliographically approved

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