Isotopic Fractionation Factor of the Hydrogen-Bonded Complex AcO(1-)...(HOAc)n and Kinetic and Equilibrium Solvent Isotope Effects on Reactions of Acetate Ion in Acetic Acid

DOI: 10.1039/P29880000919

Source and publish data:

Journal of the Chemical Society. Perkin transactions II p. 919 - 922 (1988)

Update date:2022-08-11

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Authors:

Clark, David R.

Emsley, John

Hibbert, Frank

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Article abstract of DOI:10.1039/P29880000919

A value of φ 0.58+/-0.05 has been obtained for the deuterium fractionation factor of the hydrogen-bonded complex AcO(1-)...(HOAc)n from (1)H n.m.r. studies of solutions of potassium acetate in AcOH and 97percent AcOD-3percent AcOH.The result is used to account for the kinetic solvent isotope effect 0.66+/-0.10 measured for formation of acetic anhydride from 2,4,6-trinitrophenyl acetate in AcOH and AcOD in the presence of potassium acetate.The equilibrium solvent isotope effect on complex formation between 2,4,6-trinitrophenol and acetate ion in AcOH and 97percent AcOD-3percent AcOH K^AcOH/K^AcOD 0.83+/-0.1, leads to a value φ ca. 0.7 for the complex <2,4,6-(NO2)3C6H2O...H...OAc>(1-).

Full text of DOI:10.1039/P29880000919

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