Scientific and technical conference on hygrometry

Krichevskii, E. S.

doi:10.1007/bf00986720

Cited by 1 publication

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“…The fluid in the one-phase region above the critical point can be used as the solvent for various chemical reactions. Since the first examination of oxidation reactions by Toriumi et al and dimerization and atomic recombination reactions by Krichevskii and collaborators, − the field has greatly expanded to include, for example, complex formation, unimolecular decomposition, photoreduction, dehydrogenation, and pyrolysis. The detailed results have been frequently described and reviewed. − …”

Section: Introductionmentioning

confidence: 99%

Critical Slowing Down of Chemical Reactions in Liquid Mixtures

Baird

Clunie

1998

J. Phys. Chem. A

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We have observed suppression in the specific rate of hydrolysis of five organic halides in three water-based liquid mixtures near their respective equilibrium consolute points. The systems examined were tert-amyl chloride in isobutyric acid + water, tert-butyl chloride in isobutyric acid + water, tert-butyl bromide in triethylamine + water, 3-chloro-3-methylpentane in 2-butoxyethanol + water, and 4-methylbenzylbromide in 2-butoxyethanol + water. The first two have upper consolute temperatures, while the second three have lower consolute temperatures. The slowing down effect occurred within a few tenths °C on either side of the consolute temperature. In the case of tert-amyl chloride in isobutyric acid + water, the effect followed a shift in consolute temperature produced by a change in the initial concentration of tert-amyl chloride. This indicates that all points along the critical line are equivalent. These observations demonstrate the existence of critical slowing down of chemical reaction rates in liquid mixtures.

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