Formation and decay of an aromatic vinyl cation in supercritical CF3H

Toshihiko Arita, Okitsugu Kajimoto

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)


The effect of local density enhancement on the diffusion-controlled reactions in supercritical (SC) fluids has been clearly detected in the recombination reaction of a vinyl cation, 1-(4-methoxyphenyl)-2,2-diphenyl cation, with Br- in SC CF3H. With increasing density of SC CF3H, the observed recombination rate as a whole decreased rapidly in proportion to 1/ηε, where η and ε are the bulk viscosity and dielectric constant of the medium, respectively. Near the critical density, the rate constant was found to be much smaller than the predicted value from the 1/ηε relation based on the Smolchowski-Debye scheme. This deviation indicates that the local density enhancement retards the recombination rate mainly due to the enhancement of dielectric constant.

Original languageEnglish
Pages (from-to)1770-1775
Number of pages6
JournalJournal of Physical Chemistry A
Issue number11
Publication statusPublished - 2003 Mar 20
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry


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