Linear enthalpy-spectral shift correlation for perfluoro-tert-butyl alcohol

A. D. Sherry, K. F. Purcell

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

Calorimetric enthalpy data and infrared OH frequency shifts are reported for the acid-base interaction of perfluoro-tert-butyl alcohol with a variety of Lewis bases. A reduced adduct solvation by CCl4 plus an excessive acid solvation leads to lower enthalpies measured in CCl4 solution than in hexane solution. Reaction enthalpies with six donors in hexane were used to evaluate the Ea and Ca parameters for perfluoro-tert-butyl alcohol. Seven other donor enthalpies were calculated using the double scale enthalpy equation. The following correlation was found: ΔH (±0.2) = 0.0106Δν + 3.9. This correlation along with ΔH vs. ΔH correlations with 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, and phenol indicates that van der Waals repulsions are of least importance in the perfluoro-tert-butyl alcohol reactions. The slopes and intercepts of these relations, like the Ea and Ca parameters, reveal the relative electrostatic and covalent contributions in the formation of a hydrogen bond for each of these alcohols. The data adhere nicely to a single-scale enthalpy equation (ΔHa = αAβB) and an a vs. σ* plot. This fit provides good evidence for negligible acid-base steric interactions in the perfluoro-tert-butyl alcohol reactions.

Original languageEnglish (US)
Pages (from-to)1853-1857
Number of pages5
JournalJournal of the American Chemical Society
Volume94
Issue number6
StatePublished - 1972

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Enthalpy
Alcohols
Hexanes
Acids
Solvation
Lewis Bases
Trifluoroethanol
Hexane
Phenol
Static Electricity
Hydrogen
Propanol
Phenols
perfluoro-tert-butyl alcohol
Electrostatics
Hydrogen bonds
Infrared radiation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Linear enthalpy-spectral shift correlation for perfluoro-tert-butyl alcohol. / Sherry, A. D.; Purcell, K. F.

In: Journal of the American Chemical Society, Vol. 94, No. 6, 1972, p. 1853-1857.

Research output: Contribution to journalArticle

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