Jammed acid-base reactions at interfaces

Julianne M. Gibbs-Davis, Jennifer J. Kruk, Christopher T. Konek, Karl A Scheidt, Franz M Geiger

Research output: Contribution to journalArticle

43 Scopus citations

Abstract

Using nonlinear optics, we show that acid-base chemistry at aqueous/solid interfaces tracks bulk pH changes at low salt concentrations. In the presence of 10 to 100 mM salt concentrations, however, the interfacial acid-base chemistry remains jammed for hours, until it finally occurs within minutes at a rate that follows the kinetic salt effect. For various alkali halide salts, the delay times increase with increasing anion polarizability and extent of cation hydration and lead to massive hysteresis in interfacial acid-base titrations. The resulting implications for pH cycling in these systems are that interfacial systems can spatially and temporally lag bulk acid-base chemistry when the Debye length approaches 1 nm.

Original languageEnglish (US)
Pages (from-to)15444-15447
Number of pages4
JournalJournal of the American Chemical Society
Volume130
Issue number46
DOIs
StatePublished - Nov 19 2008

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

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