Determination of Surface pKa Values of Surface-Confined Molecules Derivitized with pH-Sensitive Pendant Groups

Abstract

Two methods for in-situ electrochemical measurements of surface pKa values air, reported. The methods are applied to surface-confined monolayers consisting of organomercaptan molecules derivitized with pH-sensitive pendant groups. The first technique relies upon pH-dependent electrostatic binding of redox probe molecules to the charged monolayer surface: the surface concentration of the probe molecules reflects the degree of surface protonation. The second method relates the differential capacitance of the monolayer-modified electrode surface to the surface pKa. The two methods yield essentially identical results and are consistent with a recently developed theoretical model. The surface pKa values of 4-mercaptopyridine and 4-aminothiophenol are 3. 7 and 5.7, respectively.

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Document Details

Document Type
Technical Report
Publication Date
Jul 06, 1992
Accession Number
ADA253034

Entities

People

  • Bryan J. Johnson
  • Mark A. Bryant
  • R. M. Crooks

Organizations

  • University of New Mexico

Tags

DTIC Thesaurus Topics

  • Buffers (Chemistry)
  • Capacitance
  • Carboxylic Acids
  • Chemistry
  • Electrodes
  • Films
  • Impedance
  • Military Research
  • Molecules
  • Monomolecular Films
  • New Mexico
  • New York
  • Organic Compounds
  • Titration
  • United States
  • United States Government

Fields of Study

  • Chemistry

Readers

  • Electrochemical Surface Science