Kinetics of Chromate Adsorption and Desorption at Fused Quartz/Water Interfaces Studied by Second Harmonic Generation

Amanda L. Mifflin, Katie A. Gerth, Franz M Geiger*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

32 Scopus citations

Abstract

It is now recognized that an understanding of hexavalent chromium pollution in the environment is tied to an understanding of how hexavalent chromium binds to geosorbent surfaces. We have applied the nonlinear optical laser spectroscopy surface second harmonic generation (SHG) to study the adsorption and desorption kinetics of submonolayer amounts of chromate interacting with the fused quartz/water interface at pH 7 and at room temperature. The chromate concentrations are varied between 10-6 and 10-5 M. The adsorption and desorption behavior of chromate at the fused quartz/water interface can be described by a Langmuir adsorption and a first-order chromate desorption model with an adsorption rate constant of 3(1) × 103 s-1 M-1 and a desorption rate constant of 0.9(7) × 10-3 s-1. At 300 K and pH 7, the resulting equilibrium constant for chromate binding is in good agreement with equilibrium constants obtained from Langmuir isotherm measurements carried out between pH 4 and 9. Thus, thermodynamic and kinetic measurements carried out in separate studies result in a chromate binding constant of 3.3 × 105 ((+17 × 105)/(- 2.1 × 105)) M-1 and a corresponding standard free energy of chromate binding to fused quartz/water interfaces of 32 (+4/-3) kJ/mol. In agreement with the general notion that chromate is highly mobile in most soil environments, a simple transport model predicts that chromate would move between 2 and 9% slower than the noninteracting groundwater phase; that is, it is poorly retained.

Original languageEnglish (US)
Pages (from-to)9620-9627
Number of pages8
JournalJournal of Physical Chemistry A
Volume107
Issue number45
DOIs
StatePublished - Nov 13 2003

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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