In Situ Raman Spectroscopy Studies of Metal Ion Complexation by 8-Hydroxyquinoline Covalently Bound to Silica Surfaces

Uibel, Rory H.; Harris, Joel M.

doi:10.1021/ac020252d

In Situ Raman Spectroscopy Studies of Metal Ion Complexation by 8-Hydroxyquinoline Covalently Bound to Silica Surfaces

Journal Article · Fri Aug 23 00:00:00 EDT 2002 · Analytical Chemistry

DOI:https://doi.org/10.1021/ac020252d· OSTI ID:2480724

Uibel, Rory H. ^[1]; Harris, Joel M. ^[1]

University of Utah, Salt Lake City, UT (United States)

Raman spectroscopy is applied to an investigation of the interfacial chemistry of silica-immobilized 8-hydroxyquinoline (8HQ) for binding of metal ions over a wide range of solution conditions. Since the derivatized silica has a high specific binding capacity, the mass of silica equilibrated with solution needs to be small for studies of reactions with trace-level (μM) metal ions; otherwise, the solution volume required to reach equilibrium becomes excessive. To address this problem, a small-volume flow cell is designed for this work using a fiber-optic Raman probe inserted directly into the packed end of a microcolumn, allowing excitation and collection of Raman scattering from less than 10 mg of derivatized silica. This cell is attached to a flow system that allows control of solution conditions while the response of the 8HQ-silica material is acquired by continuous monitoring of Raman scattering from the sample. Raman spectra of the deprotonated, neutral, protonated, and copper-complexed forms of the ligand can be distinguished, allowing proton-transfer and metal ion binding reactions of the ligand to be investigated. To account for the effects of changing surface potential on these reactions, ζ-potential measurements are made on the 8HQ-silica particles under the same solution conditions that are employed in the Raman scattering measurements. Furthermore, the observed pH dependence of metal ion binding was corrected for the effect of surface potential using the Boltzmann equation, and the resulting equilibrium constant for binding of Cu²⁺ was independent of metal ion concentration over a 100-fold range from 30 μM to 5 mM.

View Accepted Manuscript (DOE)

Research Organization:: University of Utah, Salt Lake City, UT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG03-93ER14333

OSTI ID:: 2480724

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 19 Vol. 74; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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