Spectroscopic studies of proton-transfer and metal-ion binding of a solution-phase model for silica-immobilized 8-hydroxyquinoline

Uibel, Rory H.; Harris, Joel M.

doi:10.1016/s0003-2670(03)00896-1

Spectroscopic studies of proton-transfer and metal-ion binding of a solution-phase model for silica-immobilized 8-hydroxyquinoline

Journal Article · Tue Sep 02 00:00:00 EDT 2003 · Analytica Chimica Acta

DOI:https://doi.org/10.1016/s0003-2670(03)00896-1· OSTI ID:2480723

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

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

The proton-transfer and stepwise metal-ion complex formation reactions of the water-soluble 8HQ ligand, 5-(p-sulfophenylazo)-8-hydroxyquinoline, are investigated in order to understand the interfacial reactivity of the analogous ligand immobilized to silica by a phenylazo linker on the 5-position on the quinoline ring. Raman spectra of the ligand are acquired to determine whether the same tautomerization equilibrium exists for the solution-phase model compound as for the silica-immobilized ligand. UV-vis absorption spectra of aqueous solutions of the ligand are acquired as a function of pH and metal-ion concentration. The stepwise reactions are monitored, equilibrium constants are determined, and component spectra are resolved using multivariable least-squares methods. These methods were shown to be capable of resolving component spectra made up of broad bands that differ by only a 3-nm band shift. The acid dissociation constants of the ligand were determined to be: pK_A1 of 3.78 ± 0.3 and pK_A2 of 7.94 ± 0.4. The equilibrium constants for ligand binding to Cu²⁺ were also measured and found to be K₁ = 1.4 (±0.3) x 10¹⁰ and K₂ = 2.0 (±0.5) x 10⁷. The first ligand binding constant was compared to the complexation of the silica-immobilized 8HQ ligand. The formation constant for the 1:1 ligand:Cu²⁺ solution complex was ~30-times greater than that of the silica-immobilized 8HQ ligand. This is likely due to interactions of the immobilized ligand with the nearby silica surface that change its affinity for metal-ion binding.

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:: 2480723

Alternate ID(s):: OSTI ID: 20870098

Journal Information:: Analytica Chimica Acta, Journal Name: Analytica Chimica Acta Journal Issue: 1-2 Vol. 494; ISSN 0003-2670

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Immobilized ligands
Metal-ion complexation
Multiple-step equilibria
Multivariable least-squares analysis

Spectroscopic studies of proton-transfer and metal-ion binding of a solution-phase model for silica-immobilized 8-hydroxyquinoline

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