In Situ Adsorption Studies at Silica/Solution Interfaces by Attenuated Total Internal Reflection Fourier Transform Infrared Spectroscopy: Examination of Adsorption Models in Normal-Phase Liquid Chromatography

Rivera, Dion; Poston, Pete E.; Uibel, Rory H.; Harris, Joel M.

doi:10.1021/ac990968h

In Situ Adsorption Studies at Silica/Solution Interfaces by Attenuated Total Internal Reflection Fourier Transform Infrared Spectroscopy: Examination of Adsorption Models in Normal-Phase Liquid Chromatography

Journal Article · Sat Feb 26 00:00:00 EST 2000 · Analytical Chemistry

DOI:https://doi.org/10.1021/ac990968h· OSTI ID:2480727

Rivera, Dion ^[1]; Poston, Pete E. ^[1]; Uibel, Rory H. ^[1]; Harris, Joel M. ^[1]

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

ATR-FT-IR spectroscopy was employed to the study the adsorption of ethyl acetate and 2-propanol to the surface of thin silica sol–gel films in contact with n-heptane solutions. In situ vibrational spectra of silica-adsorbed species provided information regarding the mechanisms of solute retention and elution in normal-phase chromatography. Previous normal-phase chromatographic studies of ethyl acetate adsorption revealed nonlinear isotherms which were explained by both bilayer and adsorbate delocalization models. Infrared spectra of ethyl acetate at the silica surface versus concentration showed that nonlinear adsorption can be attributed to site heterogeneity, where adsorption to free silanols and surface-adsorbed water can be distinguished. Least-squares modeling of the data produced resolved spectra for the two sites and adsorption equilibrium constants that differed by about an order of magnitude. Adsorption of 2-propanol was best modeled by a single Langmuir isotherm showing no significant difference in adsorption energy for the two sites; 2-propanol was shown to easily displace ethyl acetate from the silica surface. Here, ethyl acetate could also displace 2-propanol from the silica, and least-squares modeling again revealed two-adsorbed-component spectra for ethyl acetate that were indistinguishable from spectra obtained when ethyl acetate adsorbed directly onto the surface.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: FG03-93ER14333

OSTI ID:: 2480727

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 7 Vol. 72; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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