The sorption of sodium silicate by synthetic magnetite (Fe 3 O 4 ) at different pH conditions (pH 7-11) and initial silicate concentrations (1 × 10 −3 and 10 × 10 −3 mol L −1 ) was studied using in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. The analysis of infrared spectra of sodium silicate in solution as well as adsorbed on magnetite nano-particles clearly showed the evolution of different silicate species depending on pH and silica concentration. The silicate concentration studied (10 × 10 −3 mol L −1 ) contained polymeric or condensed silicate species at lower pH as well as monomers at high pH, as evident from infrared spectra. Condensation of monomers resulted in an increased intensity of absorptions in the high frequency part (>1050 cm −1 ) of the spectral region, which contains information about both silicate in solution and sorbed silicate viz. 1300 cm −1 -850 cm −1 . In the pH range studied, infrared spectra of sorbed silicate and sorbed silicate during desorption both indicated the presence of different types of surface complexes at the magnetite surface. The sorption mechanism proposed is in accordance with a ligand exchange reaction where both monodentate and bidentate complexes could exist at low surface loading level, the relative proportion of the complexes being due to both pH and concentration in solution. Oligomerization occurred on the magnetite surface at higher surface loading.
The liquid-crystalline phases of the systems monooleoylglycerol (MO)/water, dioleoylphosphatidylcholine (DOPC)/water, and MO/DOPC/water have been studied by Fourier-transform infrared (FTIR) spectroscopy. In the latter ternary system, the sn-3 OH group of MO competes with water to interact with the polar head group of DOPC, and an intramolecular hydrogen bonding of MO is broken up. The hydration of the ester carbonyl groups in the lamellar phases of both the MO/water and DOPC/water systems increases with increasing water content. Similarly, the addition of small amounts either of MO to a DOPC/water system or of DOPC to an MO/water system also results in an increase in the hydration of the ester carbonyl groups. This leads to an unfavorable hydrocarbon-water contact which is counteracted by the formation of a cubic phase, except for the DOPC/water system, where the lamellar phase is stable also at the highest water concentrations. The phase behavior of the different systems can be described in terms of lipid monolayer curvature and molecular packing in the lipid aggregates. Finally, it is shown by the water association band in the FTIR spectrum that the water hydrogen bonding is considerably different in the liquid-crystalline phases than in bulk water.
Biobutanol produced by, e.g., acetone-butanol-ethanol (ABE) fermentation is a promising alternative to petroleum-based chemicals as, e.g., solvent and fuel. Recovery of butanol from dilute fermentation broths by hydrophobic membranes and adsorbents has been identified as a promising route. In this work, the adsorption of water and butanol vapor in a silicalite-1 film was studied using in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy to better understand the adsorption properties of silicalite-1 membranes and adsorbents. Single-component adsorption isotherms were determined in the temperature range of 35-120 °C, and the Langmuir model was successfully fitted to the experimental data. The adsorption of butanol is very favorable compared to that of water. When the silicalite-1 film was exposed to a butanol/water vapor mixture with 15 mol % butanol (which is the vapor composition of an aqueous solution containing 2 wt % butanol, a typical concentration in an ABE fermentation broth, i.e., the composition of the gas obtained from gas stripping of an ABE broth) at 35 °C, the adsorption selectivity toward butanol was as high as 107. These results confirm that silicalite-1 quite selectively adsorbs hydrocarbons from vapor mixtures. To the best of our knowledge, this is the first comprehensive study on the adsorption of water and butanol in silicalite-1 from vapor phase.
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