ABSTRACT
The bonding of mandelic acid enantiomers has been studied on benzene-leucine, dinitrobenzene-leucine and dinitrobenzene-phenylalanine type chiral stationary phases connected to zeolite A supports. The pi-donor, pi-acceptor and H-bonding interactions responsible for diastereomer pair formations can be studied under quasi in situ chromatographic conditions by Fourier transform Raman and surface enhanced Raman spectroscopic techniques. Structural differences between diastereomer pairs result in observable spectral differences at a phase load of approx. 50%. It was shown that the decreasing pi-acceptor character of the phase is associated with its increasing capability of H-bond formation. Correlating spectral data to chromatographic results it can be concluded that, in addition to H-bonding as well as to pi-donor-pi-acceptor interactions, steric hindrances due to bulky moieties of either the stationary phase or the analyte molecules are of importance in successful separations.
Subject(s)
Mandelic Acids/chemistry , Spectrum Analysis, Raman/methodsABSTRACT
The complexation of Alizarin Red S (ARS) at the surface of hydrous fluorite particles has been investigated by means of potentiometric titrations, adsorption experiments, and zeta-potential measurements in 0.1 mol dm(-3) KCl ionic medium at 25.0 degrees C, as well as by UV/visible specular reflectance, FT-IR, and FT-Raman spectroscopy. Chemical reaction models describing the equilibria of ARS (HA(2-)) at the aqueous fluorite surfaces ( identical withX) have been established as follows: Experimental data were evaluated using the computer program FITEQL on the basis of a constant capacitance model for the electric double layer. Surface complexation mechanisms involving the R-SO(3)(-), R-beta-OH, and R-alpha-OH active groups of the ARS molecule are proposed to describe coordination to the fluorite surface. Copyright 2000 Academic Press.
ABSTRACT
The acid-base characteristics of naturally occurring illites, collected from different locations, were investigated by potentiometric titrations. The experimental data were interpreted using the constant capacitance surface complexation model. Considerable release of Al and Si from illite samples and subsequent complexation or precipitation of hydroxyl aluminosilicates generated during the acidimetric forward titration and the alkalimetric back titration, respectively, were observed. Therefore, the acidimetric supernatant, rather than the neutral one, was regarded as the system blank for each illite suspension to yield the surface site concentrations. In order to describe the acid-base chemistry of aqueous illite surfaces, two surface proton-reaction models, introducing the corresponding reactions between the dissolved aluminum species and silicic acid, as well as a surface Al-Si complex on homogeneous illite surface sites, were proposed as follows: The K(f2) constant in Model II was obtained by simulating the complex formation between the dissolved aluminum species and silicic acid that occurred in acidimetric supernatant when the hydroxide was added. Additionally, the following cation exchange reaction was also considered for a special case, where a large amount of K(+) is released during the corresponding acidimetric titration, in which a high concentration of protons are consumed. Optimization results indicated that both models could provide a good description of the titration behavior for all aqueous illite systems in this study. The intrinsic acidity constants for the different illites were similar in Model I, showing some generalities in their acid-base properties. Model I may be considered as a simplification of Model II, evident in the similarities between the corresponding constants. In addition, the formation constant for surface Al-Si species (complexes or precipitates) is relatively stable in this study. Copyright 1999 Academic Press.
ABSTRACT
Surface characteristics of magnetite at 25degreesC in aqueous suspensions are systematically studied. The measured specific surface area and concentration of proton binding sites correspond well to the calculated values. Zeta potential of magnetite in the absence of multivalent cations exhibits positive values in acidic solution and becomes negative with increasing pH. pHpzc is about 6. In the presence of excess cations such as Fe2+ or Fe3+, specific adsorption takes place at the surface of magnetite, which dramatically influences the value of zeta potential. The concentrations of soluble Fe ions at pH about 4.5 increase with solid concentrations of magnetite indicating some surface-related reaction mechanisms. Copyright 1998 Academic Press. Copyright 1998Academic Press
ABSTRACT
The interaction of dextrin with colloidal ZnS has been investigated through adsorption studies and FT-IR spectroscopy in the 4000-400 cm-1 range. The adsorption capacity is estimated to be around 1 mg/m2. Maximum adsorption is found to be constant below pH approximately 7 and to increase with pH at least up to pH 11. Eighty percent of maximum adsorption is achieved within 3 min after addition of the dextrin. Based upon FT-IR studies and titration data, an adsorption mechanism is proposed. Copyright 1997 Academic Press. Copyright 1997Academic Press
ABSTRACT
The adsorption mechanism of dextrin on aqueous minerals such as fluorite, apatite, galena, magnetite, gamma-alumina, and graphite was studied by adsorption experiments, zeta potential measurements, and FT-IR studies. Depending on the nature of the mineral surface, dextrin was found to interact in three different ways viz. by chemisorption, physisorption, or hydrophobic-hydrophobic interaction. The adsorption density of dextrin was found to be pH dependent. Maximum adsorption of dextrin was obtained around the pH at which the mineral surface is highly hydroxylated. The mechanism of dextrin interaction with the surface metal hydroxy sites, ( identical withMeOH), was found to proceed via chemical complexation. A linear relationship was observed between the adsorption density of dextrin and the pH of maximum surface hydroxylation. Zeta potential measurements have indicated the possibility of dextrin adsorption by electrostatic interaction under the conditions where mineral surface and dextrin are oppositely charged. Furthermore dextrin was found to adsorb on hydrophobic minerals such as graphite by hydrophobic-hydrophobic interaction. However, the magnitude of adsorption by electrostatic and hydrophobic interaction was found to be very marginal compared to that of chemical complexation. Copyright 1997 Academic Press. Copyright 1997Academic Press
ABSTRACT
In this paper, the acid-base properties of illite/water suspensions are examined using the constant capacitance surface complexation model. On the basis of results of potentiometric titrations and solubility experiments, we conclude that the proton reactions in the supernatants of illite suspensions can be successfully represented by proton reactions of Al(H2O)63+ and Si(OH)4 in water solutions. For illustrating the acidic characteristics of aqueous illite surfaces, two surface protonation models are proposed: (1) one site-one pKa model, identical withSOH right arrow over left arrow identical withSO- + H+, pKaint = 4.12-4.23; (2) two sites-two pKas model, identical withSIOH right arrow over left arrow identical withSIO- + H+, pKintaI = 4.17-4.44, and identical withSIIOH right arrow over left arrow identical withSIIO- + H+, [dipKintaII = 6.35-7.74. Evaluation of these two models indicates that both of them can give good descriptions of the experimental data of systems with different illite concentrations and ionic strengths and that the one site-one pKa model can be considered as a simplification of the two sites-two pKas model. Since both models assume only deprotonation reactions at the illite surfaces, they suggest that the surface behavior of the illite is similar to that of amorphous SiO2. Model assumptions, experimental procedures, and evaluative criteria are detailed in the paper.
ABSTRACT
In this paper, we conducted potentiometric titrations, batch adsorption experiments and FT-IR analysis to study the uptake of copper in illite/water suspensions and then applied the constant capacitance surface complexation model to interpret the reaction mechanism at the aqueous illite surfaces. Our research shows that the copper adsorption at these surfaces is strongly dependent on pH and that the adsorption causes a deprotonation of surface groups. We propose that the uptake of copper in the carbonate-free illite suspensions can be explained by the formation of mononuclear surface complexes, identical withSOCu+ and identical withSOCuOH, and a multinuclear surface complex, identical withSOCu2(OH)2+, followed by the formation of a bulk precipitate, Cu(OH)2(s), or a surface precipitate, identical withSOCu2(OH)3(sp). For the illite suspensions containing carbonates, we propose that the copper-illite interaction can be depicted by the formation of mononuclear surface complexes, identical withSOCu+ and identical withSOCuOH, followed by the formation of a copper hydroxylcarbonate precipitate, Cu2(OH)2CO3(s), rather than a copper hydroxide precipitate. The existence of Cu2(OH)2CO3(s) in the carbonate-containing illite suspensions was identified by FT-IR analysis.
