Coupled chemical processes at clay/electrolyte interface: a batch titration study of Na-montmorillonites

The present work addresses the protolytic charge of montmorillonite, which occurs on the broken-bond sites at the particle edges. The purpose is to overcome the general difficulty arising in potentiometric titration due to coupled side reactions, which severely impede the titrant budget (partial dissolution of the clay and of secondary phases, hydrolysis and readsorption of dissolved species, cation exchange). Batch potentiometric titrations were carried out on the montmorillonite fractions extracted from two bentonites (MX80 and SWy2) to quantify their protolytic charge. The effects of equilibration time (24 h and 7 days), pH from 4 to 10, and ionic strength (0.1 and 0.01 mol L(-1)) were extensively studied for the MX80 sample. Quantification of dissolution was achieved by analysis of the equilibrium solutions for dissolved species and by La(3+) exchange of the readsorbed species. The results clearly show that secondary phases such as iron- or silica-rich minerals contribute to the dissolved species, according to the nature of the raw bentonite. Furthermore, readsorption affects significant amounts of dissolved species. The overconsumption of proton/hydroxide due to dissolution, readsorption, and hydrolysis of dissolved species was evaluated using a self-consistent thermodynamic calculation. The ability of such calculation to correct the raw titration curves in order to extract the titrable surface charge of montmorillonite was evaluated by comparison with the continuous titration procedure. Especially in the alkaline domain, correcting the raw batch titration curves for the measured side reactions failed to reproduce the continuous titration curves. These observations demonstrate the limitations of the batch titration method and the superiority of fast, continuous methods for quantifying the dissociable surface charge of clays.     

Surface-charging behavior of Zn-Cr layered double hydroxide

A Zn-Cr layered double hydroxide (LDH) having the formula Zn(2)Cr(OH)(6)Cl(0.7)(CO(3))(0.15)2.1H(2)O was synthesized and characterized by powder X-ray diffraction, infrared spectroscopy, acid-base potentiometric titration, mass titration, electrophoretic mobility, and modeling of the electrical double layer. Adsorption of alizarin was also performed in order to show some particular features of the HDL. Net hydroxyl adsorption, which increases with increasing pH and decreasing supporting electrolyte concentration, takes place above pH 5. The electrophoretic mobility of the particles was always positive and it decreased when the pH was higher than 9. An isoelectric point of 12 could be estimated by extrapolating the data. The modified MUSIC model was used to estimate deprotonation constants of surface groups and different adsorption models were compared. Good fit of hydroxyl adsorption and electrophoresis could be achieved by considering both OH(-)/Cl(-) exchange at structural sites and proton desorption from surface hydroxyl groups. The modeling, in agreement with alizarin adsorption, indicates that most of the structural positive charge of the LDH is screened at the surface by exchanged anions and negatively charged surface groups. It also suggests that only structural charge sites initially neutralized by chloride ions are active for anion exchange. The remaining sites are blocked by carbonate and do not participate in the exchange.     

Determination of structural modification in acid activated montmorillonite clay by FT-IR spectroscopy

The structural modifications and the Bronsted acid sites generated during the acid treatment of montmorillonite clay with varied concentration of sulphuric acid was determined using FT-IR spectroscopy. Octahedral sheet is affected at low acid concentration resulting into the dissolution of cations; among them Mg2+ cations are prone to dissolve than Fe2+/3+ and Al3+. Tetrahedral sheet is affected at higher acid concentration. The partial substitution of octahedral Al3+ by Mg2+ or Fe2+/3+ cations and the presence of other non-smectite minerals such as kaolinites was also been clearly identified, thus making FT-IR spectroscopy as a rapid technique for monitoring the structural features of montmorillonite clay.     

Determination of Point of Zero Charge of Tunisian Kaolinites by Potentiometric and Mass Titration Methods

This paper deals with determining points of zero charge of natural and Na⁺‐saturated mineral kaolinites using two methods: (1) acid‐base potentiometric titration was employed to obtain the adsorption of H⁺ and OH^? on amphoteric surfaces in solutions of varying ionic strengths in order to determinate graphically the point of zero net proton charge (PZNPC) defined equally as point of zero salt effect (PZSE); (2) mass titration curve at different electrolyte concentrations in order to estimate PZNPCs by interpolation and to compare with those determined by potentiometric titrations. The two methods involved points of zero charge approximately similar for the two kaolinites between 6.5‐7.8, comparable to those reported previously and were in the range expected for these clay minerals. The comparison of potentiometric surface titration curves obtained at 25 °C and those published in the literature reveals significant discrepancies both in the shape and in the pH of PZNPCs values.     

Adsorptive removal of tannin from aqueous solutions by cationic surfactant-modified bentonite clay

The removal of tannin from aqueous media by cationic surfactant-modified bentonite clay was studied in a batch system. The surfactant used was hexadecyltrimethylammonium chloride. Adsorbent characterizations were investigated using X-ray diffraction, infrared spectroscopy, surface area analysis, and potentiometric titration. The effects of pH, contact time, initial solute concentration, adsorbent dose, ionic strength, and temperature on the adsorption of tannin onto modified clay were investigated. The adsorbent exhibited higher tannin removal efficiency (>99.0%) from an initial concentration of 10.0 micromol/L at pH 3.0. Adsorption capacity decreased from 90.1 to 51.8% with an increase in temperature from 10 to 40 degrees C at an initial concentration of 25.0 micromol/L. The adsorption process was found to follow pseudo-first-order kinetics. Film diffusion was found to be the rate-limiting step. Tannin adsorption was found to decrease with increase in ionic strength. The tannin equilibrium adsorption data were fitted to Langmuir and Freundlich isotherm models, the former being found to provide the best fit of the experimental data. The maximum monolayer adsorption capacity for tannin was 69.80 micromol/g at 30 degrees C. Comparison of adsorption capacity of the modified clay with reported adsorbents in the literature was also presented. Adsorbed tannin on modified clay can be recovered by treatment with 0.1 M NaOH solution. Regeneration experiments were tried for four cycles and results indicate a capacity loss of <10.0%. From the results it can be concluded that the surfactant-modified clay could be a good adsorbent for treating tannin-contaminated waters.     

Surface Properties of Cleaved Mica

The structural characteristics of cleaved mica are studied. Cleavage of phlogopite and muscovite is shown to be accompanied by the deformation of their crystal lattices. The structural charge emerging as a result amounts to 90–95% of the total charge of the mica surface. The acid–base properties of the surfaces of these minerals are studied by the method of potentiometric titration. As is shown using constant capacitance surface complexation model, only deprotonation reactions are characteristic for muscovite, whereas phlogopite undergoes also ion-exchange reactions. The corresponding constants of acid–base equilibrium are determined.     

ESR study of aqueous micellar solutions of perfluoropolyether surfactants with the use of fluorinated spin probes

The acid-base properties of synthetically prepared and well-characterized hydroxyapatite (HAP) in contact with KNO3 solutions were investigated at 25 degrees C, through potentiometric titrations, zeta-potential measurements, and surface complex modeling. Aliquots of suspension were withdrawn every 0.5 pH unit during the titration procedure and analyzed for calcium and phosphate. It was found that, even for rapid titration experiments, a remarkable amount of H+ ions (H+dissol.) is consumed in the bulk solution in reacting with species coming from the dissolution of HAP. These H+ ions must be taken into account in the H+ mass balance, in order for true value for the point of zero charge (pzc=6.5+/-0.2) and consequently true value for the surface charge (sigma0) to be obtained. Besides the conventional potentiometric titration technique, it was found that pzc may be determined much more easily as the intersection point of the suspension titration curve and the blank one modified to include the amount of H+dissol. obtained at one ionic strength. Finally, a surface complexation model was proposed for the development of surface charge. Experimental data were satisfactorily fitted by using the value of 4.2 F m-2 for the capacitance.     

Modeling of copper(II) and lead(II) adsorption on kaolinite-based clay minerals individually and in the presence of humic acid

The aim of this study is to explain how clay minerals adsorb heavy metals individually and in the presence of humic acid, and to model heavy metal adsorption specifically based on surface-metal binary and surface-metal-ligand ternary complexation. The adsorption of Cu(II) and Pb(II) on kaolinite-based clay minerals has been modeled by the aid of the FITEQL3.2 computer program using single- and double-site binding models of the Langmuir approach. Potentiometric titrations and adsorption capacity experiments were carried out in solutions containing different concentrations of the inert electrolyte NaClO4; however, the modeling of binary and ternary surface complexation was deliberately done at high ionic strength (0.1 M electrolyte) for eliminating adsorption onto the permanent negatively charged sites of kaolinite. A "two-site, two pKa" model was adapted, and as for the two surface sites responsible for adsorption, it may be arbitrarily assigned that [triple bond]S1OH sites represent silanol and organic functional groups such as carboxyl having pKa values close to that of silanol, and [triple bond]S2OH sites represent aluminol and organic functional groups such as phenolics whose pKa values are close to that of aluminol, as all the studied clays contained organic carbon. Copper(II) showed a higher adsorption capacity and higher binding constants, while lead(II), being a softer cation (in respect to HSAB theory) preferred the softer basic sites with aluminol-phenol functional groups. Heavy metal cations are assumed to bind to the clay surface as the sole (unhydrolyzed) M(II) ion and form monodentate surface complexes. Cu(II) and Pb(II) adsorption in the presence of humic acid was modeled using a double-site binding model by the aid of FITEQL3.2, and then the whole system including binary surface-metal and surface-ligand and ternary surface-metal-ligand complexes was resolved with respect to species distributions and relevant stability constants. Electrostatic effects were accounted for using a diffuse layer model (DLM) requiring minimum number of adjustable parameters. Metal adsorption onto clay at low pH increased in the presence of humic acid, and the metal adsorption vs pH curves of metal-kaolinite-humic acid suspensions were much steeper (and distinctly S shaped) compared to the wider pH-gradient curves observed in binary clay-metal systems. The clay mineral in the presence of humic acid probably behaved more like a chelating ion-exchanger sorbent for heavy metals rather than being a simple inorganic ion exchanger.     

Aqueous suspensions of natural swelling clay minerals. 1. Structure and electrostatic interactions

In this article, we present a general overview of the organization of colloidal charged clay particles in aqueous suspension by studying different natural samples with different structural charges and charge locations. Small-angle X-ray scattering experiments (SAXS) are first used to derive swelling laws that demonstrate the almost perfect exfoliation of clay sheets in suspension. Using a simple approach based on geometrical constraints, we show that these swelling laws can be fully modeled on the basis of morphological parameters only. The validity of this approach was further extended to other clay data from the literature, in particular, synthetic Laponite. For all of the investigated samples, experimental osmotic pressures can be properly described by a Poisson-Boltzmann approach for ionic strength up to 10(-3) M, which reveals that these systems are dominated by repulsive electrostatic interactions. However, a detailed analysis of the Poisson-Boltzmann treatment shows differences in the repulsive potential strength that are not directly linked to the structural charge of the minerals but rather to the charge location in the structure for tetrahedrally charged clays (beidellite and nontronites) undergoing stronger electrostatic repulsions than octahedrally charged samples (montmorillonites, laponite). Only minerals subjected to the strongest electrostatic repulsions present a true isotropic to nematic phase transition in their phase diagrams. The influence of ionic repulsions on the local order of clay platelets was then analyzed through a detailed investigation of the structure factors of the various clay samples. It appears that stronger electrostatic repulsions improve the liquidlike positional local order.     

Cation and anion exchange on clay modified electrodes

Carbon paste electrodes modified with clay minerals were used for the study of ion-exchange properties of these clay minerals. Cation exchange of Cu(II) was studied by the dependence on the pH, ionic strength and the form of the minerals. The highest anionic exchange of Hg(II) acetates and chlorides was found on montmorillonites. Anionic exchange of Au(III) chloro complexes was found on montmorillonite, but their sorption is strongly influenced by other anions such as chlorides and thiocyanates. The results found are important with regard to the study of the anion-exchange properties of clay minerals. Received: 2 December 1999 / Accepted: 2 March 2000     

Protonation of different goethite surfaces--Unified models for NaNO3 and NaCl media

Acid-base titration data for two goethites samples in sodium nitrate and sodium chloride media are discussed. The data are modeled based on various surface complexation models in the framework of the multi site complexation (MUSIC) model. Various assumptions with respect to the goethite morphology are considered in determining the site density of the surface functional groups. The results from the various model applications are not statistically significant in terms of goodness of fit. More importantly, various published assumptions with respect to the goethite morphology (i.e., the contributions of different crystal planes and their repercussions on the "overall" site densities of the various surface functional groups) do not significantly affect the final model parameters within simple 1-pK approximations. The simultaneous fit of the chloride and nitrate data results in electrolyte binding constants, which are applicable over a wide range of electrolyte concentrations including mixtures of chloride and nitrate. Model parameters for the goethite sample with 90 m2/g specific surface area are in excellent agreement with parameters that were independently obtained by another group on different goethite titration data sets.     

Effects of solid acidity of clay minerals on the thermal decomposition of 12-aminolauric acid

In this study, the effects of four types of clay minerals on the thermal decomposition of 12-aminolauric acid (ALA) were investigated. The decomposition temperature of ALA in ALA–clay complexes was in the range of 200–500 °C. The derivative thermogravimetry results indicated that all clay minerals exhibited catalytic activity on the decomposition of ALA. Pure ALA decomposed at approximately 464 °C, a temperature higher than the decomposition temperature of ALA in the presence of clay minerals. The decomposition temperature of ALA in different ALA–clay complexes follows the order illite (452 °C) > kaolinite (419 °C) > rectorite (417 °C) > montmorillonite (400 °C). This order is negatively correlated with the amounts of solid acid sites in the clay minerals, indicating that ALA is catalyzed by the solid acid sites in these minerals.     

Adsorption and radical stabilization of humic-Acid analogues and Pb2+ on restricted phyllomorphous clay

Humic acids have stable radicals that are indigenous to their structure. Hydroxybenzoic acid derivatives such as gallic acid (GA) and protocatechuic acid are appropriate models for the radical properties of humic acids. Here we show that the adsorption or intercalation of gallic acid in Laponite clay results in a significant thermodynamic stabilization of gallic acid radicals. Moreover, the formed organoclay shows enhanced stability against acid dissolution. The structural details of the association of gallic acid with Laponite depend on the GA/Laponite loading. At low GA/Laponite ratios (approximately 10(-6) M of gallic acid per gram of clay), gallic acid is adsorbed at the variable charge sites of Laponite. This adsorption can be adequately described by surface complexation modeling. At higher GA/Laponite ratios (approximately 10(-3) M of gallic acid per gram of clay), X-ray diffraction data show that gallic acid is intercalated at the interlamellar sites of Laponite. In the presence of Pb2+ ions, the formed GA/Pb complex is associated with Laponite in an analogous structural manner, that is, adsorption at variable charge sites or intercalation at the interlamellar sites of Laponite, depending on the loading. Laponite stabilizes the GA/Pb radicals. At prolonged exposure to ambient O2, Laponite promotes the formation of stable oligomeric GA/Pb radical species, which are intercalated into interlamellar sites.     

Binding constant of thorium with gray humic acid

Humic acid sample was separated from the bottom sediments of Lake Quarun, in Egypt. It was purified and characterized by elemental analysis, potentiometric titration, IR, UV-visible and ¹³C NMR spectroscopies. The product of humic acid was very low (0.009%), gray in color and has low carboxylate capacity (2.4 meq/g). The first derivative of the titration curve indicated one maximum only, which implies one kind of carboxylate groups. The binding constant of ²³⁴Th with Lake Quarun humic acid was determined by solvent extraction. Only one parameter, β ₁, was required to fit the binding as a function of carboxylate concentration: the Th⁴⁺ bound to the carboxylate sites in the gray humic acid forming 1:1 complex only. The binding constant increased with the degree of ionization and with the pK_a of the humic acid.     

Limitations of potentiometric studies to determine the surface charge of gibbsite gamma-Al(OH)3 particles

Surface charges of gibbsite particles were probed by potentiometric titration and subsequently analyzed to estimate intrinsic proton affinity constants of OH surface groups. A detailed spectroscopic characterization of the molecular structure of surface OH groups yielded estimates of bond lengths and bond valences of OH surface sites. Based on these results, the effects of the setting parameters of a MUSIC calculation have been shown in comparison with previous predictions yielding higher pKa values (2 < -pKa < 4) for the protonation of basal doubly coordinated OH surface groups and lower pKa values (7.9 < -pKa < 9.9) for the protonation of lateral singly coordinated OH surface groups. Comparison with experimental data is complicated by reproducible hysteresis between acid and base addition in optimal raw potentiometric titration curves at different ionic strengths. Such effects prevented the determination of a univocal intersection point to provide the global point of zero charge of gibbsite particles, even though the ionic strength dependence of the point of zero net proton charge and the different crossovers between curves indicated that the point of zero charge could be estimated between 8.1 and 9.6, in relative agreement with the lateral affinity constant calculated with the MUSIC model. Still, two main drawbacks remained to differentiate the reactivity of lateral singly and basal doubly coordinated surface groups. First, significant kinetic effects observed in acidic media indicated a dissolution process and/or protonation of basal surface groups. Second, the choice of specific surface areas, especially for a heterogeneous sample, led to several cases for the calculation of the absolute surface charge of particles. Therefore, our results demonstrated the heterogeneous reactivity of gibbsite particles and that the prediction and the experimental determination of respective surface groups are still complex even if some trends emerge.     

Spectroscopic investigations of Fe2+ complexation on nontronite clay

Diffuse reflectance (visible) and attenuated total internal reflection Fourier-transform infrared (ATR-FTIR) spectroscopies were used to examine a colloidal nontronite clay in the presence of Fe2+(aq). pH-dependent changes are observed in both types of spectra. In the visible region, a broad feature at approximately 750 nm appears as the pH is raised to circumneutral values. This absorbance band overlaps with a portion of the spectrum of the chemically reduced clay which is dominated by an intervalence charge-transfer transition between Fe2+ and Fe3+ within the mineral structure. The similarities between these spectra suggest that Fe2+(aq) adsorbs to the clay in such a way that it can undergo charge transfer with structural Fe3+ within the clay. ATR-FTIR spectra at pH 5-8 reveal a transformation in the Si-O stretching region between pH 6 and pH 7 with a shift of the component peaks to lower frequency. Taken together, these spectroscopic studies indicate that Fe2+ forms an inner-sphere complex with the clay at higher pH values. The pH threshold for these observed changes in physical and electronic structure is in good agreement with the point of zero charge (pzc) of the hydroxyl groups on the edge surfaces of the clay, suggesting that complexation of Fe2+ to deprotonated edge sites leads to the observed spectroscopic features.     

Effect of supercritical fluid extraction parameters and clay properties on the efficiency of phenanthrene extraction

Clay soils have specific properties that cause difficulty in the assessment and remediation of contaminated sites. Furthermore, polyaromatic hydrocarbons, when present in soil, are difficult to extract due to their nonpolar, high molecular weight characterization. In this study, the supercritical fluid (carbon dioxide) extraction (SFE) technique, with and without methanol modifier, was used for removal of PAHs (phenanthrene) from kaolinite, illite, and montmorillonite soils. The impact of SFE parameters (fluid pressure, fluid temperature, and time), and of clay properties (such as clay minerals content, initial moisture content, soil porosity or equivalent pores size, clay surface area, cation-exchange capacity, and clay-swelling index) on the removal efficiency of PAHs from clayey soils were investigated. The results of this investigation were used to develop a semi-empirical correlation between the recovery (i.e. the extraction efficiency) at any time and above mentioned parameters and properties.     

Ab initio study of sorption on pyrophyllite: structure and acidity of the edge sites

Pyrophyllite, Al2[Si4O10](OH)2, is the simplest structural prototype for 2:1 dioctahedral phyllosilicates. Since it does not possess permanent structural charge as other clay minerals do, it is used to investigate sorption properties of the clay surfaces not related to the permanent structural charge. The bulk structure and surface geometries of pyrophyllite have been modeled using an orthorhombic constrained supercell. The results of the calculations are in excellent agreement with available experimental data and earlier ab initio simulations. It is shown that the symmetry-constrained model is able to accurately reproduce the basic structural characteristic of pyrophyllite. The electrostatic potential near the (001) surface was used to analyze a possible scenario for the water sorption on the basal plane of pyrophyllite. The calculations predict a slightly hydrophobic behavior of the basal plane. The hydronium ion was found to form a strongly bonded conformation in the siloxane cavity. The relative stability and composition of lateral facets of pyrophyllite have been studied using the supercell approach. The crystals of pyrophyllite are predicted to have a prismatic habit dominated by (110) and (-110) edge facets and basal plane. On the basis of the Fukui functions and the relative protonation/deprotonation enthalpies, the relative acidity and density of the reactive surface sites have been predicted. The triple bond Al-O-Si triple bond sites have the highest proton affinity on the (100), (110), and (130) facets and three line sign Al-OH groups on the (010) edges. The deprotonation of the triple bond Al-OH2 sites is followed by triple bond Al-OH and triple bond Si-OH groups. The calculations suggest a new scale for acidities of edge sites in pyrophyllite that should facilitate the thermodynamic modeling of the sorption processes in compacted clays.     

Studies on the polymer + plasticizer membrane-electrode-VIII Use of the PVC + tricresyl phosphate membrane as indicating electrode in potentiometric precipitation titration

Results obtained by use of the PVC + tricresyl phosphate membrane-electrode in potentiometric precipitation titration of some halides and pseudohalides are given. Solutions of Ag(+), Tl(+) and Hg(2)(2+) were used as titrants, to which the membrane is responsive. The fast response to Ag(+) ions allowed the determination of iodide by automatic recording of the potentiometric curve (or its derivative).