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The Influence of Temperature on the Adsorption of Cadmium(II) and Cobalt(II) on Goethite.

The adsorption of Cd(II) and Co(II) onto goethite was measured at five temperatures between 10 and 70 degrees C. For both cations the amount adsorbed at any given pH increased as the temperature was increased. Cd(II) adsorbed at a slightly lower pH at each temperature than Co(II). Adsorption isotherms at pH 7.00 for Cd(II) could be fitted closely by a simple Langmuir model, but a two-site Langmuir model was needed for Co(II). Potentiometric titrations of goethite suspensions in the presence and absence of added cation could be modeled closely by a constant-capacitance surface complexation model that assumed the adsorption reactions M2+ + SOH ⇋ SOM+ + H+ and M2+ + SOH + H2O ⇋ SOMOH + 2H+, where M represents Cd or Co. This model also fitted the experimental data from the adsorption edge and adsorption isotherm experiments. Thermodynamic parameters estimated from both Langmuir and surface complexation models showed that the adsorption of both metals was endothermic. Values obtained for the adsorption enthalpies from both modeling schemes were similar for both cations. Estimates of the adsorption entropies were model-dependent: Langmuir parameters yielded positive entropies, while some of the surface complexation parameters generated negative adsorption entropies. Copyright 1999 Academic Press.

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Competitive Adsorption of Cu(II)-EDTA and Cd(II)-EDTA onto TiO2.

Cu(II), EDTA, Cu(II)-EDTA, Cd(II)-EDTA, and Cu(II)/Cd(II) and Cu(II)-EDTA/Cd(II)-EDTA competitive adsorption onto TiO2 has been studied with variation of pH and concentration. For Cu(II) and EDTA, typical cationic and anionic types of adsorption are noted, respectively. Ligand-type adsorption is found for Cu(II)-EDTA and Cd(II)-EDTA under both single and competitive conditions. Surface complexation modeling considered inner-sphere complexation and the diffuse layer model employing MINTEQA2; surface complexes used include Ti-(OH2)O-Cu+, Ti-(OH)EDTAH-22, Ti-(OH)EDTA-Cu-2, and Ti-(OH)EDTA-Cd-2. Experimental and model predictions suggest no competitive adsorption between Cu(II) and Cd(II) at 5 x 10(-5) M. On the other hand, adsorption data and model predictions indicate that Cd(II)-EDTA adsorption is favored over that of Cu(II)-EDTA with some competition for adsorption sites. Cd(II)-EDTA adsorption was only slightly affected by the presence of Cu(II)-EDTA; however, Cu(II)-EDTA adsorption was strongly influenced by the presence of Cd(II)-EDTA, especially as the molar ratio of Cd(II)-EDTA/Cu(II)-EDTA increased. A modified surface complexation constant for Cd(II)-EDTA is required to explain the competitive data, suggesting surface site heterogeneity. Copyright 1999 Academic Press.

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Adsorption of Diblock Copolymers of Poly(ethylene oxide) and Poly(lactide) at Hydrophilic Silica from Aqueous Solution.

The adsorption of a series of amphiphilic poly(ethylene oxide)-poly(DL-lactide) (PEO-PL) diblock copolymers at the water/silica interface was investigated by ellipsometry and reflectometry. For all copolymers, a much higher saturation adsorption is found compared to that of the PEO homopolymers, indicating the importance of the PL block for the adsorption. The copolymers display a saturation adsorption that increases with increasing hydrophobic content of the polymer, and decreases with increasing hydrophilic content of the polymer. Despite this, however, the layer thickness observed is rather similar for all polymers, regardless of the length and composition of the copolymers. Moreover, the layer thicknesses were significantly higher than what would be expected for the unperturbered copolymer dimensions. The initial adsorption kinetics of the different copolymers are comparable. The initial adsorption rate increases cooperatively with concentration and is slower than that expected for diffusion-controlled adsorption. Moreover, the adsorption increases only slightly over a concentration the range from 20 to 50 degrees C. Furthermore, pH titrations show that all polymers exhibit a critical desorption pH of 8-9, which is lower than the corresponding value of pH 10.5 observed for the PEO homopolymer. These results are discussed in terms of the adsorption mechanism and the adsorbed layer structure and formation. Copyright 2000 Academic Press.

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Electrolyte Anion Affinity and Its Effect on Oxyanion Adsorption on Goethite.

The influence of various types of background electrolytes (NaCl, NaNO(3), and NaClO(4)) on the proton adsorption and on the adsorption of sulfate and phosphate on goethite have been studied. Below the PZC the proton adsorption on goethite decreases in the order Cl>NO(3)>ClO(4). The decreasing proton adsorption affects the adsorption of oxyanions on goethite. Anion adsorption of strongly binding polyvalent anions is lower in the studied electrolytes in the order Cl<NO(3)<ClO(4). The ion pair formation constants of monovalent electrolyte anions on the goethite surface are derived from proton adsorption data. It is shown that the derived ion pair formation constants enable the prediction of the effect of different electrolyte anions on adsorption of polyvalent anions. Especially at low oxyanion and high electrolyte concentrations the differences between the electrolytes influence the anion adsorption considerably. The effect is in principle not different for anions with a higher affinity for goethite, such as phosphate in comparison with sulfate, but the effect is only there if the particles are positively charged, which in the case of phosphate is only the case at relatively low P concentration and sufficiently low pH values. Copyright 2000 Academic Press.

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On the Applicability of the Langmuir Equation to Estimation of Adsorption Equilibrium Constants on a Powdered Solid from Aqueous Solution.

The Langmuir adsorption equation has become popular for summarizing solution-solid adsorption data and estimating adsorption equilibrium constants. The applicability of the Langmuir equation to estimation of adsorption equilibrium constants at solid-aqueous solution interfaces was theoretically examined in terms of (1) comparisons of solid-solution adsorption with solid-gas adsorption, (2) deductions of the Langmuir mathematical expression for the nonelectrolyte/solvent exchange, the phase exchange, the ion exchange, and the simple association reactions, and (3) the fitting procedure. The restrictive assumptions underlying the Langmuir equation for solid-gas adsorption may not be valid for adsorption of solute of small molecules or ions by a powdered solid surface from the aqueous solution phase. The fit of adsorption data to the Langmuir mathematical expression cannot be ascertained solely by the linearity of the commonly used equilibrium concentration/amount adsorbed versus the equilibrium concentration plot and does not provide the actual mechanism of the loss of small molecules or ions from aqueous solution. Therefore, the parameters of fitting to the Langmuir mathematical expression may not provide an unambiguous chemical meaning. In addition, we attempt to bring attention to the importance of the standard states of surface phase and solution phase. Copyright 2000 Academic Press.

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Temperature Dependence of Adsorption of Polymer Mixtures from Solutions.

Adsorption from binary (poly(butyl methacrylate)-CCl(4), poly-styrene-CCl(4)) and ternary (poly(butyl methacrylate)-polystyrene-CCl(4)) solutions has been studied at 10, 25, and 60 degrees C. It was found that with increasing temperature the values of adsorption grew due to worsening of the thermodynamic quality of the common solvent. Worsening of the quality of the solvent leads to a decrease in size of the macromolecular coils and to an increase in the critical concentrations of overlapping macromolecules in solution. As a result, the state of macromolecules in solution depends on temperature and determines adsorption values. From the temperature dependence of adsorption using the Clapeyron-Clausius equation, the differential enthalpy of adsorbate (polymer) DeltaH was calculated for each polymer, by adsorption both from binary solution and from the mixture. Determining DeltaH values from the temperature dependence of adsorption allows us to find this value simultaneously for each polymer in the polymer mixture. It was established that transition of a polymer from solution onto the surface leads to an increase in its enthalpy in the case of adsorption from both binary and ternary solutions. DeltaH increases with increasing coverage of the surface. By transition from solution onto the surface, the enthalpy of the adsorbed polymer increases; i.e., the polymer transits in an energetically less favorable state. This effect is more pronounced for adsorption from the mixture, which may be connected with the presence of the second polymer in the adsorption layer. Copyright 2000 Academic Press.

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A Study on the Adsorption Characteristics of Orthophosphates on Rutile-Type Titanium Dioxide in Aqueous Solutions.

Rutile-type titanium dioxide is widely used as a pigment for paint, coating ink, paper, plastic products, and cards because of its very whiteness and outstanding hiding property. It has two weak properties to be improved, however, one being its coagulation in compounding and the other its decreasing whiteness owing to poor heat resistance. To solve these problems, a study on the treatment of titanium dioxide surfaces by adsorption technology has been performed. Experiments have been carried out to establish the adsorption isotherms of orthophosphates on titanium dioxide and to investigate the effect of organic solvents on adsorption. It is shown that the adsorption isotherms vary with pH. A Freundlich adsorption isotherm is suitable for the acidic and basic regions, while a Langmuir adsorption isotherm is suitable for the region of pH 5-8 where a maximum adsorption has been achieved. In aqueous solutions containing organic solvents, the adsorption was strongest with aqueous solutions containing 1 wt% toluene and weakest with those containing 1 wt% ethanol. Among the alcohols used, the adsorption was strongest with the aqueous solution containing 1 wt% butanol and weakest with that containing 1 wt% ethanol, thus showing a correlation with the molecular weight of the alcohol. Copyright 2001 Academic Press.

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X-ray Absorption Spectroscopic Investigation of Arsenite and Arsenate Adsorption at the Aluminum Oxide-Water Interface.

We investigated the As(III) and As(V) adsorption complexes forming at the gamma-Al(2)O(3)/water interface as a function of pH and ionic strength (I), using a combination of adsorption envelopes, electrophoretic mobility (EM) measurements, and X-ray absorption spectroscopy (XAS). The As adsorption envelopes show that (1) As(III) adsorption increases with increasing pH and is insensitive to I changes (0.01 and 0.8 M NaNO(3)) at pH 3-4.5, while adsorption decreases with increasing I between pH 4.5 and 9.0, and (2) As(V) adsorption decreases with increasing pH and is insensitive to I changes at pH 3.5-10. The EM measurements show that As(III) adsorption does not significantly change the EM values of gamma-Al(2)O(3) suspension in 0.1 M NaNO(3) at pH 4-8, whereas As(V) adsorption lowered the EM values at pH 4-10. The EXAFS data indicate that both As(III) and As(V) form inner-sphere complexes with a bidentate binuclear configuration, as evidenced by a As(III)-Al bond distance of congruent with3.22 Å and a As(V)-Al bond distance of congruent with3.11 Å. The As(III) XANES spectra, however, show that outer-sphere complexes are formed in addition to inner-sphere complexes and that the importance of outer-sphere As(III) complexes increases with increasing pH (5.5 to 8) and with decreasing I. In short, the data indicate for As(III) that inner- and outer-sphere adsorption coexist whereas for As(V) inner-sphere complexes are predominant under our experimental conditions. Copyright 2001 Academic Press.

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Adsorption Equilibrium Equation of Carboxylic Acids on Anion-Exchange Resins in Water.

The adsorption of propionic acid and benzoic acid on anion-exchange resins was analyzed, and an adsorption equilibrium equation of carboxylic acids was proposed. The adsorption of carboxylic acids on the anion-exchange resins was considered to be the sum of the physical adsorption of the molecule and the ion-exchange adsorption of the ion, which were independent of each other. For the physical adsorption of carboxylic acids, it was conformed to the Freundlich equation. For the ion-exchange adsorption of carboxylate ions, the equilibrium equation corresponded well with the experimental results for wide ranges of concentration and pH. The equation contains a selectivity coefficient S(A)(Cl) for the chloride ion versus the carboxylate ion, which was considered essentially a constant. The influent of the bicarbonate ion from carbon dioxide in air could also be expressed by the additional equilibrium equation with the selectivity coefficient S(HCO(3))(Cl) for the chloride ion versus the bicarbonate ion. Consequently, an adsorption equilibrium equation can estimate the equilibrium adsorption amounts. Even the effect of a coexisting bicarbonate ion is inconsequential when the parameters of the Freundlich isotherm equation and the selectivity coefficients of the carboxylate ion and the bicarbonate ion in each resin are determined in advance. Copyright 2001 Academic Press.

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Specific counterion effects on the competitive co-adsorption of polyelectrolytes and ionic surfactants.

Counterions affect not only the bulk and interfacial self-assembly of ionic surfactants but also their competitive adsorption with similarly charged polyelectrolytes. Here, we explore the specific effects of bromide, chloride, and the bulky, somewhat hydrophobic tosylate counterion on the adsorption of hexadecyltrimethylammonium surfactants (CTA(+)), the adsorption of polylysine (PL), and the co-adsorption of CTA(+) and PL on negatively charged silica surfaces. Similar to bulk self-assembly, increasing the micellar binding affinity of the counterion from chloride to bromide to tosylate promoted interfacial self-assembly in the absence of polylysine. During co-adsorption, the presence of the polylysine decreased the adsorbed amount of CTA(+) in all cases. Polylysine was more effective at hindering CTA(+) adsorption when the surfactant concentration was below the critical micelle concentration. Although these systems were strongly influenced by persistent nonequilibrium states, it was possible to demonstrate that polylysine was able to prevent CTA(+) admicelle formation below the cmc only when the thermodynamic driving forces for adsorption of the polymer and the surfactant were comparable. Solution compositions where that condition was met depended on the identity of the counterion. Below the bulk cmc, CTAT adsorption displayed the greatest degree of cooperativity, and it also was the most susceptible to hindered adsorption by polylysine.

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Adsorption of molecules of biological interest onto hydroxyapatite.

Equilibrium and kinetic experiments were conducted to investigate the factors determining the adsorption of salivary macromolecules onto hydroxyapatite. Using amino acids and other small adsorbates, it was determined that the carboxyl attached to the alpha carbon does not appear to adsorb onto HA and the affinities of side-chain carboxyls are much smaller than that of the phosphate group (phosphoserine). Hydroxyl (serine) displays an extremely high affinity, but its adsorption site on HA is different and the number of such sites is much smaller than found for the rest of the functional groups investigated. It is shown that the information obtained from small molecules cannot be readily applied to prediction of the adsorption behavior of salivary macromolecules and polypeptides. The kinetics of adsorption of the salivary phosphopeptide statherin, a polyaspartate, and the salivary prolinerich phosphoprotein PRP3 are consistent with the reversibility of the adsorption process; no conclusion was possible in the case of the protein PRP1. Apparent irreversibility cannot be explained on the basis of multipoint binding or the properties of the carboxyl versus phosphate group; it appears that secondary structure determines to a significant extent the adsorption properties of the macromolecules. Calculation of the thermodynamic molar quantities of adsorption of PRP1, PRP3, and L-ASP onto HA showed that the process is entropically driven. The functional relationship between partial molar entropy and adsorption coverage is similar for the two proteins, but quite different from that for aspartate. Explanations for these results are advanced on the bases of changes in structure configurations and displacement of water from the adsorbate and the adsorbent surface, the second factor being the dominant one in the adsorption of a small molecule such as L-ASP.

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Adsorption of Co2+, Ni2+, Cu2+, and Zn2+ onto amorphous hydrous manganese dioxide from simple (1-1) electrolyte solutions.

The adsorption of Co2+, Ni2+, Cu2+, and Zn2+ onto amorphous hydrous manganese dioxide (delta-MnO2) has been studied using two methods, viz., isotherms at constant pH in the presence of buffer solution and pH variation in the absence of buffer solution from a fixed metal ion concentration. While the adsorption isotherm experiments were carried out in 0.5 M NaCl only, pH variation or batch titration experiments were carried out in 0.5 M NaCl, 0.01 M NaCl, and 0.01 M KNO3 solutions. The complex nature of adsorption isotherms at constant pH values indicates that adsorption of all the cations is non-Langmuirian (Freundlich) and takes place on the highly heterogeneous oxide surface with different binding energies. The proton stoichiometry derived from isotherms at two close pH values varies between 0.3 and 0.8. The variation of fractional adsorption with pH indicates that the background electrolyte solution influences the adsorption of cations through either metal-like or ligand-like complexes with Cl-, the former showing a low adsorption tendency. The proton stoichiometry values derived from the Kurbatov-type plot varies not only with the electrolyte solution but also with the adsorbate/adsorbent ratio. The variation of fractional adsorption with pH can be modeled either with the formation of the SOM+ type or with a combination of SOM+ and SOMOH type complexes, depending upon the cation and electrolyte medium. The equilibrium constants obtained from Kurbatov-type plots are found to be most suitable in these model calculations. Adsorption calculated on the basis of ternary surface metal-chlorocomplex formation exhibits very low values.

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Systematic studies on adsorption of lead on sea nodule residues.

Lead adsorption from aqueous solutions was studied with the aim of detoxifying industrial effluents before their safe disposal onto land or into river waters. Sea nodule residue (SNR), a waste material containing oxides and oxyhydroxides of manganese, iron, silicon, etc., was used as an effective adsorbent for lead in this study. The effect of various parameters such as contact time, initial lead concentration, pulp density, particle size of the adsorbent, pH, and temperature was studied to optimize the conditions for maximum adsorption. Adsorption followed first-order kinetics and 99% of lead adsorption was achieved at a solid:liquid ratio of 1:330, in the pH range 5.5-6.0 at a particle size of -150 microm in 8 h for solution containing 200 ppm lead. The adsorption capacity was found to be 99.0 mg of lead per gram of SNR and the adsorption isotherms followed the Langmuir and Freundlich adsorption models. The mechanism of adsorption of lead onto the sea nodule residue was also investigated. It was possible to reduce the lead level from 25-200 ppm to acceptable levels (0.1 ppm) by adsorption over this solid waste.

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Energy of adsorption interaction and surface coverage from polymer of various molecular structures.

Adsorption from solutions of mixtures of polymers which considerably differ by the parameter of thermodynamics flexibility (sigma) has been studied at various components ratio. Initial and equilibrium concentrations of solutions were determined, surface coverage (theta) and energy of adsorption interaction (Q, kJ/mol of segments) were estimated by means of IR spectroscopy. The objects of investigation were: cis-1,4-polybutadiene rubber (PB) and cellulose triacetate (CTA). Aerosil (fumed silica) was used as an adsorbent. Analysis of the experimental data testifies that polymer polarity and its affinity to the surface have the decisive influence on the adsorption. Polar stiff chain CTA has greater affinity to the surface of adsorbent and correspondingly has greater adsorption activity as compared with flexible, but nonpolar PB. The values of energy of adsorption interaction and surface coverage obtained under the adsorption from polymer systems first of all depend on whether the stiff chain polar component or flexible chain nonpolar component prevails in the system. Increase of concentration of the nonpolar PB flexible chain in the system results in diminishing of summary energy of adsorption interaction, but its great flexibility at the same components ratio provides the maximal values of surface coverage. The greater values of the surface coverage under the adsorption from the solutions of polymer mixtures in comparison with the individual solutions are explained by the simultaneous adsorption of both components for all concentration intervals.

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The influence of temperature on the adsorption of mellitic acid onto goethite.

The adsorption of mellitic acid (benzene-1,2,3,4,5,6-hexacarboxylic acid) onto goethite was investigated at five temperatures between 10 and 70 degrees C. Mellitic acid adsorption increased with increasing temperature below pH 7.5, but at higher pH the effect of increasing temperature was to reduce the amount adsorbed. Potentiometric titrations were conducted and adsorption isotherms were measured over the same temperature range, and the data obtained were used in conjunction with adsorption edge data to develop an Extended Constant Capacitance Surface Complexation Model of mellitic acid adsorption. A single set of reactions was used to model the adsorption for the three different experiment types at the five temperatures studied. The adsorption reactions proposed for mellitate ion (L(6-)) adsorption at the goethite surface (SOH) involved the formation of two outer-sphere complexes: SOH + L(6-) + 3H+ <==> [(SOH2)+ (LH2)(4-)]3-, 2SOH + L(6-) + 2H+ <==> [(SOH2)2(2+) (L)(6-)]4-. This mechanism is consistent with recent ATR-FTIR spectroscopic measurements of the mellitate-goethite system. Thermodynamic parameters calculated from the temperature dependence of the equilibrium constants for these reactions indicate that the adsorption of mellitic acid onto goethite is accompanied by a large entropy increase.

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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.

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Kinetics and adsorption behavior of carboxymethyl starch on alpha-alumina in aqueous medium.

The adsorption of carboxymethyl starch (CMS) at the alpha-alumina/aqueous solution interface has been investigated through adsorption studies, electrokinetics mobility measurements, and FTIR spectroscopy. Zeta potential measurements show that the addition of CMS results in a more dramatic increase in the absolute zeta potential in the alkaline region, as well as a shift of the isoelectric point to lower values, indicating the adsorption of CMS from the aqueous solution onto the alumina surface. The positive hydrophilic surface sites of alumina are responsible for the adsorption of CMS molecules. The adsorption of CMS is possible after charge reversal by the addition of excess CMS. Nearly 30 min of contact time are found to be sufficient for the adsorption of CMS to reach equilibrium. CMS adsorption follows a Langmuir isotherm with adsorption capacities of 91.74 mg CMS per gram of alpha-alumina. For the adsorption of CMS, pseudo-second-order chemical reaction kinetics provides the best correlation with the experimental data. FTIR analysis indicated that CMS forms outer complexes with alumina surfaces depending on the shifting of the asymmetric and symmetric bands.

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Adsorption of volatile organic compounds onto carbon nanotubes, carbon nanofibers, and high-surface-area graphites.

The adsorption of different alkanes (linear and cyclic), aromatics, and chlorohydrocarbons onto different nonmicroporous carbons--multiwalled carbon nanotubes (CNTs), carbon nanofibers (CNFs), and high-surface-area graphites (HSAGs)--is studied in this work by inverse gas chromatography (IGC). Capacity of adsorption was derived from the isotherms of adsorption, whereas thermodynamic properties (enthalpy of adsorption, surface free energy characteristics) have been determined from chromatographic retention data. HSAGs present the highest adsorption capacity, followed by CNTs and CNFs (although CNTs present an intermediate surface area between the two HSAG studied). Among the different adsorbates tested, benzene exhibits the highest adsorption capacity, and the same trend is observed in the enthalpy of adsorption. From surface free energy data, enthalpies of adsorption of polar compounds were divided into dispersive and specific contributions. The interactions of cyclic (benzene and cyclohexane) and chlorinated compounds (trichloroethylene, tetrachloroethylene, and chloroform) with the surfaces are mainly dispersive over all the carbons tested, CNTs being the material with the highest dispersive contribution, as was deduced also from the entropy parameter. Adsorption parameters were correlated with morphological and chemical properties of the materials.

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