Kinetics of adsorption of polyvinylamine on cellulose fibers. II. Adsorption from electrolyte solutions

Adsorption from electrolyte solutions of fully hydrolyzed polyvinylamine on cellulose fibers was investigated by supplying the polymer to the fibers at controlled rate. This was implemented by employing a reactor only open to the fluid in which the fiber dispersion were confined and homogenized. The adsorbed layers may be defined as diffuse or dense layers. Diffuse layers are characterized by a surface coverage limited to 0.65 mg/g cellulose in salt-free solutions. Addition of NaCl or CaCl(2) to the fiber dispersion and the polymer solution promotes the adsorption rate and increases the amount of adsorption to 1.5 mg/g cellulose. For dense polymer layers, for which the coverage amounts to values close to 10 mg/g cellulose in salt-free systems, addition of electrolyte does not change the kinetic and adsorption characteristics. Insofar as the variation of the molecular areas of the polymer within the diffuse layers as a function of the ionic strength parallels the variation of the molecular characteristics of solute molecules, the formation of diffuse layers is expected to proceed by random deposition of solute molecules which later individually sustain strong reconformation. Adsorption isotherms show a limited influence of the ionic strength. Obviously, the passage from dense layers of high surface coverage to low adsorption values at equilibrium requires extended reconformation of adsorbed macromolecules and desorption of a great part of the molecules already adsorbed.     

Thermodynamics of adsorption of organic liquids on Ni-modified solid obtained from collodal silica

Summary In order to reduce the well known silica surface inhomogeneity and to get a material suitable for selective chromatographic separations, a modified variety of the material was prepared by a controlled sorption of Ni²⁺ ions at the solid surface; its adsorption properties were then investigated using the GSC method. Since the starting material was of very high purity, it was possible to follow the influence of Ni²⁺ ion on the adsorption of various organic liquids, including n-alkanes, cyclohexane, benzene and halomethanes. Adsorption experiments, spanning zero surface coverage and the finite concentration region, were performed in the temperature range from 333 to 443 K. Both the surface activity change resulting from the modification and the possible interactions between the organic substances and the prepared adsorbent were examined using the standard free energy change of adsorption in zero coverage conditions. The adsorption isotherms of all the adsorbates listed were obtained using the Elution by Characteristic Point (ECP) technique and the data were fitted to the BET equation. To get a better insight into the adsorption process in the finite concentration region, the thermodynamic parameters of adsorption were determined and are discussed in terms of surface coverage.     

Irreversible adsorption of triple-helical soluble collagen monomers from solution to glass and other surfaces

The adsorption from various solutions of triple-helical soluble collagen monomers to solid surfaces was studied by labeling the collagen with ¹²⁵1. Adsorption to glass, siliconized glass, and Teflon, from aqueous solutions at various pH and ionic strength, was determined at collagen concentrations from 2 to 25 μg/ml. Adsorption was shown to be irreversible and little dependent on pH and ionic strength but increasing enormously as the surface is made more hydrophobic. Surface denaturation of the collagen by heat results in a substantial loss of material. The kinetics of adsorption suggest that the adsorption process may be selective and that not all collagen molecules which reach the surface are immediately adsorbed. Checking these results with earlier measurements of adsorbed layer thickness, a model for collagen adsorption is proposed.     

Electrocatalytic and adsorption properties of platinum microparticles electrodeposited onto glassy carbon and into Nafion® films

A comparative investigation of electrocatalytic and adsorption properties of platinum microparticles electrodeposited onto a glassy carbon surface (Pt/GC) and within a thin Nafion® film formed on a GC electrode (Pt/Nf/GC) is described. As test reaction the methanol oxidation in sulfuric acid solutions is used. Dependences of the steady-state specific reaction rates upon potential and methanol concentration were established, as well as those of the platinum surface coverage with methanol chemisorption products upon concentration. It was shown that at higher platinum loadings (above 60 μg cm⁻²) the specific activities of Pt/GC and Pt/Nf/GC are nearly the same and close to that of smooth platinum. At such loadings the surface coverage of the platinum deposit surface with organic particles does not differ from that of smooth platinum. At very low platinum loadings in the polymeric matrix (10–30 μg cm⁻²) a considerable decrease in the adsorption of strongly chemisorbed methanol particles is observed. These deposits are characterized by a low specific activity, which may be caused by the decrease of the platinum particle’s size, leading to a decrease in the amount of weakly bound methanol particles participating in the limiting reaction step.     

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.     

Adsorption of <Superscript>125</Superscript>Sb on alumina and titania surfaces

Adsorption of long-lived ¹²⁵Sb radioisotope (T _1/2 = 2.75 y) on alumina (Al₂O₃) and titania (TiO₂) has been studied at different pH. Both the oxides have good adsorption capability for the ¹²⁵Sb radioisotopes but the TiO₂ is much superior. Adsorption kinetics of ¹²⁵Sb radioisotopes on TiO₂ surface and desorption of ¹²⁵Sb radioisotopes from TiO₂ surface in acidic and alkaline media have also been studied. The ¹²⁵Sb-TiO₂ phase has been subjected to γ-irradiation and found to be radiation stable against antimony release.     

Effect of polyethylene oxide on the viscosity of dispersions of charged silica particles: interplay between rheology, adsorption, and surface charge

In this study a systematic investigation on the adsorption of polyethylene oxide (PEO) onto the surface of silica particles and the viscosity behavior of concentrated dispersions of silica particles with adsorbed PEO has been performed. The variation of shear viscosity with the adsorbed layer density, concentration of free polymer in the solution (depletion forces), polymer molecular weight, and adsorbed layer thickness at different salt concentrations (range of the electrostatic repulsion between particles) is presented and discussed. Adsorption and rheological studies were performed on suspensions of silica particles dispersed in solutions of 10⁻² M and 10⁻⁴ M NaNO₃ containing PEO of molecular weights 7,500 and 18,500 of different concentrations. Adsorption measurements gave evidence of a primary plateau in the adsorption density of 7,500 MW PEO at an electrolyte concentration of 10⁻² M NaNO₃. Results indicate that the range of the electrostatic repulsion between the suspended particles affects both adsorption density of the polymer onto the surface of the particles and the viscosity behavior of the system. The adsorbed layer thickness was estimated from the values of zeta potential in the presence and absence of the polymer and was found to decrease with decreasing the range of the electrostatic repulsive forces between the particles. Experimental results show that even though there is a direct relation between the viscosity of the suspension and the adsorption density of the polymer onto the surface of the particles, variation of viscosity with adsorption density, equilibrium concentration of the polymer, and range of the electrostatic repulsion cannot be explained just in term of the effective volume fraction of the particles and needs to be further investigated. Received: 15 February 2000/Accepted: 26 June 2000     

How silanization of silica particles affects the adsorption of PDMS chains on its surface

A series of six fumed silica types, with different surface areas in the 50–400 m²/g range, were modified by grafting with trimethylchlorosilane. The grafting reaction was controlled by elemental analyses, surface hydroxyl titration, and combustion techniques. The silica surface energy was determined as a function of silanization degree by inverse gas chromatography (IGC). Adsorption of a series of poly(dimethylsiloxane) elastomers with molecular weights ranging between 4 and 420 kg/mol on silica was followed using flow microcalorimeter (FMC). IGC results show that free adsorption energies of two series of alkanes and siloxanes as well as the dispersive component of the surface energy were found to decrease monotonously with surface silanization and so does the polymer molar heat of adsorption. FMC results indicate, however, that the conformation of the macromolecules on silica depends on the silica surface area but remains unaffected by the surface treatments. A given polymer chain was found to remain adsorbed on the surface preserving its same conformation until its molar heat of adsorption falls bellow a critical value. These findings offer a better monitoring of surface–polymer interactions as it defined a comprehensive relationship between the degree of modifications of the filler surface and polymer adsorption conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Adsorption of water on a platinum electrode from dimethylsulphoxide solution

Adsorption of water from DMSO solution on platinum was studied by the use of the direct tritium radioelectrochemical method. It was found that adsorption occurs in the second ad-layer of the Pt-DMSO interface with the maximum surface concentration 1.1×10¹⁵ mol cm^?2. This value was attributed to the monolayer of the adsorbate. Formally, Temkin conditions were found. No potential dependence of HTO adsorption was observed. Some remarks on the double-layer structure of the Pt electrode in DMSO are included.The potential dependence of DMSO adsorption previously determined with the ³⁵S compound has now been confirmed by using T-labelled DMSO. This is considered as evidence that no H-T isotope exchange between chemisorbed DMSO and water from the solution phase occurs.     

Tin underpotential deposition on platinum and its catalytic influence on the kinetics of molecular oxygen electroreduction

The formation and dissolution of tin ad-layers on polycrystalline platinum were analysed by cyclic voltammetry in aqueous 10^–4 M tin(II)/1 M sulfuric acid in the 0.05–0.70 V versus RHE range. At this concentration level it was possible to observe that platinum sites involving (110) planes are mainly related to tin underpotential deposition. In contrast to previous results, no irreversible adsorption was found in the course of the electrodeposition. Thermodynamic adsorption parameters were calculated from the potential dependence of tin surface coverage. Catalytic properties of this new surface were studied on the basis of oxygen electroreduction as a model. Kinetic runs were performed with rotating ring-disk electrodes on bare and tin-modified platinum surfaces. Molecular oxygen reduction on tin-modified platinum takes place through the production of both water and hydrogen peroxide. This interpretation was confirmed by calculating the reaction order with respect to oxygen. Electronic Publication     

Influence of size and functionality of polymeric nanoparticles on the adsorption behavior of sodium dodecyl sulfate as detected by isothermal titration calorimetry

Isothermal titration calorimetry was used to monitor the adsorption of the surfactant sodium dodecylsulfate (SDS) on different sized pure and carboxy functionalized polystyrene nanoparticles prepared by the mini-emulsion process. The ITC experiment gives, additionally to the CMC values, information about the interaction of the surfactant molecules to the particle’s surface due to the particle surface properties. The adsorption heat depends on the chemical composition of the polymer as well on the particle size. It also provides information about the surface coverage with surfactant and the number of additional adsorbed molecules per particle until full coverage by surfactant is obtained. The surfactant adsorption increases from 0.3 molecules per nm² for 50 nm to 8.5 molecules per nm² for carboxy functionalized particles with diameters larger than 160 nm. The area A _Surf-dens after the adsorption process gives information about the packing density of surfactant molecules on the particles in dependence of carboxy groups: an increasing number of carboxylic groups decreases the area occupied per SDS molecule. The adsorption process was also monitored by zeta potential measurements, where an increasing potential during the adsorption was detected.     

Electrosorption of β-naphthol on graphite

Isotherms for the adsorption of β-naphthol from a buffered aqueous solution of 0.5 M K₂SO₄ onto graphite were detemrined over a range of potential of 1.27 V. The adsorbent was a packed bed of ?100 + 120 mesh graphite powder. Sufficient surface area was available to calculate accurately the amount adsorbed by measuring spectrophotometrically the change in adsorbate concentration in the bulk solution.At all potentials, a Langmuir adsorption isotherm, modified for the displacement of solvent molecules, was followed up to 60–65% of monolayer coverage. The ratio of projected areas of β-naphthol and water molecules was consistent with the experimentally derived number of solvent molecules displaced, six. The largest amount of adsorption observed, 2.5×10^?10 mol cm^?2, agreed with the calculated monolayer coverage of β-naphthol molecules lying in flat orientation on the graphite surface. Adsorption increased at more positive potentials. Over the range of potential investigated, the adsorbability constant increased sixfold. Desorption was only partially reversible.     

Metal Nanoparticles on Polymer Surfaces: 2. Catalytic Activity of Platinum Nanoparticle Ensembles on Polystyrene

Catalytic properties of platinum nanoparticles deposited onto polystyrene surface from their hydrosol stabilized with sodium polyacrylate are studied. It is shown that, during the adsorption on polymer substrate, metal nanoparticles form rather densely packed ordered monolayer ensembles with high catalytic activity in the model reaction of hydrogen reduction of methyl viologen. This allows one to measure the reaction rate with standard spectrometric method using polymer film with the surface area of 1 cm² or less as a catalyst support.     

Single‐Molecule Measurement of Adsorption Free Energy at the Solid–Liquid Interface

Adsorption plays a critical role in surface and interface processes. Fractional surface coverage and adsorption free energy are two essential parameters of molecular adsorption. However, although adsorption at the solid–gas interface has been well‐studied, and some adsorption models were proposed more than a century ago, challenges remain for the experimental investigation of molecular adsorption at the solid–liquid interface. Herein, we report the statistical and quantitative single‐molecule measurement of adsorption at the solid–liquid interface by using the single‐molecule break junction technique. The fractional surface coverage was extracted from the analysis of junction formation probability so that the adsorption free energy could be calculated by referring to the Langmuir isotherm. In the case of three prototypical molecules with terminal methylthio, pyridyl, and amino groups, the adsorption free energies were found to be 32.5, 33.9, and 28.3 kJ mol^?1, respectively, which are consistent with DFT calculations.     

DFT study of interaction of O, O2, and OH with unreconstructed Pt(hkl) (h, k, l = 0, 1) surfaces—similarities, differences, and universalities

Adsorption of O, O₂, and OH on Pt(111), Pt(100), and Pt(110) surfaces was studied using periodic DFT calculations. It was found that generally adsorbate-surface interaction strengths increase with the decrease in surface packing density. On the Pt(111) surface the dissociation of O₂ molecule was not predicted, but it was predicted on Pt(100) and Pt(110) surfaces. While the strength of the adsorbate-substrate interaction decreases with the rise in surface coverage by O atoms, in the case of OH adsorption adsorbate layer gets stabilized at higher surface coverage through the hydrogen bonding. In spite of all the mentioned differences, single parameter of surface electronic structure was identified, being useful for the explanation of the adsorption trends at different adsorption sites for O and OH adsorption on Pt surfaces of various crystallographic orientations and also provided a deeper understanding of atomic oxygen adsorption as a function of surface coverage.     

Adsorption of n-alkanes on a graphitized carbon black and its activation products in dry air

Summary Adsorption of n-alkanes (n-heptane to n-decane) on a graphitized carbon black and its activation products in dry air was carried out by a gas chromatographic technique. Adsorption runs were performed at finite surface coverage, to obtain the surface area and the London component of the surface free energy of the solids from the adsorption isotherms. On the other hand, the adsorption of n-alkanes carried out at zero surface coverage gave the differential heats of adsorption. The results show that, after the activation in dry air of the graphitized carbon black used, the surface area has a linear relationship with the degree of activation, whereas the surface heterogeneity changes in a parabolic fashion.     

Adsorption of benzoic acid onto high specific area activated carbon cloth

The adsorption of benzoic acid from aqueous solution onto high area carbon cloth at different pH values has been studied. Over a period of 125 min the adsorption process was found to follow a first-order kinetics and the rate constants were determined for the adsorption of benzoic acid at pH 2.0, 3.7, 5.3, 9.1, and 11.0. The extents of adsorption and the percentage coverage of carbon cloth surfaces were calculated at 125 min of adsorption. Adsorption isotherms at pH values of 2.0, 3.7, and 11.0 were derived at 25 degrees C. Isotherm data were treated according to Langmuir and Freundlich equations and the parameters of these equations were evaluated by regression analysis. The fit of experimental isotherm data to both equations was good. It was found that both the adsorption rate and the extent of adsorption at 125 min were the highest at pH 3.7 and decreased at higher or lower pH values. The types of interactions governing in the adsorption processes are discussed considering the surface charge and the dissociation of benzoic acid at different pH values.     

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.     

Adsorption of mycotoxins by organozeolites

Adsorption of zearalenone (ZEN), ochratoxin A (OCHRA) and aflatoxin B1 (AFB1) on natural zeolite, clinoptilolite, modified with different amounts of octadecyldimethylbenzyl ammonium (ODMBA) ions was investigated. Results showed that adsorption of hydrophobic ionizable ZEN on unmodified zeolite tuff was very low and that adsorption on organozeolites increased with increasing hydrophobicity of the zeolitic surface. The adsorption was independent of the form of ZEN in solution and the solution pH, indicating that hydrophobic interactions with ODMBA are responsible for ZEN adsorption. Adsorption of low polar ionizable OCHRA on organozeolites also increased with increasing hydrophobicity of the zeolitic surface, however, OCHRA showed moderate adsorption on unmodified zeolitic tuff at pH 3. OCHRA adsorption on unmodified zeolite as well as on lower surface coverage of organozeolite was dependent on the form of OCHRA in solution; there was a decrease of adsorption at high pH, where OCHRA is in the anionic form. It indicated that at acidic pH, low surface coverage allows some combination of hydrophobic interaction with ODMBA and interactions with the surface of the zeolite. At higher surface coverage, the OCHRA adsorption was higher and practically independent of pH, indicating that the hydrophobic interactions of OCHRA with ODMBA are responsible for its adsorption. Nonionizable low polar AFB1 had a high affinity for the unmodified zeolitic tuff and the adsorption of AFB1 was greatly reduced for organozeolites, indicating that AFB1 does not have high tendency for hydrophobic interactions with ODMBA. pH dependence of AFB1 adsorption, while AFB1 has the same form at all pHs, demonstrated that the surface modification of the zeolite depends on pH and that these modifications have influence on its adsorption. The calculated dipole moments of neutral mycotoxin molecules: AFB1-9.5D, OCHRA-6.9D and ZEN-2.2D are in qualitative agreement with adsorption experimental data.     

Adsorption of PtCl62- anions on the surface of carbon black?

Summary Adsorption of PtCl₆^2- anions on surface of carbon black was studied. It was found that the absence of surface oxygen groups led to a higher Pt loading amount, and the Pt loading amount would decrease as using a higher H₂PtCl₆ impregnating solution concentration. The π sites in the basal planes of carbon black surface act as the chemical adsorption sites, playing a more important role than surface oxygen groups in PtCl₆^2- adsorption. Adsorption of large amounts of H₃O⁺ in the π sites would lead to a decrease of chemical adsorption capacity.