In situ investigation of the adsorption of alkyltrimethoxysilanes on iron surfaces

Summary The adsorption of methyl and butyl-trimethoxysilane onto iron surfaces from the gas phase at different humidity levels has been investigated in situ with a quartzcrystal micro-balance and with ATR-IR spectroscopy. The thickness of the resulting siloxan polymer depends on the humidity during the film preparation. The polymer coating inhibits the corrosion of iron in an SO₂-containing atmosphere.     

In-situ investigation of aerosol particles by atomic force microscopy

In-situ imaging of aerosol particles deposited on mica in the TM-AFM liquid cell has been performed in order to study their dissolution behavior. The results show that the implementation of in-situ experiments is very useful for obtaining information on the physical and chemical behavior of individual particles. Experiments were carried out using ammonium sulfate and soot-like particles as test aerosols. Water soluble fractions can be easily distinguished from insoluble fractions. This can also be utilized to proof the existence of internally mixed particles. These model experiments are an important basis for further investigations on airborne particles involving other solvent systems and time resolved measurements.     

Collagen adsorption and structure on polymer surfaces observed by atomic force microscopy

The structure and adsorption patterns of type I and type III collagen were imaged on various polymer substrates with atomic force microscopy. Type I collagen had higher adsorption on polystyrene than on a series of polymethacrylates and formed a network of tightly, interwoven strands. Upon adsorption to different polymethacrylates, with varying side chain lengths, the collagen molecules formed long, branching fibrils. Types I and III collagen had different adsorption patterns, in some cases, on the identical substrate material. For example, instead of forming a tightly packed network, type III forms long, branching fibers on the polystyrene surface. On other materials, such as poly(n-butyl methacrylate), the two types of collagen showed similar adsorption pattern and structure. Adsorbed collagen was also imaged on various blends of polystyrene and polymethacrylates to determine how the polymer surface chemical structure and surface topography mediates protein adsorption.     

Bismuth(V) iron(III) tris(phosphate) oxide

Bi^V_0.4Fe₃^IIIO(PO₄)₃ crystallizes with two Fe atoms (one on an inversion centre and one on a mirror plane) displaying octahedral geometry and a third Fe atom (on a mirror plane) with trigonal bipyramidal coordination. Fe atoms are seen in oxy­gen‐bridged chains. Bi^V atoms are found in the interstitial sites between these chains. Bi shows sevenfold coordination, with Bi—O distances between 2.357 (7) and 2.529 (6) Å.     

Chemical force titrations of functionalized Si(111) surfaces

Chemical force titrations-plots of the adhesive force between an atomic force microscope tip and sample as a function of pH-were acquired on alkyl monolayer-derivatized Si(111) surfaces. Gold-coated AFM tips modified with thioalkanoic acid self-assembled monolayers (SAM) were employed. Alkyl monolayer-derivatized Si(111) surfaces terminated with methyl, carboxyl, and amine groups were produced via hydrosilylation reactions between 1-alkene reagents and H-terminated silicon. The functionalized surfaces were characterized using standard surface science techniques (AFM, FTIR, and XPS). Titration of the methyl-terminated surface using the modified (carboxyl-terminated) atomic force microscope tip resulted in a small pH-independent hydrophobic interaction. Titration of the amine-terminated surface using the same tip resulted in the determination of a surface pKa of 5.8 for the amine from the pH value from the maximum in the force titration curve. A pK(1/2) of 4.3 was determined for the carboxyl-terminated Si(111) in a similar way. These results will be discussed in relation to the modified Si(111) surface chemistry and organic layer structure, as well as with respect to existing results on Au surfaces modified with SAMs bearing the same functional groups.     

Irreversible adsorption of particles on heterogeneous surfaces

Methods of theoretical and experimental evaluation of irreversible adsorption of particles, e.g., colloids and globular proteins at heterogeneous surfaces were reviewed. The theoretical models were based on the generalized random sequential adsorption (RSA) approach. Within the scope of these models, localized adsorption of particles occurring as a result of short-ranged attractive interactions with discrete adsorption sites was analyzed. Monte-Carlo type simulations performed according to this model enabled one to determine the initial flux, adsorption kinetics, jamming coverage and the structure of the particle monolayer as a function of the site coverage and the particle/site size ratio, denoted by lambda. It was revealed that the initial flux increased significantly with the site coverage theta(s) and the lambda parameter. This behavior was quantitatively interpreted in terms of the scaled particle theory. It also was demonstrated that particle adsorption kinetics and the jamming coverage increased significantly, at fixed site coverage, when the lambda parameter increased. Practically, for alpha = lambda2theta(s) > 1 the jamming coverage at the heterogeneous surfaces attained the value pertinent to continuous surfaces. The results obtained prove unequivocally that spherically shaped sites were more efficient in binding particles in comparison with disk-shaped sites. It also was predicted that for particle size ratio lambda < 4 the site multiplicity effect plays a dominant role, affecting significantly the structure of particle monolayers and the jamming coverage. Experimental results validating main aspects of these theoretical predictions also have been reviewed. These results were derived by using monodisperse latex particles adsorbing on substrates produced by covering uniform surface by adsorption sites of a desired size, coverage and surface charge. Particle deposition occurred under diffusion-controlled transport conditions and their coverage was evaluated by direct particle counting using the optical and electron microscopy. Adsorption kinetics was quantitatively interpreted in terms of numerical solutions of the governing diffusion equation with the non-linear boundary condition derived from Monte-Carlo simulations. It was proven that for site coverage as low as a few percent the initial flux at heterogeneous surfaces attained the maximum value pertinent to homogeneous surfaces. It also was demonstrated that the structure of larger particle monolayers, characterized in terms of the pair correlation function, showed much more short-range ordering than predicted for homogeneous surface monolayers at the same coverage. The last part of this review was devoted to detection of polyelectrolyte multilayers on various substrates via particle deposition experiments.     

Spectroscopic investigation of the adsorption mechanisms of polyacrylamide polymers onto iron oxide particles

The mechanisms of high-molecular-weight polyacrylamide nonionic homopolymer and 25 mol% anionic acrylate-substituted copolymer adsorption onto iron oxide particles were investigated via DRIFT and UV-vis spectroscopies at three pH values (6, 8.5, and 11). While electrostatic interactions play an important role in charged polymer adsorption, this information is not spectroscopically available. At pH values above and below pH 8.5 (the isoelectric point for the anionic polymer), bidentate chelation and hydrogen bonding were the main adsorption mechanisms. At the isoelectric point, monodentate chelation was observed to be the main mode of adsorption, along with hydrogen bonding. For the nonionic polymer, in all cases, hydrogen bonding through the carbonyl group was the main mode of adsorption. The adsorption of both polymers conformed well to the Freundlich model, suggesting that the adsorbed polymer amount increases with increasing polymer concentration up to 7500 g/t solid, rather than approaching monolayer coverage. Spectroscopic evidence was found to suggest that hydrolysis of nonionic polyacrylamide occurs at high pH.     

Direct STM investigation of cinchona alkaloid adsorption on Cu(III)

Scanning tunneling microscopy (STM) combined with cyclic voltammetry has been employed to investigate the adsorption of cinchonine on Cu(111). Similar to cinchonidine, cinchonine forms a long-range ordered adlayer with (4 x 4) symmetry on the substrate. The structural details on molecular adsorption were obtained by high-resolution STM images. On the basis of the previous results and obtained STM images, the quinoline ring is proposed to lie parallel to Cu(111) and serve as an anchoring group. The chiral quinuclidine moiety extends out of the surface to facilitate the interaction with the prochiral reactants.     

Chelate adsorption for trace voltammetric measurements of iron(III)

Summary A very sensitive electrochemical stripping procedure for trace measurements of iron(III) is described. The chelate of iron with Solochrome Violet RS is adsorbed on the hanging mercury drop electrode, and the reduction current of the accumulated chelate is measured by voltammetry. The adsorption and redox behaviours are explored by cyclic voltammetry. The height of the chelate peak, which is about 0.28 V more negative than the peak of the free dye, is shown to be proportional to the iron concentration. Optimal experimental conditions include a preconcentration potential of –0.40 V, solution pH of 5.1 and a linear scan mode. The sharp chelate peak, associated with the effective interfacial accumulation, coupled with the flat baseline, facilitates measurements at the nanomolar and submicromolar concentration levels using short preconcentration times. The limit of detection after 1 min preconcentration is 0.04 gl^–1 (7 × 10^–10 M), and the relative standard deviation at the 10^–7 M level is 4.7%. The effects of possible interferences, due to coexisting metal ions or organic surfactants, are evaluated. The ability of measuring iron(III) in the presence of iron(II) is illustrated. Actual analyses of sea and tap waters are reported.

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Chelat-Adsorption für voltammetrische Spurenanalyse von Eisen(III)

     

Kinetics of iron(III) chloride extraction with n-tributyl phosphate

The equilibrium and rate of solvent extraction of FeCl₃ complexes from HCl solutions into benzene solutions of tributyl phosphate (TBP) has been studied. The extracted species was found to be FeCl₃·3TBP. The results show that the extraction is first order in both Fe(III) and TBP. The rate constant of adduct formation equals ～1.24M min^?1. The reaction order is zero for the aqueous phase acidity. The rate-controlling steps are discussed in the light of the results.     

Kinetics of iron(III) bromide extraction with n-tributyl phosphate

The equilibrium and rate of solvent extraction of FeBr₂ complexes from HBr solutions into benzene solutions of tributyl phosphate (TBP) have been investigated. It is found that two reactions control the iron(III)-TBP extraction from hydrobromic acid solutions. From HBr activity of 1.2–1.55 (molarity based) the reaction is inverse third order with respect to the aqueous phase acidity. From HBr activity of 1.7–6 (molarity based) the reaction is first order in HBr concentration in the aqueous phase. Both of these reactions are first order for both Fe(III) and TBP. The rate constants for these reactions were calculated and the rate-controlling steps are discussed.     

An X-ray investigation on the structure of iron(III) perchlorate solutions

Ferric perchlorate solutions have been investigated by an X-ray scattering technique. The main features of the radial distribution functions are consistent with the presence of ClO₄⁻ ions and of hydrated Fe(H₂O)₆³⁺ complexes in octahedral configuration. Structural parameters have been derived for these two species from the outermost parts of the reduced intensity functions. An hydrogen bonded structure outside the inner coordination sphere of iron(III) is strongly suggested by the presence of a large peak at 4 Å in the radial distribution curves. In this respect a comparison between iron(III) perchlorate and nitrate solutions has made possible to evidentiate a similar structural arrangement for Fe³⁺ ions in both media. Some indications have been also obtained supporting the existence of an outer-sphere FeClO₄ complex and of hydration water around the perchlorate group.     

Thermoanalytical investigation of the aluminothermic reduction of iron(III) oxide

Differential thermal analysis technique has been applied to determine the heat of reduction of iron oxide by aluminium. It has been observed that the DTA curve can be used for quantitative determination of heats of reactions at high temperature ranges where differential scanning calorimetry is not applicable. The experimental results obtained agree closely with the theoretical value of the heat of reaction.

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Zusammenfassung Unter Anwendung von DTA wurde die Bestimmung der Reaktionswärme der Reduktion von Eisenoxid mit Aluminium durchgeführt. Es konnte festgestellt werden, daß DTA zur quantitativen Bestimmung von Reaktionswärmen bei hohen Temperaturen geeignet ist, bei denen DSC nicht mehr angewendet werden kann. Die ermittelten experimentellen Ergebnisse stimmen gut mit dem theoretischen Wert für die Reaktionswärme überein.

     

Precipitation of monodispersed basic iron(III) sulfate (sodium jarosite) particles

Uniform sodium jarosite particles were obtained by forced hydrolysis of ferric salt solutions to which copper sulfate, sodium sulfate, and sodium nitrate were added. It was found that at the same concentrations of ferric and sulfate ions the particle size and yield decreased with the lowering of the concentration of sodium ions, but the morphology remained the same. At a sufficiently small content of sodium in the reacting solution, no precipitation of sodium jarosite particles was observed. Finally, chemical and XRD analyses showed that small amounts of copper ions are incorporated in the crystal lattice which, with the change in the Na⁺/H₃O⁺ ratio, slightly affected the structure of this mineral, but not its other properties. Received: 12 July 2000 Accepted: 18 August 2000     

Structural controls on OH site availability and reactivity at iron oxyhydroxide particle surfaces

Iron oxyhydroxides (FeOOH) are highly reactive minerals of widespread occurrence in natural and industrial settings. These minerals chiefly occur as nano- to submicron-sized particles and are covered by hydroxyl functional groups coordinated to one (-OH), two (μ-OH), or three (μ(3)-OH) underlying iron atoms. These groups are reaction centers for gases, solutes as well as solvents and thereby play important roles in the fate and transformation of natural and industrial compounds. In this work we provide tools to identify hydroxyl groups on distinct crystallographic planes of two important FeOOH polymorphs, namely lepidocrocite (γ-FeOOH) and goethite (α-FeOOH). Fourier transform infrared spectroscopy was used to monitor O-H stretching vibrations of groups on particles with well-defined and distinct morphologies. Spectral responses to proton loadings and thermal gradients were used to assign bands to hydroxyl groups. These efforts were facilitated by the extraction of pure spectral components obtained by multivariate curve resolution. Molecular dynamics simulations of dominant crystallographic planes of the particles guided band assignment procedures by identifying feasible hydrogen bond networks between surface groups. Our findings provide new possibilities for molecular-scale resolution of important gas-phase processes on the surfaces of these important minerals.     

Kinetic study of the thermal decomposition of cobalt(III) oxyhydroxide

The kinetics of thermal decomposition of CoOOH have been studied by analysis of isothermal weight loss data under vacuum. The comparison of linear correlation coefficients of different kinetic expressions applied to these data does not allow an understanding of the mechanism, even when significance tests are performed (t test). A single value of the activation energy (193 kJ mol^?1) is obtained from the Arrhenius plots, and is relatively independent of the choice of rate law. On the other hand, a change in the mechanism of formation of Co₃O₄ with temperature cannot be inferred from analysis of isothermal data. Thus, the statement of some authors that from formal kinetics it is possible to distinguish the proton and electron transfers involved in the transformation appears unacceptable.     

Preconcentration of some phosphorus-containing anions by adsorption on hydrated iron(III) oxide

The adsorption behaviour of orthophosphate, triphosphate, pyrophosphate, monomethylphosphate, phosphite, α- and β-glycerophosphates, dimethylphosphate, and hypophosphite on hydrated iron(III) oxide precipitate is studied as a function of pH. Orthophosphate is adsorbed quantitatively at pH 4.0–8.0, triphosphate and pyrophosphate at pH 4–9.3 and the next three compounds at pH 4–6.8. The last two ions were only slightly adsorbed at any pH examined.