Quantitative adsorption and local structures of gallium(III) at the water-alpha-FeOOH interface

The adsorption of Ga(III) at the water-alpha-FeOOH (goethite) interface has been investigated by means of quantitative adsorption experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy, and surface complexation modeling. Under the conditions studied, pH range 3-11 and surface coverages of 0.9-3.2 micromol/m2, Ga(III) was found to adsorb strongly to alpha-FeOOH, and the surface species were more resistant toward hydrolysis and formation of soluble Ga(OH)4- than either solid gallium hydroxides or soluble polynuclear complexes. The EXAFS measurements revealed the presence of octahedral Ga(III) complexes at the water-alpha-FeOOH interface, with practically no structural variations as a function of pH or total gallium concentration. Analysis of the first coordination shell required an anharmonic model indicating a distorted geometry of the GaO6 octahedra, with mean Ga-O distances at 1.96-1.98 angstroms. A method based on the continuous Cauchy wavelet transforms (CCWT) was used to identify backscattering atoms in the higher coordination shells. This analysis indicated predominately Fe backscattering, and the quantitative data fitting resulted in three Ga-Fe paths at 3.05, 3.2, and 3.55 angstroms, which correspond to two edge-sharing and one corner-sharing linkage, respectively. The collective results from EXAFS spectroscopy showed that Ga(III) adsorbs to Fe equivalent sites at the surface alpha-FeOOH as an extension of the rows of Fe octahedra in the bulk structure. This interpretation was further corroborated by a Ga-Fe-Fe multiple scattering path at 6.13 angstroms. The quantitative adsorption and proton data were modeled using a surface complexation formalism based on a 1 pK(a) constant capacitance model. In agreement with the EXAFS results, the model obtained included one predominating surface complex with the stoichiometry [triple bond]FeOGa(OH)2(-0.5) and the stability constant log beta(intr.) = -2.55 +/- 0.04 ([triple bond]FeOH(-0.5) + Ga3+ + 2H2O <--> [triple bond]FeOGa(OH)2(-0.5) + 3H+).     

Surface complexes of monomethyl phosphate stabilized by hydrogen bonding on goethite (α-FeOOH) nanoparticles

Typically, a significant fraction of phosphorus in soils is composed of organic phosphates, and this fraction thus plays an important role in the global phosphorus cycle. Here we have studied adsorption of monomethyl phosphate (MMP) to goethite (α-FeOOH) as a model system in order to better understand the mechanisms behind adsorption of organic phosphates to soil minerals, and how adsorption affects the stability of these molecules. The adsorption reactions and stability of MMP on goethite were studied at room temperature as a function of pH, time and total concentration of MMP by means of quantitative batch experiments, potentiometry and infrared spectroscopy. MMP was found to be stable at the water-goethite interface within the pH region 3-9 and over extended periods of time, as well as in solution. The infrared spectra indicated that MMP formed three predominating pH-dependent surface complexes on goethite, and that these interacted monodentately with surface Fe. The complexes differed in hydrogen bonding interactions via the auxiliary oxygens of the phosphate group. The presented surface complexation model was based on the collective spectroscopic and macroscopic results, using the Basic Stern approach to describe the interfacial region. The model consisted of three monodentate inner sphere surface complexes where the MMP complexes were stabilized by hydrogen bonding to a neighboring surface site. The three complexes, which had equal proton content and thus could be defined as surface isomers, were distinguished by the distribution of charge over the 0-plane and β-plane. In the high pH-range, MMP acted as a hydrogen bond acceptor whereas it was a hydrogen bond donor at low pH.     

Surface complexation of mellitic acid to goethite: an attenuated total reflection Fourier transform infrared study

The nature of the interaction between mellitic acid (benzene hexacarboxylic acid) and the common soil mineral goethite (alpha-FeOOH) has been investigated as a function of pH and ionic strength by use of attenuated total reflection Fourier transform infrared spectroscopy. Molecular orbital calculations of the theoretical vibrational frequencies of the mellitate ion (L6-) and dihydrogen mellitate (H2L4-) have allowed the measured absorption frequencies to be accurately assigned. At pH values above 6, adsorption involves outer-sphere complexation of the deprotonated L6- ion. At lower pH values, there is evidence of a second outer-sphere surface complex involving a partially protonated species, although the extent of protonation of the surface species is significantly less than that found for the solution species at the same pH. While there is no evidence of inner-sphere complexation, increasing the ionic strength to 2.0 M does not displace the adsorbed species but does increase the fraction present on the surface as the fully deprotonated L6-. The small effect of ionic strength suggests that the adsorptive interaction, although outer-sphere in character, is still relatively strong, which indicates that hydrogen bonds may play a significant role. Hydrogen bonding may also help to account for the observed outer-sphere complexation at pH values above the pHiep of goethite.     

Airborne chemistry: acoustic levitation in chemical analysis

This review with 60 references describes a unique path to miniaturisation, that is, the use of acoustic levitation in analytical and bioanalytical chemistry applications. Levitation of small volumes of sample by means of a levitation technique can be used as a way to avoid solid walls around the sample, thus circumventing the main problem of miniaturisation, the unfavourable surface-to-volume ratio. Different techniques for sample levitation have been developed and improved. Of the levitation techniques described, acoustic or ultrasonic levitation fulfils all requirements for analytical chemistry applications. This technique has previously been used to study properties of molten materials and the equilibrium shape and stability of liquid drops. Temperature and mass transfer in levitated drops have also been described, as have crystallisation and microgravity applications.The airborne analytical system described here is equipped with different and exchangeable remote detection systems. The levitated drops are normally in the 100 nL–2 L volume range and additions to the levitated drop can be made in the pL-volume range.The use of levitated drops in analytical and bioanalytical chemistry offers several benefits. Several remote detection systems are compatible with acoustic levitation, including fluorescence imaging detection, right angle light scattering, Raman spectroscopy, and X-ray diffraction. Applications include liquid/liquid extractions, solvent exchange, analyte enrichment, single-cell analysis, cell–cell communication studies, precipitation screening of proteins to establish nucleation conditions, and crystallisation of proteins and pharmaceuticals.     

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution—10. A potentiometric study of aluminium(III) pyrocatecholates and aluminium(III) hydroxo pyrocatecholates in 0.6 M Na(Cl)

Equilibria between aluminium(III), pyrocatechol (1,2-dihydroxybenzene, H₂L) and OH⁻ were studied in 0.6 M Na(Cl) medium at 25°C. The measurements were performed as emf titrations (glass electrode) within the limits 1.5 ≤ − log[H⁺] ≤ 9; 0.0005 ≤ B ≤ 0.015 M; 0.006 ≤ C ≤ 0.03 M and 2 ≤ C/B ≤ 30 (B and C stand for the total concentrations of aluminium(III) and pyrocatechol respectively). All data can be explained with a main series of complexes: A1L⁺, log β_−2,1,1 = − 6.337 ± 0.005; A1L₂⁻, log β_−4,1,2 = −15.44 ± 0.017 and A1L₃³⁻, log β_−6,1,3 = − 28.62 ± 0.024 together with two minor species: Al(OH)L₂²⁻, log β_−5,1,2 = − 23.45 ± 0.079 and Al₃(OH)₃L₃, log β_−9,3,3 = − 29.91 ± 0.066. Of the two, the latter probably is a type of average composition complex principally occurring at low C/B quotients. The first acidity constant for pyrocatechol as determined in separate experiments is log β_−1,0,1 = − 9.198 ± 0.001. The standard deviations given are 3σ(log β p,q,r). Data were analyzed with the least squares computer program LETAGROPVRID. In a model calculation using kaolinite as solid phase, we compared the complexation ability of this system with that of the system Al³⁺-OH⁻-salicylic acid, reported earlier in this series.     

3D Passive Walkers: Finding Periodic Gaits in the Presence of Discontinuities

This paper studies repetitive gaits found in a 3D passivewalking mechanism descending an inclined plane. By using directnumerical integration and implementing a semi-analytical scheme forstability analysis and root finding, we follow the corresponding limitcycles under parameter variations. The 3D walking model, which is fullydescribed in the paper, contains both force discontinuities andimpact-like instantaneous changes of state variables. As a result, thestandard use of the variational equations is suitably modified. Theproblem of finding initial conditions for the 3D walker is solved bystarting in an almost planar configuration, making it possible to useparameters and initial conditions found for planar walkers. The walkeris gradually transformed into a 3D walker having dynamics in all spatialdirections. We present such a parameter variation showing the stabilityand the amplitude of the hip sway motion. We also show the dependence ofgait cycle measurements, such as stride time, stride length, averagevelocity, and power consumption, on the plane inclination. The paperconcludes with a discussion of some ideas on how to extend the present3D walker using the tools derived in this paper.     

Optimum conditions for pulse generation in diaphragm-free Karl Fischer coulometry

A flexible instrument was designed in order to investigate the influence of current magnitude, current duration and the frequency of the pulse generation on the error obtained in coulometric Karl Fischer titrations carried out in diaphragm-free cells. For a given current magnitude the lowest errors were obtained for current durations more than 60% of the total time for the pulse cycle. No significant influence of the pulse frequency (5–1000 Hz) was found independently of the pulse current duration for three different types of reagents intended for diaphragm-free coulometry. For all reagents, the errors obtained with the home-built instrument were significantly smaller than those obtained with an optimized commercial titrator based on pulsed current generation. Using optimum conditions for the former instrument, in combination with an imidazole-buffered reagent at pH 10 containing chloroform as modifier, the accuracy was close to 100%. Thus, it is now possible to achieve the same high accuracy with diaphragm-free coulometry as with the conventional diaphragm based technique. The precision of the water determinations was affected by the size of the background. Received: 16 March 2000 / Revised: 17 May 2000 / Accepted: 22 May 2000     

Progress in pulsed-current Karl Fischer coulometry using diaphragm-free cells

Factors influencing the accuracy of water determinations using diaphragm-free, pulsed current Karl Fischer (KF) coulometry were investigated with the new Metrohm 756 instrument. Results obtained with commercially available reagents from Riedel-deHaën and Merck were compared with home-made ones that were especially designed to minimize the formation of iodine-consuming reduction products generated in the cathode reaction. Positive errors in the range 2–5% were found for the commercial reagents as compared to 0.2–1% for the home-made ones which were buffered at about pH 10 containing modifiers like chloroform, hexanol or ethylene glycol. Except for the composition of the KF-reagent, the cathode current density and the titration rate were found to be critical parameters for the accuracy of the determinations. For all reagents investigated, the best results were obtained for the maximum generator current 400 mA (corresponding to a current density of 1400 mA cm^–2) in combination with a maximum titration rate of 2000 μg min^–1. Surprisingly, the errors found under optimum conditions for the pulse technique were always somewhat larger than the corresponding values obtained with continuous coulometry.     

Measurements of Transitional and Turbulent Flow in a Randomly Packed Bed of Spheres with Particle Image Velocimetry

Particle image velocimetry (PIV) has been used to investigate transitional and turbulent flow in a randomly packed bed of mono-sized transparent spheres at particle Reynolds number, \(20<{{ Re}}_{\mathrm{p}}< 3220\). The refractive index of the liquid is matched with the spheres to provide optical access to the flow within the bed without distortions. Integrated pressure drop data yield that Darcy law is valid at \({{ Re}}_{\mathrm{p}} \approx 80\). The PIV measurements show that the velocity fluctuations increase and that the time-averaged velocity distribution start to change at lower \({{ Re}}_{\mathrm{p}}\). The probability for relatively low and high velocities decreases with \({{ Re}}_{\mathrm{p}}\) and recirculation zones that appear in inertia dominated flows are suppressed by the turbulent flow at higher \({{ Re}}_{\mathrm{p}}\). Hence there is a maximum of recirculation at about \({{ Re}}_{\mathrm{p}} \approx 400\). Finally, statistical analysis of the spatial distribution of time-averaged velocities shows that the velocity distribution is clearly and weakly self-similar with respect to \({{ Re}}_{\mathrm{p}}\) for turbulent and laminar flow, respectively.