Chemical structure of adsorbable

We now extend the work to in situ measurements on metal ions adsorbed at the metal oxide/aqueous solution interface. In this report, our previous results are combined with new measurements to yield specific information on the chemical structure of adsorbed species at the solid/aqueous solution interface. Here, we describe the principles of emission Mossbauer spectroscopy, experimental techniques, and some results on divalent Co-57 and pentavalent Sb-119 ions adsorbed at the interface between hematite (a-Fe203) and aqueous solutions. 

Effects of Pentavalent Sb Ions on the Adsorption of Divalent Co-57 on Hematite. Benjamin and Bloom reported that arsenate ions enhance the adsorption of cobaltous ions on amorphous iron oxyhydroxide (J 6). Similarly, when divalent Co-57 ions were adsorbed on hematite together with pentavalent Sb ions, an increase of adsorption in the weakly acidic region was observed. For example, when 30 mg of hematite was shaken with 10 cm3 of 0.1 mol/dm3 KC1 solution at pH 5.5 containing carrier-free Co-57 and about 1 mg of pentavalent Sb ions, 95 % of Co-57 and about 30 % of Sb ions were adsorbed. The emission spectra of the divalent Co-57.ions adsorbed under these conditions are shown in Figure 8 together with the results obtained under different conditions. As seen in Figure 8, the spectra of divalent Co-57 co-adsorbed with pentavalent Sb ions are much different from those of Co-57 adsorbed alone (Figure 3). These observations show a marked effect of the.co-adsorbed pentavalent Sb ions on the chemical structure of adsorbed Co-57. 

In situ emission Mossbauer spectroscopic measurement of the hyper-fine magnetic fields on trivalent Fe-57 and tetravalent Sn-119 arising from divalent Co-57 and pentavalent Sb—119, respectively, yields valuable information on the chemical structure of adsorbed metal ions at the interface between hematite and an aqueous solution. 

Determination of surface functional groups, e.g., —OH, —C - C—, and >C = O, and identificadon of adsorbed molecules comes principally from comparison with vibrational spectra (infixed and Raman) of known molecules and compounds. Quick qualitative analysis is possible, e.g., stretching modes involving H appear for v(C—H) at 3000 cm and for v(0—H) at 3400 cm L In addition, the vibrational energy indicates the chemical state of the atoms involved, e.g., v(C=C) " 1500 cmT and v(C=0) " 1800 cm"L Further details concerning the structure of adsorbates... 

Effectiveness of selective adsorption of phenanthrene in Triton X-100 solution depends on surface area, pore size distribution, and surface chemical properties of adsorbents. Since the micellar structure is not rigid, the monomer enters the pores and is adsorbed on the internal surfaces. The size of a monomer of Triton X-100 (27 A) is larger than phenanthrene (11.8 A) [4]. Therefore, only phenanthrene enters micropores with width between 11.8 A and 27 A. Table 1 shows that the area only for phenanthrene adsorption is the highest for 20 40 mesh. From XPS results, the carbon content on the surfaces was increased with decreasing particle size. Thus, 20 40 mesh activated carbon is more beneficial for selective adsorption of phenanthrene compared to Triton X-100. 

In situ emission Mossbauer spectroscopy provides valuable information on the chemical structure of dilute metal ions at the metal oxide/aqueous solution interface The principles of the method are described with some experimental results on divalent Co-57 and pentavalent Sb-119 adsorbed on hematite. 

The chemical structure of the adsorbed ions was found to be dependent on pH of the aqueous phase. Most of the divalent Co-57 and pentavalent Sb-119 ions form strongly bonded surface complexes under alkaline and acidic conditions, respectively. 

The ferric oxide, hematite, used in the present work was a high purity powder reagent with a BET surface area of 27 m2/g 30 mg was employed in each run. Some measurements were made on hematite calcined in air to see the effects of sintering the surface on the chemical structure of the adsorbed metal ions. The hematite samples were checked by Mossbauer absorption and powder X-ray diffraction measurements. The Mossbauer absorption spectra consisted of a magnetic sextet with no superparamagnetic component due to fine particles ( ). 

In contrast to the case of divalent Co-57 ions described above, the spectra show no hysteresis against the lowering of pH. Conversely, the spectrum of a sample previously adjusted to a pH of 2.5 was found to remain broadened after the pH had been raised to 8.6 (Figure 5(F)). Thus, the chemical structure of pentavalent Sb-119 adsorbed from an acidic solution is considered to be retained when the pH of the solution is raised above 7. 

CO2 production time series, 39 88 equation structure, 39 87-88 Kurtanjek s mechanism, 39 91 oxide models, 39 89-92 subsurface oxygen model, 39 90-91 selective, 30 136-137 small organic molecules, chemical identity of adsorbed intermediates, 38 21 states... 

It is essential to have tools that allow studies of the electronic structure of adsorbates in a molecular orbital picture. In the following, we will demonstrate how we can use X-ray and electron spectroscopies together with Density Functional Theory (DFT) calculations to obtain an understanding of the local electronic structure and chemical bonding of adsorbates on metal surfaces. The goal is to use molecular orbital theory and relate the chemical bond formation to perturbations of the orbital structure of the free molecule. This chapter is complementary to Chapter 4, which... 

A number of contradictory views have been published concerning the structure of adsorbed alcohols and the nature of adsorption sites (for review see ref. 69). Experimental evidence from IR investigations has shown that, on alumina, alcohols form several surface complexes of very different chemical natures (e.g. refs. 31, 32, 117, 133—137) (i) alcohol molecules weakly bonded to the surface, very probably by hydrogen bonds (I) (such complexes are sometimes denoted as physically sorbed alcohols) (ii) surface alkoxides (alcoholates) (II) (iii) surface carboxy-lates (III). Less certain is the existence of species with partial double bonds or of ketone-like species. The formation of the various surface complexes is dependent on the structure of the alcohol. For examples, weakly bonded species (I) have been found with all alcohols, alkoxides (II) mostly with primary alcohols, sometimes also with secondary alcohols, but have never been reported for tertiary alcohols. 

Internal transfer transfer of adsorbate from particle surface to interior site by diffusion in the void space of the pores, by surface migration on the pore surface, or by volume diffusion, for example, in the holes in the chemical structure of the solid phase. 

The preferential adsorption behavior of poly(vinylpyrrolidone) (PVP) in binary solvent containing aromatic components has been also studied [110]. In this case, it was concerned with the influence of the chemical structure of different binary solvents in the preferential adsorption of this polymer. 2 - propanol - cumene, 2 -propanol - mesitylene, 2 - propanol - p-xylene, 2 - propanol - ethylbenzene and 2 - propanol - toluene. Figure 1.15 shows the variation of X with the solvent composition. In both cases aromatic components are adsorbed in the range 0 to 40%, but the amount of adsorbed molecules is rather different for the two isomers. This result could be explained in terms of steric hindrance due to the isopropyl groups of cumene, which would be reflected in the lower X value. 

Preliminary models of the surface topography, for example, can be determined by atomic-probe methods, ion-scattering, electron diffraction, or Auger spectroscopy. The chemical bonds of adsorbates can be estimated from infrared spectroscopy. The surface electronic structure is accessible by photoelectron emission techniques. In case the surface structure is known, its electronic structure has to be computed with sophisticated methods, where existing codes more and more rely on first principles density functional theory (DFT) [16-18], or, in case of tight-binding models [19], they obtain their parameters from a fit to DFT data [20]. The fit is not without ambiguities, since it is unknown whether the density of states used for the fit is really unique. 

Fig. 1. (a) A chemical structure of a 2.5th generation carboxylic acid-terminated poly(amido amine) (PAMAM) dendrimer. (b) Transmission surface enhanced infrared absorption spectra (SEIRAS) of dendrimer adlayers prepared at 30 min adsorption from aqueous solutions (0.01 wt.%) of a dendrimer at different pHs. Numerical values are pHs of the solutions, (c) Adsorption-desorption profiles as a function of time at different pHs and adlayer thicknesses at adsorption and desorption equilibrium as a function of pH for aqueous solutions (0.1 wt.%) of the dendrimer. The symbols, j and J, in the top figure denote start of adsorption and desorption, respectively. In the bottom figure, filled circle and opened square denote adlayer thicknesses at adsorption and desorption equilibrium, respectively. The dark tie denotes the calculated dendrimer size width. A solid curve is drawn to be visual, (d) Schematic illustration of dendrimers adsorbed at different pHs. Reprinted with permission from Ref. [69], 2006, American Scientific Publishers. 

Fig. 19. Possible structures of adsorbed ester group of a-PMMA on a silver particle (a) gauche conformer and (b) trans conformer. (Reproduced with permission from Ref. [66]. Copyright (2002) American Chemical Society.)...

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