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  • Adsorption  (1)
  • solution structure  (1)
  • 1
    ISSN: 1435-1536
    Keywords: Key words Liquid/solid interfaces ; solution structure ; in microemulsions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  Mössbauer spectra of liquid solutions fixed as submicroscopic (nanosize) droplets in solid carriers were taken at room temperature and 77 K. A porous silicate (“thirsty glass”) and microemulsions prepared with a paraffin/naphthalene mixture as dispersion medium served as carriers. Solutions of Mössbauer-active tin(IV) and iron(II) complexes were incorporated in these carriers as nanosize droplets. The Mössbauer effect was observed at temperatures above the freezing point of the solutions. For comparison, the systems were also studied in frozen state. Depending on the nature of the system (carrier–solute–solvent) the presence of three types of species was shown in the droplets on the basis of the Mössbauer parameters: (a) situated in bulk position with no interaction with the walls; (b) adsorbed on the internal surface of the holes in the carrier and (c) in bulk position, but with Mössbauer parameters reflecting the influence of the carrier. In some cases surface-bound and bulk species were present together in the sample. The appearance of the Mössbauer effect in liquid state reveals that the Mössbauer-active atoms are fixed in the nanosize pores by a network of hydrogen bonds which form between the solvent molecules, between solvent and solute molecules and between the solvent molecules and the walls of the pores in the carrier. The main parameters determining the rigidity of the network and the situation of the probe molecules are the hydrogen-bonding ability and the polarity of the components of the system. On the basis of the above observations, a new procedure was elaborated for the Mössbauer study of solutions fixed as nanosize droplets in rigid carriers. The analysis of the Mössbauer parameters gives a qualitative picture regarding the solution structure in the interior of the pores, and the adsorption and wetting properties of the system.
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  • 2
    ISSN: 1435-1536
    Keywords: Key words Humic acid ; Aluminium oxide ; Adsorption ; Heterocoagulation ; Surface complexation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The effect of pH and neutral electrolyte on the interaction between humic acid/humate and γ-AlOOH (boehmite) was investigated. The quantitative characterization of surface charging for both partners was performed by means of potentiometric acid–base titration. The intrinsic equilibrium constants for surface charge formation were logK a,1 int=6.7±0.2 and logK a,2 int = 10.6±0.2 and the point of zero charge was 8.7±0.1 for aluminium oxide. The pH-dependent solubility and the speciation of dissolved aluminium was calculated (MINTEQA2). The fitted (FITEQL) pK values for dissociation of acidic groups of humic acid were pK 1 = 3.7±0.1 and pK 2 = 6.6±0.1 and the total acidity was 4.56 mmol g−1. The pH range for the adsorption study was limited to between pH 5 and 10, where the amount of the aluminium species in the aqueous phase is negligible (less than 10−5 mol dm−3) and the complicating side equilibria can be neglected. Adsorption isotherms were determined at pH ∼ 5.5, ∼8.5 and ∼9.5, where the surface of adsorbent is positive, neutral and negative, respectively, and at 0.001, 0.1, 0.25 and 0.50 mol dm−3 NaNO3. The isotherms are of the Langmuir type, except that measured at pH ∼ 5.5 in the presence of 0.25 and 0.5 mol dm−3 salt. The interaction between humic acid/humate and aluminium oxide is mainly a ligand-exchange reaction with humic macroions with changing conformation under the influence of the charged interface. With increasing ionic strength the surface complexation takes place with more and more compressed humic macroions. The contribution of Coulombic interaction of oppositely charged partners is significant at acidic pH. We suppose heterocoagulation of humic acid and aluminium oxide particles at pH ∼ 5.5 and higher salt content to explain the unusual increase in the apparent amount of humic acid adsorbed.
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