Adsorption of dicarboxylates on nano-sized gibbsite particles: effects of ligand structure on bonding mechanisms

The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition ⁻O₂C---C_n---CO₂⁻; n=0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n=2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n=1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) at the surface. This showed the importance of chelate ring structure for the formation of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n=2 only small variations in surface speciation were observed as a function of steric factors; irrespective of the relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption mode. Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles.     

AB initio SCF LCAO MO Calculations on styrene

Minimal basis set ab initio SCF LCAO MO calculations with gaussian-type have been performed for different conformations of the styrene molecule. The computations show the molecule to be planar and the rotational barrier of the vinyl group is estimated to 3.9 kcal/mole.     

Molecular properties of hemicelluloses located in the surface and inner layers of hardwood and softwood pulps

The molecular properties of hemicelluloses located in the surface and inner layers of fibers present in hardwood and softwood pulps, together with the effects of different bleaching processes on these properties, have been investigated in this study. In order to separate the hemicelluloses located in these two layers, fibers were subjected to mechanical peeling and then separated by filtration into surface (filtrate) and inner layer materials. The materials thus obtained were characterized with respect to their polysaccharide compositions and uronic acid contents. The molar mass parameters of the hemicelluloses (extracted by alkali) were determined by employing size-exclusion chromatography in combination with off-line MALDI mass spectrometry. For all of the pulps examined, the relative content of xylan was found to be greater in the surface layer of the fiber than in the corresponding inner layer. The xylan polymers of the surface layer exhibited higher molar masses and lower frequencies of uronic acid side groups than did the xylans in the inner fiber layer. In connection with ozone treatment, hexenuronic acid residues in the surface layer xylan were removed to a greater extent than in the case of the inner layers, indicating a gradient for the reaction with ozone across the fiber wall. The xylan polymer remaining on the surface of the softwood pulps after completion of the chlorine dioxide bleaching process was predominantly uncharged.     

The state of water in finely disperse hydrogels based on acrylamide and acrylic acid

The sorption capacity (upon water sorption from the bulk and vapor phases) of copolymeric hydrogels based on acrylamide and acrylic acid and the state of water in the hydrogels are studied. It is established that, for hydrogels prepared in the form of fine powders, pore sizes vary from 90 to 770 Å and the pore radius of hydrogels obtained as monolithic plates ranges from 27 to 200 Å. The acrylamide-to-acrylic acid unit ratio in the hydrogels is found to affect both the amount and the state of sorbed water. It is shown that the properties of water sorbed by hydrogels are governed by carboxyl group concentration rather than by the density of macromolecular chains.     

The influence of different reclamation agents and microorganisms on the aggregative stability of the colloidal fraction of meadow chernozem soil

The influence of various reclamation agents (montmorillonite, peat, activated sludge microbocenosis) on the stability of dispersions of the colloidal fraction of meadow chernozem soil is studied. It is established that biocolloids possess the strongest coagulating action in the aforementioned series of reclamation agents. It is shown that, in the process of microorganism growth involving glucose or polypeptides as a carbon source, exopolymers are synthesized that caused the coagulation of soil dispersions. Upon the growth of microorganisms on polypeptides (alkaligeneous metabolism), precipitates are formed that are denser and less peptized by water than those grown on glucose (acidogeneous metabolism). The addition of montmorillonite and peat intensifies the aggregation processes in soil-microbe heterodispersions. The inverse relationship between the content of an organic substance in a colloidal system and the stability of aggregates of soil colloids is revealed.