When hexadedyltrimethylammonium (HDTMA) ion is exchanged for metal cations like calcium in smectite, the sorptive properties of the clay are greatly modified. The resultant HDTMA‐smectite complex behaves as a dual sorbent, in the sorption of organic compounds, in which the mineral fraction functions as a solid adsorbent and the organic (HDTMA) phase as a partition medium. Capacities of mineral adsorption and partition uptake by HDTMA in the HDTMA‐smectites are illustrated by sorption of benzene, trichloroethene (TCE), and water as vapors on the dry sample and by sorption of benzene and TCE from water. The exchanged HDTMA in clay is found to be a much more powerful partition medium than ordinary soil organic matter in the uptake of benzene and TCE. Based on this finding, HDTMA‐smectite appears to be an effective sorbent for removing organic contaminants from water. It is suggested that such sorptive organo‐clay complexes could be used to enhance the containment capabilities of clay landfill liners and bentonite slurry walls.
Abstract--Several clay-organic complexes were synthesized by placing quaternary ammonium cations on smectite by cation exchange. They were then examined for their ability to adsorb phenol and several of its chlorinated congeners. The organic cations used were: hexadecylpyridinium (HDPY+), hexadecyltrimethyl ammonium (HDTMA+), trimethylphenyl ammonium (TMPA+), and tetramethylammonium (TMA+). The complexes containing long-chain alkyl (hexadecyl) groups were the most hydrophobic and adsorbed the phenols from water in proportion to their hydrophobicities, which increase with chlorine addition (phenol < chlorophenol < dichloropohenol < trichlorophenol). With n-hexane as the solvent, different adsorption was found which depended on the type and degree of solvent interactions with the compound and the clay-organic complex. Thus, the amount of adsorption of these phenols on clay-organic complexes was dependent on the relative energies of adsorbent-adsorbate and adsorbate-solvent interactions.
Abstract-Equilibrium studies on clay films exposed to N H3 and H20 vapors demonstrate the effect of exchangeable cations on surface acidity and its relationship to hydration. At a relative humidity of 98 per cent the order of acidity on the clay surface as indicated by protonation of N H3 was AI > Mg > Ca = Li > Na = K for Wyoming bentonite and AI > Mg > Li > Ca = Na = K for nontronite. At a relative humidity of 20 per cent, however, the order was AI= Mg > Ca > Li > Na > K for the bentonite and AI = Mg > Li > Ca > Na > K for nontronite. The largest change in proton donation properties due to hydration effects was in the calcium clays. For Ca-bentonite the NH4 + formation was 16 me/100 g at 98 per cent and 80 me/100 g at 20 per cent relative humidity. In Ca-nontronite, the NH4 § formation was 14 and 64 me/100 g for the wet and dry systems respectively. The differences in proton donation between the bentonite and nontronite clays are believed to be due to charge site location and its effects on ion hydration. The NH4 + formed by the protonation process seemed to exist in different environments in the bentonite and nontronite as indicated in the i.r. absorption spectra.
The adsorption of aromatic compounds by smectite exchanged with tetramethylammonium (TMA) has been studied. Aromatic compounds adsorbed by TMA-smectite are assumed to adopt a tilted orientation in a face-to-face arrangement with the TMA tetrahedra. The sorptive characteristics of TMA-smectite were influenced strongly by the presence of water. The dry TMA-smectite showed little selectivity in the uptake of benzene, toluene and xylene. In the presence of water, TMA-smectite showed a high degree of selectivity based on molecular size/shape, resulting in high uptake of benzene and progressively lower uptake of larger aromatic molecules. This selectivity appeared to result from the shrinkage of interlamellar cavities by water.
Abstract--A high-charge smectite from Arizona [cation-exchange capacity (CEC) = 120 meq/100 g] and a low-charge smectite from Wyoming (CEC = 90 meq/100 g) were used to prepare homoionic tetramethylammonium (TMA)-clay complexes. The adsorption of benzene, toluene, and o-xylene as vapors by the dry TMA-clays and as solutes from water by the wet TMA-clays was studied. The adsorption of the organic vapors by the dry TMA-smectite samples was strong and apparently consisted of interactions with both the aluminosilicate mineral surfaces and the TMA exchange ions in the interlayers. In the adsorption of organic vapors, the closer packing of TMA ions in the dry high-charge TMA-smectite, compared with the dry low-charge TMA-smectite, resulted in a somewhat higher degree of shape-selective adsorption of benzene, toluene, and xylene. In the presence of water, the adsorption capacities of both samples for the aromatic compounds were significantly reduced, although the uptake of benzene from water by the low-charge TMA-smectite was still substantial. This lower sorption capacity was accompanied by increased shape-selectivity for the aromatic compounds. The reduction in uptake and increased selectivity was much more pronounced for the water-saturated, high-charge TMA-smectite than for the low-charge TMA-smectite. Hydration of the TMA exchange ions and/or the mineral surfaces apparently reduced the accessibility of the aromatic molecules to interlamellar regions. The resulting water-induced sieving effect was greater for the high-charge TMA-smectite due to the higher density of exchanged TMAions. The low-charge Wyoming TMA-smectite was a highly effective adsorbent for removing benzene from water and may be useful for purifying benzene-contaminated water.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.