This work examined the influence of a leonardite humic acid on the sorption of Co(II), Sr(II), and Se(IV) onto goethite as a function of pH. The sorption of humic acid and ions alone was first studied. The humic acid sorbs appreciably to the goethite surface according to a reversible process, with a maximum sorption of 19 mg of total organic carbon per g of goethite reached at lower pH values (» 5). Cobalt and selenium are significantly sorbed on goethite while strontium is only weakly sorbed. In the presence of humic acid, the cobalt sorption is enhanced in acidic media due to the humic acid sorption on goethite, which modified the surface properties by making it more negative. However, it decreases in alkaline media due to the complexation of Co(II) by soluble humic acid. The sorption of Sr(II) is significantly increased in the presence of humic acid even in alkaline media. The sorption of selenite ions (SeO3 2–) decreases in the presence of humic acid because a competition with humate ions occurs at the surface sites of the goethite. The results presented here constitute a good set of data for modelling the effect of humic acid on the sorption of ions on goethite.
Keyword: sorption, humic acid, goethite, cobalt, strontium, selenium
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How DOC Composition May Explain the Poor Correlation Between Specific Trihalomethane Formation Potential and Specific UV Absorbance
Trihalomethane formation potential, ultra-violet light absorbance, and aromatic carbon content of dissolved organic carbon in natural water from grab sampling in watersheds across the USA and from detailed sampling in one watershed, the Sacramento-San Joaquin Delta, California, were examined in order to better understand the compositional nature of trihalomethane precursor material. Specific trihalomethane formation potential and specific ultra-violet light absorbance were not tightly correlated in either dataset, indicating that ultra-violet light absorbance cannot be used for accurate prediction of specific trihalomethane formation potential in drinking water derived from a broad spectrum of watershed types. Specific trihalomethane formation potential was not closely related to the aromatic carbon content of dissolved organic carbon isolates or to the partitioning of the dissolved organic carbon by nonionic macroporous resins, suggesting that neither of these measures are related to the compositional features of the dissolved organic carbon responsible for trihalomethane formation.
Keyword: DOC Composition, Poor Correlation, Trihalomethane, UV Absorbance
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Organic ligands for copper(II) were isolated from lake waters in Lake Biwa and its river waters by immobilized metal ion affinity chromatography (IMAC), and were characterized by three-dimensional excitation/emission matrix spectroscopy (3DEEM) and fluorescence quenching titration. The results show that the contribution of total organic ligands was 0.63–4.68% of the bulk dissolved organic matter (DOM), in terms of UV absorbance, in lake and river waters. Three characteristic excitation/emission (Ex/Em) fluorescence peaks were identified in organic ligands from both lake and river waters, at Ex/Em 310–330/ 374–434 nm (Peak A), 250/414–454 nm (Peak B), and 260–270/306–330 nm (Peak C). Peaks A and B were referred to as humic-like fluorescence, Peak C as protein-like fluorescence. All Ex/Em maxima of organic ligands in lake waters were shifted towards shorter wavelength, and the fluorescence intensities were higher than those in river waters. The results of fluorescence quenching titration show that the IMAC ligands were weak ligands, with conditional stability constants (logK′CuL) around 7.27 for river ligands, and 7.84–9.23 for lake ligands. The differences of fluorescence properties indicate the variability of fluorescent ligands between river terrestrial and lake aquatic environments.
Keyword: Fluorescence, organic ligands, copper(II), Lake Biwa
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Kesetimbangan Adsorpsi Optional Campuran Biner Cd(II) dan Cr(III) dengan Zeolit Alam Terimpregnasi 2-merkaptobenzotiazol
Natural zeolite is one of adsorbents widely used in adsorption processes to treat water polution caused by heavy metal waste. In some cases, the modification of the zeolit active surface is important to improve its adsorpability and its selectivity. Characteristic of modified natural zeolite can be obtained from the analysis of adsorption equilibrium data which useful for adsorption process design. The aim of the research is to find and analyzing the adsorption equilibrium data for binary mixture adsorption process of Cd and Cr metals using the modified natural zeolite which impregnated with 2-metrcaptobenzotiazole (zeolite-MBT). The adsorption equilibrium experiments were carried out in a flask batch method using a shaker bath with experimental temperatures were varied from 27°C to 50°C. An amount of 0.1 gram of zeolite-MBT adsorbent was immersed in 60 ml of Cd and or Cr solution then shook until the equilibrium condition (6 hours) was reached. The quantity of metal ionic adsorbed was measured through the concentration of metal solution at equilibrium condition. Each series of equilibrium data were obtained by varying the initial solution concentration in such a way that they could be ploted to create the adsorption isotherm curve. The Langmuir competitif model was used to draw the adsorption isotherm curve for the binary mixture of Cd and Cr by zeolit-MBT adsorbent. The smallest relative mean error correction, i.e. 12.9% and 23 % for Cd and Cr adsorption respectively. Separation performance in the adsorption process of Cd and Cr by the zeolit-MBT adsorbent is five to eight times better than the zeolit-Na adsorbent that wide commercially being used.
Keywords: adsorption, impregnation, zeolite-MBT
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Reaction of a 3-butenyl -diketone with a catalytic amount of PdCl2(CH3CN)2 in dioxane at room temperature led to olefin hydroalkylation and formation of the corresponding 2-acylcyclohexanone in good yield as a single regioisomer. Deuterium-labeling experiments for the hydroalkylation of 7-octene-2,4-dione were in accord with a mechanism involving outer-sphere attack of the pendant enol on a palladium-complexed olefin to form a palladium cyclohexyl species, followed by palladium migration via iterative -hydride elimination/ addition and protonolysis from a palladium enolate complex. In comparison to a 3-butenyl -diketone, reaction of a 4-pentenyl -diketone with a catalytic amount of PdCl2(CH3CN)2 in the presence of CuCl2 led to oxidative alkylation and formation of the corresponding 2-acyl-3-methyl-2-cyclohexenone in good yield as a single isomer.
Unactivated olefins tethered to less reactive carbon nucleophiles such as -keto esters, -aryl ketones, and even dialkyl ketones underwent palladium-catalyzed hydroalkylation in the presence of Me3SiCl or HCl to form the corresponding cyclohexanones in moderate-to-good yield with high regioselectivity.
Keyword : Palladium, Catalyzed Alkylation, Olefins.
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Adsorption and ion exchange share so many common features in regard to application in batch and fixed-bed processes that they can be grouped together as sorption for a unified treatment. These processes involve the transfer and resulting distribution of one or more solutes between a fluid phase and particles. The partitioning of a single solute between fluid and sorbed phases or the selectivity of a sorbent toward multiple solutes makes it possible to separate solutes from a bulk fluid phase or from one another.
This section treats batch and fixed-bed operations and reviews process cycles and equipment. As the processes indicate, fixed-bed operation with the sorbent in granule, bead, or pellet form is the predominant way of conducting sorption separations and purifications. Although the fixed-bed mode is highly useful, its analysis is complex. Therefore, fixed beds including chromatographic separations are given primary attention here with respect to both interpretation and prediction.
Adsorption involves, in general, the accumulation (or depletion) of solute molecules at an interface (including gas-liquid interfaces, as in foam fractionation, and liquid-liquid interfaces, as in detergency). Here we consider only gas-solid and liquid-solid interfaces, with solute distributed selectively between the fluid and solid phases. The accumulation per unit surface area is small; thus, highly porous solids with very large internal area per unit volume are preferred. Adsorbent surfaces are often physically and/or chemically heterogeneous, and bonding energies may vary widely from one site to another. We seek to promote physical adsorption or physisorption, which involves van der Waals forces (as in vapor condensation), and retard chemical adsorption or chemisorption, which involves chemical bonding (and often dissociation, as in catalysis). The former is well suited for a regenerable process, while the latter generally destroys the capacity of the adsorbent.
Adsorbents are natural or synthetic materials of amorphous or microcrystalline structure. Those used on a large scale, in order of sales volume, are activated carbon, molecular sieves, silica gel, and activated alumina [Keller et al., gen. refs.]. Ion exchange usually occurs throughout a polymeric solid, the solid being of gel-type, which dissolves some fluid-phase solvent, or truly porous. In ion exchange, ions of positive charge in some cases (cations) and negative charge in others (anions) from the fluid (usually an aqueous solution) replace dissimilar ions of the same charge initially in the solid. The ion exchanger contains permanently bound functional groups of opposite charge-type (or, in special cases, notably weak-base exchangers act as if they do). Cation-exchange resins generally contain bound sulfonic acid groups; less commonly, these groups are carboxylic, phosphonic, phosphinic, and so on. Anionic resins involve quaternary ammonium groups (strongly basic) or other amino groups (weakly basic).
Most ion exchangers in large-scale use are based on synthetic resins—either preformed and then chemically reacted, as for polystyrene, or formed from active monomers (olefinic acids, amines, or phenols). Natural zeolites were the first ion exchangers, and both natural and synthetic zeolites are in use today.
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