Investigation of Metal Ion Removal Selectivity Properties of the Modified Polyacrylamide Hydrogels Prepared by Transamidation and Hofmann Reactions

Modified crosslinked polyacrylamides having different functional groups prepared by transamidation reaction in aqueous and non‐aqueous medium and by Hofmann reaction were used as chelating agents for removal of Cu(II), Cd(II) and Pb(II) ions from aqueous solutions at different pH values. Under non‐competitive conditions, polymers adsorbed different amounts of metal ions, depending on their functional groups and swelling abilities. The metal ion adsorption capacities of polymers changed between 0.11–1.71 mmol/g polymer. Under competitive conditions, while the polymers having mainly secondary amine groups were highly selective for Cu(II) ions (99.4%), those having mainly secondary amide and carboxylate groups have shown high selectivity towards Pb(II) ions (99.5%). The selectivity towards Cu(II) ion decreased and Pb(II) ion selectivity increased by the decrease of the pH of the solutions. The high initial adsorption rate (<10 min) suggests that the adsorption occurs mainly on the polymer surface. A regeneration procedure by treatment with dilute HCl solution showed that the modified polymers could be used several times without loss of their adsorption capacities.     

Improved recovery of trace amounts of gold (III), palladium (II) and platinum (IV) from large amounts of associated base metals using anion-exchange resins

The adsorption and desorption behaviors of gold (III), palladium (II) and platinum (IV) were surveyed in column chromatographic systems consisting of one of the conventional anion-exchange resins of large ion-exchange capacity and dilute thiourea solutions. The noble metals were strongly adsorbed on the anion-exchange resins from dilute hydrochloric acid, while most base metals did not show any marked adsorbability. These facts made it possible to separate the noble metals from a large quantity of base metals such as Ag (I), Al (III), Co (II), Cu (II), Fe (III), Mn (II), Ni (II), Pb (II), and Zn (II). Although it used to be very difficult to desorb the noble metals from the resins used, the difficulty was easily overcome by use of dilute thiourea solutions as an eluant. In the present study, as little as 1.00 microg of the respective noble metals was quantitatively separated and recovered from as much as ca. 10 mg of a number of metals on a small column by elution with a small amount of dilute thiourea solution. The present systems should be applicable to the separation, concentration and recovery of traces of the noble metals from a number of base metals coexisting in a more extended range of amounts and ratios.     

Improved recovery of trace amounts of gold (III), palladium (II) and platinum (IV) from large amounts of associated base metals using anion-exchange resins

The adsorption and desorption behaviors of gold (III), palladium (II) and platinum (IV) were surveyed in column chromatographic systems consisting of one of the conventional anion-exchange resins of large ion-exchange capacity and dilute thiourea solutions. The noble metals were strongly adsorbed on the anion-exchange resins from dilute hydrochloric acid, while most base metals did not show any marked adsorbability. These facts made it possible to separate the noble metals from a large quantity of base metals such as Ag (I), Al (III), Co (II), Cu (II), ¶Fe (III), Mn (II), Ni (II), Pb (II), and Zn (II). Although it used to be very difficult to desorb the noble metals from the resins used, the difficulty was easily overcome by use of dilute thiourea solutions as an eluant. In the present study, as little as 1.00 μg of the respective noble metals was quantitatively separated and recovered from as much as ca. 10 mg of a number of metals on a small column by elution with a small amount of dilute thiourea solution. The present systems should be applicable to the separation, concentration and recovery of traces of the noble metals from a number of base metals coexisting in a more extended range of amounts and ratios.     

Sorption of mercury(II), zinc(II), and iron(III) thiocyanate complexes on AV-17 anion exchanger and KU-2 cation exchanger modified with rhodamine Zh

Sorption of anionic mercury(II), zinc(II), and iron(III) thiocyanate complexes on KU-2 cation exchanger modified with Rhodamine Zh and on AV-17-8 strongly basic anion exchanger were studied in relation to the concentration of SCN^? ions and solution pH. Optimal conditions of sorption of metal complexes from dilute solutions were found.     

The effect of triethylenetetraamine (Trien) on the ion flotation of Cu(2+) and Ni(2+)

Ion flotation is a separation process involving the adsorption of a surfactant and counterions at an air/aqueous solution interface. It shows promise for removing toxic heavy metal ions from dilute aqueous solutions. Here we report the effect of a neutral chelating ligand, triethylenetetraamine (Trien), on the ion flotation of cations with dodecylsulfate, DS(-), introduced as sodium dodecylsulfate, SDS. Ion flotation in the aqueous SD-Cu(II)-Ca(II)-Trien system gave strongly preferential removal of Cu(II) over Ca(II), which is a reversal of the order of selectivity seen in the SDS-Cu(II)-Ca(II) system containing no Trien. The removal rates of Cu(2+) and Ni(2+) with DS(-) were much faster in the presence of Trien than for simple aquo ions, and the final metal concentration was significantly lower. Surface tension measurements showed that Trien enhanced the surface activity and adsorption density for SDS-Cu(II) and SDS-Ni(II) solutions. The overall change in the Gibbs free energy for adsorption resulting from complexation was -3.60 kJ/mol for Cu(II) and -3.50 kJ/mol for Ni(II). This included the effects of hydrophobic interactions between the metal-Trien complexes at the air/solution interface, along with changes in the amount of dehydration associated with cosorption of the metal-Trien complex with DS(-) at the air/solution interface.     

Adsorption of mercury(II) on macroreticular styrene-divinylbenzene copolymer beads

The adsorption characteristics of mercury(II) on several kinds of styrene-divinylbenzene copolymer beads having different surface properties were studied. It was found that the polymer beads selectively adsorbed mercury(II) from solutions over a wide range of pH with high efficiency. The amount of mercury(II) adsorbed increased with increase in specific surface area of the polymer beads and the adsorption behaviour was found to be of the Langmuir type. The presence of chloride strongly reduced the adsorption, but this interference was not observed with nitrate, sulphate, perchlorate, cadmium(II), cobalt(II), copper(II), nickel(II), silver(I) and zinc(II). More than 95% of the mercury(II) adsorbed on a column of polymer beads could be recovered with dilute hydrochloric acid.     

Biosorption of precious metal ions by chicken feather

Chicken feather (C-feather) is an intricate network of stable and water-insoluble protein fibers with high surface area and is an abundant bioresource. C-feather protein was found to accumulate various precious metal ions (gold and platinum metals) selectively from their dilute aqueous solutions in high yield and in short contact time, depending on pH and characteristics of the individual precious metal ions. Under certain condition, the sequestering level of precious ions, Au(III), Pt(II), and Pd(II) approaches about 17, 13, and 7% of dry wt of C-feather, respectively. Gold(III) potassium cyanade was also accumulated up to 5.5% at pH 2.0. The presence of 100-fold (mol) of coexisting cations, such as Na⁺, Fe(III), Cu(II), and Ni(II), did not show a discernible effect on the precious metal uptake rate and capacity of C-feather. Experiment suggested C-feather is promising for use in the removal/recovery of precious metals as well as water pollution control. A qualitative discussion is given about the excellent adsorption behavior of C-feather.

     

Ion-Sensitive Monolayers and Langmuir–Blodgett Films of Amphiphilic Cyclen: Selectivity and Regeneration

Complexation of dicetyl cyclen with transition metal ions in the monolayers on the surface of aqueous solutions of Cu(II), Ni(II), Zn(II), Ag(I) and their mixtures was studied. It was established that the selectivity of the interaction of the monolayer composed of this ligand with transition metal ions is determined by the subphase pH value. It is disclosed that, in the acidic region of subphase pH values, dicetyl cyclen in the monolayer bounds predominantly the Ni(II) ions from solutions containing Cu²⁺ and Ni²⁺ ions, although its complexes with Ni(II) in the bulk under these conditions are less stable than similar complexes with Cu(II). The effect of conformational and charge states of the ligand on the protonation of macrocycle and the stability of its complexes is discussed. The possibility of the reversible regeneration of the monolayers and the Langmuir–Blodgett films of the complexes of dicetyl cyclen and copper(II) ions is shown to occur with no changes in the structure and properties of this planar system. It is shown that the Langmuir–Blodgett films based on dicetyl cyclen can be used as a sensor element for the quantitative analysis of the content of Cu(II) ions in dilute solutions.     

Interlaboratory comparisons of the determination of pH in poorly buffered fresh waters

Ten participants gathered at one location to compare measurements, made in the field and laboratory, of the pH of quiescent solutions of natural waters and dilute acids. The total error associated with a single routine measurement in the laboratory can be controlled to within ±0.2 pH, comprising a standard deviation of 0.05 pH and a bias of 0.1 pH. Inaccurate preparation of standard solutions is an appreciable source of bias. Larger errors observed for field measurements made with commercial equipment arise from poorly defined analytical procedures, the use of inappropriate electrodes, and probably dampness affecting the electronics. Stirring dilute solutions depresses the pH. This bias error, which is similar for all dilute solutions, depends on the type of liquid junction used in the reference electrode. Combination electrodes produce the largest stirring shifts (>0.2 pH) and separate electrodes, especially those with free-flowing junctions, the smallest. Correct choice of equipment and use of well-defined proven procedures are essential for the accurate and precise determination of pH.     

Separation and preconcentration of iron(II) and iron(III) from natural water on a melamine-formaldehyde resin

A combined method for the preconcentration and selective spectrophotometric determination of both valencies of iron, i.e., Fe(II) and Fe(III), down to 0.4 mug l(-1) has been developed. Iron(III) from synthetic and natural water samples has been concentrated on a melamine-formaldehyde resin at pH 5; iron(II) was not retained under identical conditions. The oxidized iron was concentrated on a second resin column. The iron in both columns was eluted with 1 M HCl solution and separately analyzed by the 1,10-phenanthroline-citrate spectrophotometric method. The effect of pH, adsorption and elution rates, and interferences on the developed procedure were investigated. Metal ions that can be retained by the resin at moderate concentrations, e.g., Al(3+), do not cause interference in more dilute solutions encountered in natural water samples. At least 160-fold volume enrichment can be easily obtained using an adsorption flowrate of 50 ml min(-1). A hydrothermal water sample was analyzed by the recommended procedure and by a literature method, and the results were statistically compared by t- and F-tests.     

Radiometric studies on the reaction of some metals with potassium pentacyanonitrosyl manganate

The nature and composition of complexes formed by the reaction of Fe(III), Cr(III), Zn(II), and Co(II) with potassium pentacyanonitrosyl manganate K₃ [Mn(CN)₅NO] has been investigated by radiometric method. The metals form 1∶1 complexes with K₃ [Mn(CN)₅NO], the optimum pH for maximum precipitation being 3.6 for Fe(III), 7.3 for Cr(III), 5.4 for Zn(II), and 8.3 for Co(II). The solubility of the complexes as computed from activity at maximum precipitation point follows the order: chromium complex > iron complex > cobalt complex > zinc complex. The radiometric titration curves also show the formation of colloidal precipitates with dilute Zn(II) solutions.     

Coordination of ions in aqueous solutions of dysprosium chloride according to the X-ray diffraction data

Aqueous solutions of dysprosium chloride in a wide concentration range are studied by X-ray diffraction analysis under standard conditions. The scattered X-ray radiation intensity curves are characterized by prepeaks at low values of the wave vector. Their interpretation and an analysis of changes at different concentrations are performed. The structure of concentrated solutions is formed due to interionic interactions of different types. On the contrary, dilute solutions are characterized by the determining role of the quasi-tetrahedral structure of the solvent. The prepeaks are also observed on the intensity curves of dilute solutions, indicating that these solutions retain the “long-range” ordering.     

Activity coefficients of single electrolytes in concentrated solutions derived from a quasi-lattice model

This paper describes a new model to calculate the mean activity coefficients of dissociated electrolytes in concentrated solutions. It is based on three assumptions: (i) a quasi-lattice arrangements of ions in solution; (ii) a contribution from ion-water interactions to the mean activity coefficients; (iii) a concentration dependence of the dielectric constant. The mean activity coefficients of thirteen strong electrolytes from moderately dilute solutions to saturated solutions are found to correlate well by this model. For dilute solutions, a limiting equation in which only ion-specific parameters are required is proposed. It is suggested that specific ionwater interactions might be the major source of the nonideality of strong electrolyte solutions at high concentrations.     

Concentration dependence of the structure of aqueous solutions of samarium trichloride according to X-ray diffraction

Aqueous solutions of samarium chloride in a wide range of concentration under ambient conditions are studied by X-ray diffraction analysis. The small-angle peaks in experimental scattering intensity curves are interpreted. It is shown that highly concentrated solutions are characterized by a unique structure that differs heavily from the structure of dilute systems. It is found that small-angle peaks also appear in the intensity curves of dilute solutions, indicating that the so-called long-range order is preserved in these solutions. It is revealed that the contributions to the total scattering pattern that govern the appearance of prepeaks are interionic interactions of different types (e.g., cation-cation, anion-cation, and anion-anion interactions) in concentrated systems and the distances between the cations in dilute solutions.     

Reexamining protein-protein and protein-solvent interactions from Kirkwood-Buff analysis of light scattering in multi-component solutions

The classic analysis of Rayleigh light scattering (LS) is re-examined for multi-component protein solutions, within the context of Kirkwood-Buff (KB) theory as well as a more generalized canonical treatment. Significant differences arise when traditional treatments that approximate constant pressure and neglect concentration fluctuations in one or more (co)solvent/co-solute species are compared with more rigorous treatments at constant volume and with all species free to fluctuate. For dilute solutions, it is shown that LS can be used to rigorously and unambiguously obtain values for the osmotic second virial coefficient (B(22)), in contrast with recent arguments regarding protein interactions deduced from LS experiments. For more concentrated solutions, it is shown that conventional analysis over(under)-estimates the magnitude of B(22) for significantly repulsive(attractive) conditions, and that protein-protein KB integrals (G(22)) are the more relevant quantity obtainable from LS. Published data for α-chymotrypsinogen A and a series of monoclonal antibodies at different pH and salt concentrations are re-analyzed using traditional and new treatments. The results illustrate that while traditional analysis may be sufficient if one is interested in only the sign of B(22) or G(22), the quantitative values can be significantly in error. A simple approach is illustrated for determining whether protein concentration (c(2)) is sufficiently dilute for B(22) to apply, and for correcting B(22) values from traditional LS regression at higher c(2) values. The apparent molecular weight M(2, app) obtained from LS is shown to generally not be equal to the true molecular weight, with the differences arising from a combination of protein-solute and protein-cosolute interactions that may, in principle, also be determined from LS.     

Numerical Simulation of pH Measurement in Dilute Solutions of the System H<Subscript>2</Subscript>O–KCl–HCl

Potentiometric pH measurements on cells with liquid junctions are known to be biased with respect to the notional pH in dilute acid solutions, but detailed evaluation of the problem is obstructed by experimental difficulties. In this work, pH measurements are simulated numerically on a kind of the Harned cell with a free-diffusion junction between the saturated solution of KCl and dilute solutions of HCl + KCl with ionic strength and acid concentration varying from 0.0001 to 0.1 in terms of molarity. The pH is standardized against the solution 0.0001 M HCl + 0.05 M KCl, and the simulations are based on known solution properties (transport numbers, activity coefficients and diffusion coefficients). The bias is found to range from ?0.012 to 0.056 in the composition range studied. The cell response is nearly linear in the notional pH in solutions with varying acid concentration, but no such relation is found in solutions with varying ionic strength at fixed acid concentration. It is shown that the Henderson equation underestimates the residual liquid-junction effect in very dilute solutions, largely due to failure to account for activity coefficients varying along the junction.     

Biosorption of Au (III) and Cu (II) from aqueous solution by a non-living Cetraria islandica (L.) Ach

Biosorption of Au(III) and Cu(II) from dilute aqueous solutions was investigated by biomass of the non-living Cetraria islandica (L.) Ach. The removal and recovery of gold and copper were studied by applying batch technique. The experimental parameters such as the pH of the solution, contact time, the amount of Cetraria islandica (L.) Ach. (dried lichen), the concentration of metals on retention and eluents kind and amount have been investigated. Au(III) and Cu(II) were adsorbed on the dried lichen at pH 3 and pH 8, respectively. Quantitative retention (> or = 90%) was obtained within 60 minutes for metals. Maximum capacity of 1.0 g of dried lichen for biosorption of Au(III) and Cu(II) were found as 7.4 mg of Au(III) and 19.2 mg of Cu(II). It was seen that the adsorption equilibrium data conformed well to the Langmuir model and Freundlich equation for Au(III) and only Freundlich equation for Cu(II). The method proposed in this study was applied to spiked mineral water analysis and metals adsorbed on the lichens were quantitatively (> or = 90%) recovered from mineral water samples by using 0.5 mol L(-1) HCl.     

Investigations of Cobalt, Nickel, and Copper Diethyldithiocarbamates Using Thermal Lens Spectrometry

Thermal lens spectrometry was used to study the dissociation kinetics of diethyldithiocarbamate complexes of copper(II), cobalt(III), and nickel(II) as a function of pH in the presence of chloride and sulfate ions. It is shown that, as distinct from conventional spectrophotometric and potentiometric measurements, the reversible dissociation of the test complexes and the irreversible oxidation of the ligand can be studied separately (at a level of n × 10^–8–n × 10^–6 M) using thermal lens spectrometry. Because of work in more dilute solutions and due account of the kinetic features of the systems in question, thermal lens spectrometry provides a higher accuracy of the determination of stability constants for diethyldithiocarbamate complexes of copper(II), cobalt(III), and nickel(II). The adsorption of the diethyldithiocarbamate complexes in question from water–ethanol solutions (1 : 3) on Silasorb C₁₈ silica is studied, and the adsorption constants are determined. The limits of detection of copper(II), cobalt(III), and nickel(II) diethyldithiocarbamates obtained in extraction–thermal-lens determination are n × 10^–8 M.     

Preparation and characterization of potassium copper nickel hexacyanoferrate(II) as an ion exchanger for cesium

Potassium copper nickel hexacyanoferrate(II) [KCNF] was prepared by treating potassium nickel hexacyanoferrate(II) with copper nitrate solution in 0.1M HNO₃. The resulting material was dried at various temperatures. Chemical analysis, i.r., thermal decomposition and surface property measurements were used to characterize the material. The adsorption of cesium from aqueous solutions on KCNF was investigated and optimized as a function of equilibration time and pH. The material dried at 110°C was found to be fairly stable in dilute acids, salt solutions, high doses of gamma-radiation and at high temperature. It also showed better surface properties and a high value of ion exchange capacity (2.25 mmol·g^–1) for cesium.     

Efficient Adsorption and Recovery of Pb(II) from Aqueous Solution by a Granular pH-Sensitive Chitosan-based Semi-IPN Hydrogel

A series of granular pH-sensitive semi-interpenetrating polymer network (semi-IPN) hydrogels based on chitosan (CTS), acrylic acid (AA) and gelatine (GE) were utilized for the adsorption and recycle of Pb(II) from aqueous solutions. The composite hydrogels have been characterized by FT-IR and TGA. The effects of contact time, pH value and initial Pb(II) concentration on the adsorption were investigated. Results indicated that the adsorption capacity of the hydrogel increased with increasing pH value and initial Pb(II) concentration, and a pH-sensitive adsorption characteristic was presented. The adsorption rate of the semi-IPN hydrogels on Pb(II) is fast with an adsorption rate constant of 14.9790 mg/(g·s), and adsorption equilibrium could be reached within 10 min. The adsorption isotherms of the hydrogels for Pb(II) could be described well by the Langmuir equation, rather than the Freundlich equation. The as-prepared hydrogels showed good reusability with 0.05 mol/l HNO₃ solutions as the desorbing agent and 0.1 mol/l NaOH solutions as the regeneration agent, respectively. After five consecutive adsorption-desorption processes, the semi-IPN hydrogel with 20 wt% GE may reach 85.26% of its initial adsorption capacity. In addition, the adsorbed Pb(II) can be quantitatively recovered by simply eluting the hydrogel with dilute HNO₃ solution, and a recovery ratio of 89.27% was reached for the semi-IPN hydrogel. The satisfactory adsorption amount is mainly derived from the chelating of functional groups (i.e. –COO^? and –NH₂) with Pb(II) ions. The hydrogel adsorbents exhibited excellent affinity for Pb(II), and can be applied to treat wastewater containing heavy metal ion and simultaneously recover the valuable metal sources.