L. K. Neudachina

Selective adsorption of silver(I) ions over copper(II) ions on a sulfoethyl derivative of chitosan

This study presents a simple and effective method of preparation of N-(2-sulfoethyl) chitosan (NSE-chitosan) that allows obtaining a product with a degree of modification up to 1.0. The chemical structure of the obtained polymers was confirmed by FT-IR and 1H NMR spectroscopies. Cross-linking of N-(2-sulfoethyl) chitosans by glutaraldehyde allows preparation of sorbents for removal and concentration of metal ions. Capacity of sorbents towards hydroxide ions was determined depending on the degree of sulfoethylation under static and dynamic conditions. Dissociation constants of functional amino groups of the analyzed sorbents were determined by potentiometric titration. It was shown that basicity of the amino groups decreased (wherein pKa decreased from 6.53 to 5.67) with increase in degree of sulfoethylation. It explains the significant influence of sulfo groups on selectivity of sorption of metal ions on N-(2-sulfoethyl) chitosan-based sorbents. The investigated substances selectively remove copper(II) and silver(I) ions from solutions of complex composition. Wherein the selectivity coefficient KAg/Cu increased to 20 (pH 6.5, ammonium acetate buffer solution) with increase in degree of sulfoethylation of the sorbent up to 1.0.

Simple synthesis and chelation capacity of N-(2-sulfoethyl)chitosan, a taurine derivative

This study presents a simple and effective synthesis method of N-(2-sulfoethyl)chitosan (NSE-chitosan) via a reaction between sodium 2-bromoethanesulfonate and chitosan that allows polymer transformation without using additional reagents and organic solvents. The chemical structure of the obtained NSE-chitosan was characterized by FT-IR and (1)H NMR spectroscopies. Thermogravimetric study of NSE-chitosan coupled with FT-IR analysis has shown stability of the polymer up to 200 °C, which almost does not change with the increase of degree of substitution (DS). The sorption of transition and alkaline earth metal ions from multicomponent solutions on NSE-chitosan was investigated. The synthesized sorbents showed the selective recovery of silver(I) and copper(II) ions from ammonium acetate buffer solution. The increase of DS enhanced the selectivity to silver(I) ions sorption in comparison with copper(II) ions. Selectivity coefficients K(Ag/Cu) increase from 1.3 to 10.9 with DS increasing up to 0.7 (ammonium acetate buffer solution, pH 6.5). Sorption isotherms of transition metal ions on NSE-chitosan with DS = 0.5 have been fitted using Langmuir, Freundlich, and Redlich-Peterson models. The maximum sorption capacities of sorbent in ammonium acetate buffer solution at pH 6.0 were 1.72 mmol/g for Cu(II), 1.23 mmol/g for Ag(I) and below 0.5 mmol/g for Co(II), Zn(II), Cd(II), Pb(II), Mn(II) and Ni(II) ions.

Removal of metal ions in fixed bed from multicomponent solutions using N-(2-sulfoethyl) chitosan-based sorbents

ABSTRACT This work focuses on the dynamic removal of transition and alkaline earth metal ions using N-(2-sulfoethyl) chitosan-based sorbents (NSE) with various degrees of substitution (DS) in fixed-bed columns. The breakthrough curves for Ag(I), Cu(II), Co(II), Ni(II), Zn(II), Mn(II), Cd(II), Mg(II), Ca(II), Sr(II), Ba(II) and Pb(II) ions sorption onto chitosan-based materials were obtained. Experimental data allows concluding that the mechanisms of sorption of these metals are different. Thomas, Adams-Bohart and Yoon-Nelson models were applied to the experimental data to predict the breakthrough curves and the rate constants. The surface of chitosan-based materials could be fully regenerated by a 0.1 mol/dm3 nitric acid solution.

Effect of the degree of cross-linking of N-2-sulfoethylchitosan on the sorption selectivity of copper(II) and silver(I)

Sorption materials based on N-2-sulfoethylchitosan (SECH) with various degrees of cross-linking by glutaric aldehyde were synthesized. The composition and structure of the materials were characterized by elemental analysis and IR Fourier spectroscopy. The selectivity coefficients KAg/Cu were determined for sorbents with a degree of substitution equal to 0.5. It was shown that the sorption selectivity of silver(I) grows with increasing degree of SECH cross-linking, compared with copper(II) in an ammonia-acetate buffer solution.

Synthesis of sorption materials based on dithiooxamidate aminopropyl polysiloxane

Reaction of reamidation of rubeanic acid with aminopropyl polysiloxane was systematically studied. It was found that the given type of transformations make it possible to obtain a derivative of aminopropyl polysiloxane with surface dithiooxamide groups in a concentration of up to 0.78 mmol g−1 at a total degree of substitution of up to 0.25. The composition and structure of the derivatives obtained were characterized by elemental analysis, IR spectroscopy, thermogravimetry, and method of low-temperature adsorption of nitrogen. The sorption of Ni(II), Pd(II), and Pt(II) in a 0.2 M solution of hydrochloric acid was evaluated for the products obtained.

Methods for correction of selectivity of N-(2-sulfoethyl)chitosan-based materials towards platinum(IV) and palladium(II) ions

ABSTRACT In this paper, we report methods for correction of selectivity of sorbents based on N-(2-sulfoethyl)chitosan towards platinum(IV) and palladium(II) in HCl solutions. The common method for correction of selectivity of the sorbents is variation of their modification degree with complexing groups. An increase in the degree of sulfoethylation of the chitosan leads to the significant increase in selectivity of sorption of palladium(II) over platinum(IV). Application of the N-(2-sulfoethyl)chitosan with the highest degree of sulfoethylation allows for selective separation palladium(II) from platinum(IV) (рН = 5.0). Palladium is quantitatively desorbed from the surface of the N-(2-sulfoethyl)chitosans by 3.5 mol/dm3 solution of HCl.

Effect of Complex-Former Ion Concentration on the Selectivity of Metal Ion Sorption on Cross-Linked N-2-Sulfoethylchitosan

Copper(II), silver(I), cobalt(II), nickel(II), zinc(II), manganese(II), and magnesium(II) sorption isotherms on cross-linked sulfoethylated chitosan with the degree of sulfoethylation DS = 0.7 (SEC 0.7) have been plotted for the individual or collective presence of these ions in solution have been constructed. The capacities of the studied sorbents for the studied metal ions have been calculated by processing the sorption isotherms. SEC 0.7 is found to have the greatest affinity to copper(II) and silver(I); their presence almost completely suppresses the sorption of associated metal ions. The Redlich–Peterson model gives the best fit to the sorption isotherms for collectively present metal ions, indicating the chemical inhomogeneity of the sorbent surface.

Influence of the Degree of Chitosan Sulfoethylation on the Sorption of Palladium(II) Chloride Complexes from Multicomponent Solutions

The influence exerted by the degree of substitution of sulfoethylated chitosan cross-linked with glutaraldehyde on the sorption of Pd(II) chloride complexes from multicomponent solutions containing Pt(IV), Cu(II), Ni(II), Co(II), Cd(II), and Zn(II) was studied. The sorption of transition metal ions under the conditions of the experiment at pH 0.5–5.0 is virtually fully suppressed. The strongest interfering effect on the Pd(II) sorption is exerted by Pt(IV). Calculation of the selectivity coefficients KPd/Pt shows that the selectivity of the Pd(II) sorption relative to Pt(IV) increases with an increase in the degree of substitution of chitosan from 0.3 to 0.5. Integral kinetic curves of the Pd(II) sorption were obtained, and the dependences were subjected to mathematical processing using the models of diffusion and chemical kinetics. The equilibrium in the palladium(II) chloride solution–sorbent system is attained within 40 min. Pd and Pt are quantitatively desorbed from the sorbent surface under dynamic conditions with 3.5 M HCl solution.

Sorption isotherms of metal ions onto an N-(2-sulfoethyl)chitosan-based material from single- and multi-component solutions

ABSTRACT The scope of work is to study the mutual influence of metal ions during their sorption by sulfoethylated chitosan. The sorption isotherms of metal ions from single- and multi-component solutions are obtained. The sorption capacity of the sorbent towards Ag(I) and Cu(II) is revealed to be 1.63 and 1.41 mmol/g in single-, and 1.40 and 0.85 mmol/g in five-component solution. By comparing the affinity parameter and capacity of sulfoethylated chitosan towards ions in single- and multi-component solutions, it is concluded that Ag(I) and Cu(II) ions suppress the sorption of cobalt(II), nickel(II), zinc(II), cadmium(II), magnesium(II), calcium(II), strontium(II), barium(II), manganese(II) and lead(II).

Dynamics of the sorption of copper(II) and silver(I) by materials based on sulfoethylchitosan with various degrees of crosslinking

Optimum conditions of the dynamic concentration of copper(II) and silver(I) ions simultaneously present in a solution with N-(2-sulfoethyl)chitosan with a degree of modification equal to 0.5 and different degrees of crosslinking by glutaraldehyde are determined. The values of coefficients of selectivity KAg/Cu are determined under dynamic conditions. It is shown that the selectivity of the sorption of silver(I) increases (compared to copper(II)) as the degree of crosslinking of sorbents based on N-(2-sulfoethyl)chitosan is raised. Mathematical treatment of the obtained dynamic curves is performed according to the Thomas, Adams–Bohart, and Yoon and Nelson models. As a result, the values of dynamic capacity of sorbents, the rate constant of the reaction, and the release time of 50% of the sorbate are determined. The quantitative desorption of copper and silver from the surface of sorbents is achieved by using 1 mol/dm3 solution of nitric acid.