Immobilization of ethylene sulfide in aminated cellulose for removal of the divalent cations.

Cellulose (Cel) was first chemically modified with thionyl chloride to increase its reactivity. In the next step CelCl was reacted with ethylenediamine (CelEn) and subsequently reacted with ethylene sulfide to obtain a solid substance, CelEnEs. The modification reactions were confirmed by elemental analysis, TG, XRD, (13)C NMR and FTIR. The chemically modified biopolymer CelEnEs had an order of divalent metal sorption of Pb(2+)>Cd(2+)>Ni(2+)>Co(2+)>Cu(2+)>Zn(2+), and the maximum adsorption capacities were found to be 6.282±0.023, 5.783±0.015, 5.561±0.017, 4.694±0.013, 1.944±0.062 and 1.733±0.020 mmol g(-1), respectively. The equilibrium data were fitted to Langmuir, Freundlich and Temkin models, and in general, the experimental data best fit the Freundlich model. This newly synthesized biopolymer proved to be a chemically useful material for cations removal from aqueous solution.

Ethylenesulfide as a useful agent for incorporation into the biopolymer chitosan in a solvent-free reaction for use in cation removal.

Chitosan (Ch) was chemically modified with ethylenesulfide (Es) under solvent-free conditions to give (ChEs), displaying a high content of thiol groups due to opening of the three member cyclic reagent. Elemental analysis showed a decrease in nitrogen content. This result indicated the incorporation of two ethylenesulfide molecules for each unit of the polymeric structure of the precursor biopolymer. Infrared spectroscopy, thermogravimetry, and (13)C NMR in the solid state demonstrated the effectiveness of the reaction, with signals at 30 ppm for ChEs due to the change in the methylene group environment. Divalent metal uptake by chemically modified biopolymer gave the order Cu>Ni>Co>Zn, reflecting the corresponding acidity of these cations in bonding to the sulfur and the basic nitrogen atoms available on the pendant chains. The equilibrium data were fitted to Freundlich, Temkin, and Langmuir models. The maximum monolayer adsorption capacity for the cations was found to be 1.54+/-0.02, 1.25+/-0.03, 1.13+/-0.01, and 0.83+/-0.03 mmol g(-1), respectively. The Langmuir model best explained the cation-sulfur bond interactions at the solid-liquid interface. The thermodynamics for these interactions gave exothermic enthalpic values of -43.02+/-0.03, -28.72+/-0.02, -26.27+/-0.04, and -17.32+/-0.02 kJ mol(-1), respectively. The spontaneity of the systems is given by negative Gibbs free energies of -31.2+/-0.1, -32.7+/-0.1, -31.7+/-0.1, and -32.2+/-0.1 kJ mol(-1), respectively, in spite of the unfavorable negative entropic values of -39+/-1, -13+/-1, -18+/-1, and -49+/-1 J K(-1)mol(-1) due to solvent ordering in the course of complexation. This newly synthesized biopolymer is presented as a chemically useful material for cation removal from aqueous solution.