Characterisation and utilisation of solid waste from coal combustion to modelling of sorption equilibrium in a bi-component system metal-dye.

It was found that the chemical enhancement of fly ash from coal combustion by tetrabutylammonium bromide treatment yields an effective and economically feasible material for the treatment of chromium and basic dye Rhodamine B containing effluents. Characterisation of coal fly ash and treatment with tetrabutylammonium bromide were done by using a Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, confocal three-dimensional microscope, X-ray diffraction and laser particle sizer. The studies of equilibrium in a bi-component system by means of extended Langmuir, extended Langmuir-Freundlich and Jain-Snoeyink models were analysed. The estimation of parameters of sorption isotherms in a bi-component system metal-dye has shown that the best-of-fit calculated values of experimental data for both sorbates have been the Jain-Snoeyink model and the extended Langmuir model, but only in the case of a Rhodamine B. The maximum monolayer adsorption capacity of the fly ash-tetrabutylammonium bromide was found to be 863 mg g-1 and 670 mg g-1 for chromium and Rhodamine B, respectively.

Enhanced sorption capacity of a metal-dye system from water effluents by using activated industrial waste.

Activated coal fly ash (FA) treated with NaOH and hexadecyltrimethylammonium bromide (HDTMABr) was used as adsorbent for removal of cadmium(II) ions and rhodamine B (RB) from an aqueous solution. Characterization of fly ash and FA-HDTMABr were done using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The sorption equilibrium in the system was analysed using isotherm models, such as Freundlich, Langmuir, generalized Langmuir-Freundlich, Redlich-Peterson, Jovanovic, extended Jovanovic, Tóth, Frumkin-Fowler-Guggenheim, Fowler-Guggenheim-Jovanovic-Freundlich, Temkin, Dubinin-Radushkevich, Halsey, Brunauer, Emmett and Teller. The evaluation of the fit of the isotherms studied experimentally was carried out by means of the reduced chi-square test and the coefficient of determination. The maximum monolayer adsorption capacity of the FA-HDTMABr was found to be 744 mg·g-1 and 666 mg·g-1 for Cd(II) and RB, respectively. The PFO, PSO, Elovich mass transfer, liquid film diffusion and intra-particle diffusion models were analysed. Sorption kinetics data were well fitted by the PSO model. The Elovich and intra-particle model also revealed that there are two separate stages in the sorption process, namely, external diffusion and intra-particle diffusion.

Syntheses, crystal structures and antioxidant study of Zn(II) complexes with morin-5'-sulfonic acid (MSA).

The study of modified synthetic procedure of water soluble morin-5'-sulfonic acid sodium salt (NaMSA) involving less aggressive chemicals and carried out at mild conditions was described. The NaMSA salt is a convenient source of anionic morin-5'-sulfonic ligand (MSA) in ion exchange reactions. The coordination ability of MSA ligand towards the zinc cations was investigated in aqueous solution and in solid state. Novel zinc complexes of morin-5'-sulfonate were obtained by a reaction of Zn(NO3)2 with morin-5'-sulfonate in water. Resulting compounds were characterized by single-crystal X-ray diffraction analysis, as well as spectral and thermal methods. The coordination interaction, hydrogen bond and π-π stacking lead to the formation of a 1D chain or 3D coordination polymers. The antioxidant activity of the Zn(II)-MSA complexes was evaluated by means of 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging method. In this work, we have shown that the studied compounds are more effective free radical scavengers than the natural flavonoids like plain morin.

Tautomeric and Microscopic Protonation Equilibria of Anthranilic Acid and Its Derivatives.

The acid-base chemistry of three zwitterionic compounds, namely anthranilic (2-aminobenzoic acid), N-methylanthranilic and N-phenylanthranilic acid has been characterized in terms of the macroconstants Ka1, Ka2, the isoelectric point pHI, the tautomerization constant Kz and microconstants k11, k12, k21, k22. The potentiometric titration method was used to determine the macrodissociation constants. Due to the very poor water solubility of N-phenylanthranilic acid the dissociation constants pKa1 and pKa2 were determined in MDM-water mixtures [MDM is a co-solvent mixture, consisting of equal volumes of methanol (MeOH), dioxane and acetonitrile (MeCN)]. The Yasuda-Shedlovsky extrapolation procedure has been used to obtain the values of pKa1 and pKa2 in aqueous solutions. The pKa1 and pKa2 values obtained by this method are 2.86 ± 0.01 and 4.69 ± 0.03, respectively. The tautomerization constant Kz describing the equilibrium between unionized form ⇌ zwitterionic form was evaluated by the Kz method based on UV-VIS spectrometry. The method uses spectral differences between the zwitterionic form (found at isoelectric pH in aqueous solution) and the unionized form (formed in an organic solvent of low dielectric constant). The highest value of the Kz constant has been observed in the case of N-methylantranilic acid (log10Kz = 1.31 ± 0.04). The values of log10Kz for anthranilic and N-phenylanthranilic acids are similar and have values of 0.93 ± 0.03 and 0.90 ± 0.05, respectively. The results indicate that the tested compounds, in aqueous solution around the isoelectric point pHI, occur mainly in the zwitterionic form. Moreover, the influence of the type of substituent and pH of the aqueous phase on the equilibrium were analyzed with regard to the formation and the coexistence of different forms of the acids in the examined systems.

Studies on equilibrium of anthranilic acid in aqueous solutions and in two-phase systems: aromatic solvent-water.

The acid-base equilibria of anthranilic acid have been characterized in terms of macro- and microdissociation constants (dissociation constants K(a1), K(a2) and tautomeric constant K(z)). On the basis of spectrophotometric investigations the values of the distribution ratio D of anthranilic acid in the two-phase systems: aromatic solvent (benzene, ethylbenzene, toluene, chlorobenzene, bromobenzene)-aqueous solution were obtained. Employing the results of potentiometric titration in the two-phase systems: aromatic solvent-aqueous solution the distribution constant K(D) and dimerization constant K(dim) values were calculated. The influence of organic solvent polarity and pH of the aqueous phase on the contents of the particular forms of the acid in the two-phase systems were analyzed.

Investigations of chemical fraction of Co and Ni in industrial fly ash and mobility of metals in environmental conditions.

The quantitative evaluation of chemical fraction of Co and Ni in the industrial fly ash by methods of five step sequential extraction was carried out in order to characterize metal mobility in environmental conditions. The research involved (i) water-soluble (pH=7), (ii) acid-soluble (pH=5), (iii) oxide, (iv) sulfide and (v) residue metal fractions. It was discovered, that the total extraction of the studied metals from fly ash to solutions take place in the following quantities Co - 35.5 and Ni - 153.0mgkg(-1). The investigations of chemical fractions proved that the subject metals occur mainly in fly ash as: oxide (Co - 7.0, Ni - 28.5mgkg(-1)) and residue (Co - 11.5, Ni - 42.5mgkg(-1)) as well as sulfide (Co - 8.5, Ni - 46.5mgkg(-1)). Low concentrations of metals for water-soluble fraction (Co - 0.7, Ni - 1.2mgkg(-1)) and acid-soluble fraction (Co - 4.5, Ni - 23.5mgkg(-1)) were observed. The fractions of Co and Ni leachable from the ash in environmental conditions contain: 24.0% (Co) and 23.3% (Ni) of metal total amount in the industrial fly ash. The obtained mobility parameter of Co and Ni can be applied to estimate the concentration increase of mobile and hardly mobile forms of these metals in soil polluted with the ash.

Investigations of sequential leaching behaviour of Cu and Zn from coal fly ash and their mobility in environmental conditions.

The quantitative evaluation of chemical fraction of Cu and Zn in the coal fly ash by methods of five-step sequential extraction was carried out in order to characterize metal mobility in environmental conditions. The research involved (i) water-soluble (pH 7), (ii) acid-soluble (pH 5), (iii) oxide, (iv) difficult reducible and (v) residual metal fractions. It was discovered, that the total extraction of the studied metals from coal fly ash to solutions take place in the following quantities Cu-39.0mgkg(-1) and Zn-89.0mgkg(-1). The investigations of chemical fractions proved that the subject metals occur mainly in coal fly ash as: oxide (Cu-12.0mgkg(-1), Zn-37.0mgkg(-1)) and residual (Cu-9.5mgkg(-1), Zn-27.0mgkg(-1)) as well as difficult reducible (Cu-16.5mgkg(-1), Zn-22.0mgkg(-1)). Low concentrations of metals for water-soluble fraction (Cu

Studies on the distribution of N-phenylanthranilic acid in two-phase system: Aromatic solvent-water.

The detailed description of equilibria of N-phenylanthranilic acid in the aqueous solutions and in the two-phase systems: aromatic solvent-aqueous solution were obtained. The isoelectric point, pH(I), the dissociation constants of the protonated form, K(a1), and the neutral form, K(a2), in the aqueous solutions were determined from the apparent ionization constant in methanol-water solutions of various proportions by extrapolation to zero co-solvent using Yasuda-Shedlovsky procedure. On the basis of the spectrophotometric investigations, the values of the distribution ratio, D, of N-phenylanthranilic acid in the two-phase systems: aromatic solvent (benzene, ethylbenzene, toluene, chlorobenzene, bromobenzene)-aqueous solution were obtained. Employing the results of the potentiometric titration in the two-phase systems: aromatic solvent-aqueous solution, and using models of singular and multistep equilibria the values of the distribution constants, K(D), dimerization constants, K(dim), were calculated. The significant influence of the polarity of the applied aromatic solvents and pH of the aqueous phase on the percentage of the particular forms of N-phenylanthranilic acid in the two-phase systems was proved.