Química

URI permanente desta comunidadehttps://locus.ufv.br/handle/123456789/11782

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    Chromium speciation using aqueous biphasic systems: Development and mechanistic aspects
    (Separation and Purification Technology, 2016-01-28) Patrício, Pamela R.; Cunha, Roselaine C.; Vargas, Silvia J. Rodriguez; Coelho, Yara Luiza; Silva, Luis Henrique Mendes da; Silva, Maria C. Hespanhol da
    The two principal oxidation states of chromium diverge significantly in their biological and toxicological properties, and it is very important to distinguish between them. Develop procedures that are efficient, fast, easier and cheaper for chromium speciation is an analytical challenge. Chromium speciation was investigated using aqueous biphasic systems (ABS) formed by polyethylene oxide (PEO1500) or a triblock copolymer (L64), an electrolyte (Li2SO4, Na2SO4, MgSO4, C6H5Na3O7, or C4H4Na2O6) and water, without the presence of any extractant. Cr(III) was favorably partitioned to the electrolyte-rich phase (ERP) of the ABS, whereas the Cr(VI) was preferentially concentrated in the macromolecule-rich phase (MRP) in most analyzed ABS. The fluorescence spectroscopy data revealed that the Cr(III) and Cr(VI) separation process is governed by specific interactions between the ethylene oxide segments in the macromolecules and the Cr(VI) species, which do not occur for Cr(III) species. The extraction percentage (%E) of chromium species from the ERP to the MRP was affected by pH, tie-line length (TLL), electrolyte nature, and macromolecule hydrophobicity. For the ABS comprising of PEO1500 + Na2SO4 + H2O, TLL = 50.89% (m/m), 25 °C and pH 2.0, the %E values for Cr(III) and Cr(VI) were 0.0100 and 99.9%, respectively. The speciation of Cr(III) and Cr(VI) that was achieved in this ABS resulted in an excellent separation factor (SCr(VI),Cr(III)) of 1.00 × 10 8.
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    In situ determination of the syringyl/guaiacyl ratio of residual lignin in pre-bleached eucalypt kraft pulps by analytical pyrolysis
    (Journal of Analytical and Applied Pyrolysis, 2015-03) Lima, Cláudio Ferreira; Barbosa, Luiz CLaudio Almeida; Silva, Marcela N. N.; Colodette, Jorge Luiz; Silvério, Flaviano Oliveira
    Pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS) was used for evaluating the syringyl/guaiacyl (S/G) ratios of residual lignins in oxygen pre-bleached kraft pulps from 24 Eucalyptus wood clones. The optimization of the method showed that the best conditions were achieved when pyrolysis is carried out at 550 °C, using a 60 m length SPB-1701 capillary column and the mass spectrometer operating in SIM mode. Pulp pyrograms were analyzed and the compounds produced by pyrolysis of residual lignins identified by mass spectrometry. A total of 18 compounds were identified, being nine derived from guaiacyl units and nine derived from syringyl lignin. The S/G ratios were calculated using the relative area of S-lignin (syringol, 4-methylsyringol, 4-vinylsyringol and trans-4-(prop-2-enyl) syringol) and G-lignin (guaiacol, 4-methylguaiacol, 4-vinylguaiacol and trans-isoeugenol) as lignin markers. These studies showed that Py-GC/MS-SIM is an efficient tool to characterizing the chemical composition of residual lignin in oxygen pre-bleached Eucalyptus pulps.