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101.
Chemical oxygen demand (COD) is one of the most relevant chemical parameters for the management of wastewater treatment facilities including the control of the quality of an effluent. The adequacy of decisions based on COD values relies on the quality of the measurements. Cost effective management of the minor sources of uncertainty can be applied to the analytical procedure without affecting measurement quality. This work presents a detailed assessment of the determination of COD values in wastewaters, according to ISO6060:1989 standard, which can support reduction of both measurement uncertainty and cost of analysis. This assessment includes the definition of the measurement traceability chain and the validation of the measurement procedure supported on sound and objective criteria. Detailed models of the measurement performance, including uncertainty, developed from the Differential Approach, were successfully validated by proficiency tests. The assumption of the measurement function linearity of the uncertainty propagation law was tested through the comparison with the numerical Kragten method. The gathered information supported the definition of strategies for measurement uncertainty or cost reduction. The developed models are available as electronic supplementary material, in an MS-Excel file, to be updated with the user's data. 相似文献
102.
Silvana E. Vignaduzzo Luciana Vera-Candioti Patricia M. Castellano H��ctor C. Goicoechea Teodoro S. Kaufman 《Chromatographia》2011,74(7-8):609-617
A capillary zone electrophoresis method for the simultaneous determination of pridinol mesylate (PRI) and meloxicam (MEL) employing epinastine hydrochloride and piroxicam as internal standards, was developed and optimized employing experimental design and response surface methodologies. The separation was optimally achieved in less than 2 min at 30 kV in an uncoated fused-silica capillary (41.4 cm × 75 ??m I.D.), employing an 18 mmol L?1 sodium phosphate buffer solution (pH 5.90) at 25 °C. Samples were injected in hydrodynamic mode (50 mbar, 5 s) and the analytes were spectrophotometrically detected at 200 nm. Method robustness was demonstrated by ANOVA of determinations performed under conditions slightly different from the optimum. The method was validated regarding separation selectivity (peak purity factors > 0.99), linearity and range (PRI = 17.6?C31.4 mg L?1; MEL = 66.5?C122.5 mg L?1), accuracy (PRI = 100.2?C101.9%; MEL = 98.9?C100.7%) and precision. The RSD values obtained were ??1.3% for injection repeatability and ??1.9% for intra-day precision. The limits of detection (1.0 and 0.9 mg L?1) and quantification (3.3 and 16.5 mg L?1) of PRI and MEL, respectively, were also determined. The method was successfully applied to the determination of both drugs in three brands of tablet formulations. No statistically significant differences were observed when these results were compared with those of a RP-HPLC method. 相似文献
103.
Saviour A. Umoren Mauro J. Banera Teodoro Alonso-Garcia Claudio A. Gervasi Maria V. Mirífico 《Cellulose (London, England)》2013,20(5):2529-2545
The efficiency of chitosan (a naturally occurring polymer) as a corrosion inhibitor for mild steel in 0.1 M HCl was investigated by gravimetric, potentiodynamic polarization, electrochemical impedance spectroscopy measurements, scanning electron microscopy, and UV–visible analysis. The polymer was found to inhibit corrosion even at a very low concentration. Inhibition efficiency increases with a rise in temperature up to 96 % at 60 °C and then drops to 93 % at 70 °C, while it slightly increases with an increase in chitosan concentration. Polarization curves indicate that chitosan functions as a mixed inhibitor, affecting both cathodic and anodic partial reactions. Impedance results indicate that chitosan was adsorbed on the metal/solution interface. Adsorption of chitosan at the mild steel surface is found to be in agreement with Langmuir adsorption isotherm model. Chemical adsorption is the proposed mechanism for corrosion inhibition considering the trend of protection efficiency with temperature. Calculated kinetic and thermodynamic parameters corroborate the proposed mechanism. 相似文献
104.
In this paper we continue the analysis of the blow-up of low energy sign-changing solutions of semi-linear elliptic equations with critical Sobolev exponent, started in [M. Ben Ayed, K. El Mehdi, F. Pacella, Blow-up and nonexistence of sign-changing solutions to the Brezis-Nirenberg problem in dimension three, Ann. Inst. H. Poincaré Anal. Non Linéaire, in press]. In addition we prove axial symmetry results for the same kind of solutions in a ball. 相似文献
105.
Carla Cannas Giorgio Piccaluga Filomena Serra Stefano Enzo 《Journal of solid state chemistry》2005,178(5):1526-1532
The Y2O3-SiO2 1:1 composition doped with a weak concentration of europium ions was prepared with the sol-gel technique and the products studied by X-ray diffraction as a function of temperature in the range from 900 to 1300 °C, using the method of Rietveld for quantitative evaluation of amorphous and crystalline evolving phases. The amorphous profile of the yttrium oxyorthosilicate glasses has been described following the “Rietveld for Disordered Materials” method and subsequently included in the patterns of semicrystalline samples that have been heat-treated for temperatures above 900 °C at 1000, 1100, 1150, 1200 and 1300 °C. The quantitative evaluation of the amorphous phase is obtainable from the Rietveld approach equivalent to the method after Ruland. This enabled us to study in fine detail the structural rearrangements and growth mechanisms that take place during the crystal-to-amorphous transformation in terms of coordination numbers, average interatomic distances, average crystallite size and microstrain and to identify the polymorphous transformation involving the Y2SiO5 phase from low-to-high-temperature forms, as well as some minor quantities of other phases namely α-Y2Si2O7 phase, Y2O3 and Y4.67(SiO4)3O. 相似文献
106.
M.J.Guiomar H.M. Lito M.Filomena G.F.C. Camões M.Isabel A. Ferra Arthur K. Covington 《Analytica chimica acta》1990
Making the simplest possible assumption about the activity coefficient of the charged species, pH values of standard buffer solutions have been evaluated from the thermodynamic acidity constants, K, of the weak acids involved. A general equation is given for a triprotic acid, H3A, as it can be simplified to derive the equations for other systems. A computer program for the solution of the equation was written giving mH values, species distribution coefficients, α, buffer capacities, β, species activity coefficients, γ, and ionic strength, I. Iteration was continued until agreement between successive values to within 1 ± 10?6 was reached.The activity coefficients of singly charged ions were taken as equal to γCl, where log γCl=?AI1/2 (1 + 1.5I1/2), which is the Bates-Guggenheim convention, and those of doubly and triply charged ions were given by the valence relations of the Debye-Hückel theory as γ4Cl and γ9Cl, respectively. 相似文献
107.
108.
Couto N Ramos MJ Fernandez MT Rodrigues P Barros MT Costa ML Cabral BJ Duarte MF 《Rapid communications in mass spectrometry : RCM》2008,22(4):582-590
The present work describes a study of the complexation of calcium and magnesium by 3-azidopropionitrile by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of calcium and magnesium salts of the type CaX2 and MgX2 (where X = Cl or NO3) in water and methanol/water. The complexes detected were mainly double positively charged, with various stoichiometries not depending on the solvent, since water and 3-azidopropionitrile were always the main ligands. Solvation with methanol was not observed unlike in a previous study of complexation of nickel and cobalt by 3-azidopropionitrile. The complex ions [M(II)Az4(H2O)](2+), [M(II)Az5](2+) (where M = Ca and Mg) are the most abundant for both metals, and both counter ions. Tandem mass spectrometric (MS/MS) analysis showed that, under collision-induced dissociation (CID) conditions, the most important processes occurring were loss of neutral ligands and the replacement of 3-azidopropionitrile by water. A complex species containing reduced alkaline earth metal was due to radical loss, resulting from homolytic cleavage in the azide ligand. Some terminal ions, in the fragmentation sequences, point to the nitrile group as the coordination site in the 3-azidopropionitrile. Density functional theory (DFT) calculations confirmed this coordination site and proved that 3-azidopropionitrile behaves as a monodentate ligand in the systems under study. Moreover, the theoretical study proved that the presence of water ligand introduces stability through a hydrogen bond established between the water molecule and one nitrogen atom of the azido group. In addition, the strong dipole moment of 3-azidopropionitrile (4.76 D), which is mainly related to presence of the nitrile group, favors the stabilization of the metal-ligand complexes through charge-dipole interactions and the coordination of the metal to the nitrile group. 相似文献
109.
Marc Alexandre Duarte Gigonzac Lilian Souza Teodoro Lysa Bernardes Minasi Thaís Cidália Vieira Aparecido Divino da Cruz 《Electrophoresis》2016,37(23-24):3076-3078
Fragile X syndrome (FXS) is the most common cause of inherited intellectual disability. The most common etiology of the syndrome is expansion and methylation of a CGG trinucleotide at chromosome region Xq27.3 involving FMR1 (fragile X mental retardation 1 gene). This disorder is commonly underdiagnosed in children and adolescents, given the high clinical variability. In Brazil, molecular diagnosis of FXS by CE does not exist in the public health system. The current standard for separation and identification of DNA fragment sizes is 50 cm CE, which is uncommon in public genotyping laboratories. This study describes the standardization of 36 cm CE for fragment analysis of samples from patients with intellectual disability suggestive of FXS. Genomic dsDNA was isolated from patients and amplified by PCR using the FMR1 AmplideX® Kit. It was then possible to detect changes in repeat length of FMR1, such as full mutation and premutation. Thus, the proposed standardization proved to be effective for the diagnosis of FXS, permitting suitable genetic counseling for families. Inclusion of molecular testing such as this in the Brazilian public health service bridges the gap between available technologies and effective diagnosis, universalizing access to genetic testing in central Brazil. 相似文献
110.
Structural Chemistry - Although several studies have attempted to deduce by theoretical calculations the reaction mechanism of carmustine with DNA, no study has presented data on the reaction sites... 相似文献