Highly improved chromium (III) uptake capacity in modified sugarcane bagasse using different chemical treatments

The present paper focuses on improving chromium (III) uptake capacity of sugarcane bagasse through its chemical modification with citric acid and/or sodium hydroxide. The chemical modifications were confirmed by infrared spectroscopy, with an evident peak observed at 1730 cm-1, attributed to carbonyl groups. Equilibrium was reached after 24 h, and the kinetics followed the pseudo-second-order model. The highest chromium (III) maximum adsorption capacity (MAC) value was found when using sugarcane bagasse modified with sodium hydroxide and citric acid (58.00 mg g-1) giving a MAC value about three times greater (20.34 mg g-1) than for raw sugarcane bagasse.

Hydrogels of cellulose acetate crosslinked with pyromellitic dianhydride: part I: synthesis and swelling kinetics

This work describes the synthesis of hydrogels of cellulose acetate (AC) crosslinked with 1,2,4,5-benzenotetracarboxylic dianhydride (PMDA). The crosslinking reaction was monitored by FTIR. Analysis of aromatic fragments from the alkaline hydrolysis of the gels by UV spectroscopy indicated that an increase in the stoichiometric ratio of dianhydride resulted in higher degrees of crosslinking. The non-porous nature of the gels was confirmed by analysis of nitrogen adsorption. Water absorption isotherms showed that as the temperature and degree of crosslinking increased, the percentage of water absorbed at equilibrium (%Seq) also increased. The hydrogels presented second order swelling kinetics.

Adsorção do corante Reativo Azul 19 em solução aquosa por lama vermelha tratada quimicamente com peróxido de hidrogênio

Adsorption of Reactive Blue 19 dye onto activated red mud was investigated. Red mud was treated with hydrogen peroxide (LVQ) and heated at both 400 ºC (LVQ400) and 500 ºC (LVQ500). These samples were characterized by pH, specific surface area, point of zero charge and mineralogical composition. Adsorption was found to be significantly dependent on solution pH, with acidic conditions proving to be the most favorable. The adsorption followed pseudo-second-order kinetics. The Langmuir isotherm was the most appropriate to describe the phenomenon of dye removal using LVQ, LVQ400 and LVQ500, with maximum adsorption capacity of 384.62, 357.14 and 454.54 mg g-1, respectively.

Kinetic modeling of the biosorption of Cd2+ ions from aqueous solutions onto Eichhornia crassipes roots using potentiometry: low-cost alternative to conventional methods

This work presents the use of potentiometric measurements for kinetic studies of biosorption of Cd2+ ions from aqueous solutions on Eichhornia crassipes roots. The open circuit potential of the Cd/Cd2+ electrode of the first kind was measured during the bioadsorption process. The amount of Cd2+ ions accumulated was determined in real time. The data were fit to different models, with the pseudo-second-order model proving to be the best in describing the data. The advantages and limitations of the methodology proposed relative to the traditional method are discussed.

Dinâmica não-linear e reagente limitante: um exemplo de bifurcação transcrítica

The nonlinear analysis of a general mixed second order reaction was performed, aiming to explore some basic tools concerning the mathematics of nonlinear differential equations. Concepts of stability around fixed points based on linear stability analysis are introduced, together with phase plane and integral curves. The main focus is the chemical relationship between changes of limiting reagent and transcritical bifurcation, and the investigation underlying the conclusion.

Removal of Pb(II) ions and malachite green dye from wastewater by activated carbon produced from lemon peel

In the present study, a high-surface area activated carbon was prepared by chemical activation of lemon peel with H3PO4 as the active agent. Then, the adsorption behavior of Malachite green dye and Pb(II) ions on the produced activated carbon was studied. Batch process was employed for sorption kinetics and equilibrium studies. Experimental data were fitted to various isotherm models. According to the Langmuir model, the maximum adsorption capacities of Malachite green dye and Pb(II) ions were found to be 66.67 and 90.91 mg g-1, respectively, at room temperature. Kinetic studies showed the adsorption process followed a pseudo second-order rate model. The sorption kinetics were controlled by intra-particle diffusion. The results indicated that the produced activated carbon can be economically and effectively used as an adsorbent for the removal of Malachite green dye and Pb(II) ions from wastewaters.

Modulating the electronic structure of amino acids: interaction of model lewis acids with anthranilic acid

On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293) illustrated that beryllium ions are capable of significantly modulating (changing) the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+), AlF2+, and Al3+) were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H), and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O) to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O) that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577) and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form.

Resolução multivariada de curvas com mínimos quadrados alternantes: descrição, funcionamento e aplicações

Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS) is a resolution method that has been efficiently applied in many different fields, such as process analysis, environmental data and, more recently, hyperspectral image analysis. When applied to second order data (or to three-way data) arrays, recovery of the underlying basis vectors in both measurement orders (i.e. signal and concentration orders) from the data matrix can be achieved without ambiguities if the trilinear model constraint is considered during the ALS optimization. This work summarizes different protocols of MCR-ALS application, presenting a case study: near-infrared image spectroscopy.

Preparation and evaluation of magnetic chitosan particles modified with ethylenediamine and Fe(III) for the removal of Cr(VI) from aqueous solutions

The adsorption of Cr(VI) in aqueous solution by magnetic particles of crosslinked chitosan-ethylenediamine-Fe(III) (MPCh-EDA-FeCL) was studied in a batch system. Fe3+ in the MPCh-EDA-FeCL permitted that adsorption of Cr(VI) occurred with maximum efficiency between pH 3 and 11. The maximum adsorption capacity at pH 7.0 was 81.04 mg g-1 at 25 ºC. The adsorption kinetic process was described by the pseudo-second-order model. Thermodynamic parameters indicated spontaneous, exothermic and chemical adsorption nature. The adsorbent was successively regenerated using a 0.1 mol L-1 NaOH solution. Results were satisfactory for treatment of wastewater from the electroplating industry.

COMPARAÇÃO DE PROCESSAMENTOS MATEMÁTICOS DE DADOS VOLTAMÉTRICOS: APLICAÇÃO NA DETERMINAÇÃO SIMULTÂNEA DE FLUOROQUINOLONAS

This paper describes a comparative study between the procedures of deconvolution and the second-order derivative of square wave voltammograms to achieve separation of the voltammetric peaks of levofloxacin (LEVO) and norfloxacin (NOR), for their simultaneous quantification in urine samples. The obtained results indicate that the use of second-derivative voltammograms coupled with carbon screen-printed electrodes is the most efficient approach for completely separating the voltammetric peaks of LEVO and NOR. In addition, this approach has produced detection limits lower than 1.0 µmol L-1 and a wide linear range for both drugs. The proposed method was successfully used to simultaneously determine LEVO and NOR in spiked human and bovine urine samples with recovery percentages close to 100% for all analyzed samples.

Sorption kinetics and intrapaticulate diffusivity of As(III) bioremediation from aqueous solution, using modified and unmodified coconut fiber

The pollution and toxicity problems posed by arsenic in the environment have long been established. Hence, the removal and recovery remedies have been sought, bearing in mind the efficiency, cost effectiveness and environmental friendliness of the methods employed. The sorption kinetics and intraparticulate diffusivity of As (III) bioremediation from aqueous solution using modified and unmodified coconut fiber was investigated. The amount adsorbed increased as time increased, reaching equilibrium at about 60 minutes. The kinetic studies showed that the sorption rates could be described by both pseudo-first order and pseudo-second order process with the later showing a better fit with a value of rate constant of 1.16 x 10-4 min-1 for the three adsorbent types. The mechanism of sorption was found to be particle diffusion controlled. The diffusion and boundary layer effects were also investigation. Therefore, the results show that coconut fiber, both modified and unmodified is an efficient sorbent for the removal of As (III) from industrial effluents with particle diffusion as the predominant mechanism.

THE LOGICAL SYSTEM OF FREGE'S GRUNDGESTZE: A RATIONAL RECONSTRUCTION

This paper aims at clarifying the nature of Frege's system of logic, as presented in the first volume of the Grundgesetze . We undertake a rational reconstruction of this system, by distinguishing its propositional and predicate fragments. This allows us to emphasise the differences and similarities between this system and a modern system of classical second-order logic.

Three-dimensional supersonic flow over a spike-nosed body of revolution

The unsteady, viscous, supersonic flow over a spike-nosed body of revolution is numerically investigated by solving the Navier-Stokes equations. The time-accurate computations are performed employing an implicit algorithm based on the second-order time-accurate LU-SGS scheme with the incorporation of a subiteration procedure to maintain time accuracy. The characteristics of the flow field for a Mach number of 3.0, Reynolds number of 7.87 x 10(6)/m, and angles of attack of 5 and 10 degrees are described. Self-sustained asymmetric shock wave oscillations were observed in the numerical computations for these angles of attack. The main characteristic of the flow field, as well as its influence on drag coefficient is discussed.

Modelling of hydrogen stratification and gas mixing in containment using the APROS code

Hydrogen stratification and atmosphere mixing is a very important phenomenon in nuclear reactor containments when severe accidents are studied and simulated. Hydrogen generation, distribution and accumulation in certain parts of containment may pose a great risk to pressure increase induced by hydrogen combustion, and thus, challenge the integrity of NPP containment. The accurate prediction of hydrogen distribution is important with respect to the safety design of a NPP. Modelling methods typically used for containment analyses include both lumped parameter and field codes. The lumped parameter method is universally used in the containment codes, because its versatility, flexibility and simplicity. The lumped parameter method allows fast, full-scale simulations, where different containment geometries with relevant engineering safety features can be modelled. Lumped parameter gas stratification and mixing modelling methods are presented and discussed in this master’s thesis. Experimental research is widely used in containment analyses. The HM-2 experiment related to hydrogen stratification and mixing conducted at the THAI facility in Germany is calculated with the APROS lump parameter containment package and the APROS 6-equation thermal hydraulic model. The main purpose was to study, whether the convection term included in the momentum conservation equation of the 6-equation modelling gives some remarkable advantages compared to the simplified lumped parameter approach. Finally, a simple containment test case (high steam release to a narrow steam generator room inside a large dry containment) was calculated with both APROS models. In this case, the aim was to determine the extreme containment conditions, where the effect of convection term was supposed to be possibly high. Calculation results showed that both the APROS containment and the 6-equation model could model the hydrogen stratification in the THAI test well, if the vertical nodalisation was dense enough. However, in more complicated cases, the numerical diffusion may distort the results. Calculation of light gas stratification could be probably improved by applying the second order discretisation scheme for the modelling of gas flows. If the gas flows are relatively high, the convection term of the momentum equation is necessary to model the pressure differences between the adjacent nodes reasonably.

Stiffness based trajectory planning and feedforward based vibration suppression control of parallel robot machines

The dissertation proposes two control strategies, which include the trajectory planning and vibration suppression, for a kinematic redundant serial-parallel robot machine, with the aim of attaining the satisfactory machining performance. For a given prescribed trajectory of the robot's end-effector in the Cartesian space, a set of trajectories in the robot's joint space are generated based on the best stiffness performance of the robot along the prescribed trajectory. To construct the required system-wide analytical stiffness model for the serial-parallel robot machine, a variant of the virtual joint method (VJM) is proposed in the dissertation. The modified method is an evolution of Gosselin's lumped model that can account for the deformations of a flexible link in more directions. The effectiveness of this VJM variant is validated by comparing the computed stiffness results of a flexible link with the those of a matrix structural analysis (MSA) method. The comparison shows that the numerical results from both methods on an individual flexible beam are almost identical, which, in some sense, provides mutual validation. The most prominent advantage of the presented VJM variant compared with the MSA method is that it can be applied in a flexible structure system with complicated kinematics formed in terms of flexible serial links and joints. Moreover, by combining the VJM variant and the virtual work principle, a systemwide analytical stiffness model can be easily obtained for mechanisms with both serial kinematics and parallel kinematics. In the dissertation, a system-wide stiffness model of a kinematic redundant serial-parallel robot machine is constructed based on integration of the VJM variant and the virtual work principle. Numerical results of its stiffness performance are reported. For a kinematic redundant robot, to generate a set of feasible joints' trajectories for a prescribed trajectory of its end-effector, its system-wide stiffness performance is taken as the constraint in the joints trajectory planning in the dissertation. For a prescribed location of the end-effector, the robot permits an infinite number of inverse solutions, which consequently yields infinite kinds of stiffness performance. Therefore, a differential evolution (DE) algorithm in which the positions of redundant joints in the kinematics are taken as input variables was employed to search for the best stiffness performance of the robot. Numerical results of the generated joint trajectories are given for a kinematic redundant serial-parallel robot machine, IWR (Intersector Welding/Cutting Robot), when a particular trajectory of its end-effector has been prescribed. The numerical results show that the joint trajectories generated based on the stiffness optimization are feasible for realization in the control system since they are acceptably smooth. The results imply that the stiffness performance of the robot machine deviates smoothly with respect to the kinematic configuration in the adjacent domain of its best stiffness performance. To suppress the vibration of the robot machine due to varying cutting force during the machining process, this dissertation proposed a feedforward control strategy, which is constructed based on the derived inverse dynamics model of target system. The effectiveness of applying such a feedforward control in the vibration suppression has been validated in a parallel manipulator in the software environment. The experimental study of such a feedforward control has also been included in the dissertation. The difficulties of modelling the actual system due to the unknown components in its dynamics is noticed. As a solution, a back propagation (BP) neural network is proposed for identification of the unknown components of the dynamics model of the target system. To train such a BP neural network, a modified Levenberg-Marquardt algorithm that can utilize an experimental input-output data set of the entire dynamic system is introduced in the dissertation. Validation of the BP neural network and the modified Levenberg- Marquardt algorithm is done, respectively, by a sinusoidal output approximation, a second order system parameters estimation, and a friction model estimation of a parallel manipulator, which represent three different application aspects of this method.