Reações multicomponentes de Biginelli e de Mannich nas aulas de química orgânica experimental: uma abordagem didática de conceitos da química verde

The introduction of Mannich and Biginelli multicomponent reactions in a practical Organic Chemistry course is presented in this article. Procedures described in the literature were adapted for use under the simple conditions available in undergraduate laboratories and were selected on the basis of Green Chemistry principles and practicality of synthesis. The reactions are easy to carry out and all products are readily isolated as crystalline solids with yields ranging from moderate to high.

Caracterização de resíduo sólido formado em biodiesel de sebo bovino

The nature of the solid residue formed in beef tallow biodiesel from two commercial producers in Brazil was determined by comparative analytical techniques, namely, gas chromatography with flame ionization detector (GC-FID) and thermogravimetry (TG). Pure monopalmitin and monostearin were used as reference standards for both methodologies. Analyses were carried out before and after filtration of the solids formed, which allowed the observation that the formation of precipitate reduced the levels of monoglycerides in the beef tallow biodiesel. The chromatographic and thermogravimetric results confirmed the nature of the residue as saturated monoglycerides, predominantly monostearin and monopalmitin.

Enzyme loading dependence of cellulose hydrolysis of sugarcane bagasse

The enzymatic hydrolysis of steam-pretreated sugarcane bagasse, either delignified or non-delignified, was studied as a function of enzyme loading. Hydrolysis experiments were carried out using five enzyme loadings (2.5 to 20 FPU/g cellulose) and the concentration of solids was 2% for both materials. Alkaline delignification improved cellulose hydrolysis by increasing surface area. For both materials, glucose concentrations increased with enzyme loading. On the other hand, enzyme loadings higher than 15 FPU/g did not result in any increase in the initial rate, since the excess of enzyme adsorbed onto the substrate restricted the diffusion process through the structure.

Uso de materiais recicláveis na determinação gravimétrica de CO2 no ar ambiente e tratamento dos resíduos de laboratório gerados

An alternative system was tested for the determination of CO2 in air using recyclable materials. The results indicate that the proposed system allows for reliable, accurate, robust and efficient collection, comparable to the standard gravimetric method. Laboratory wastes are easily treated using a filtrate that can be discharged into the sewer and solids that can be reused. The proposed system is a simple and low-cost tool that encompasses important aspects of environmental education, which should be part of the education in chemistry of undergraduate students and technicians.

TUNGSTOPHOSPHORIC ACID HETEROGENIZED ONTO NH4ZSM5 AS AN EFFICIENT AND RECYCLABLE CATALYST FOR THE PHOTOCATALYTIC DEGRADATION OF DYES

Materials based on tungstophosphoric acid (TPA) immobilized on NH4ZSM5 zeolite were prepared by wet impregnation of the zeolite matrix with TPA aqueous solutions. Their concentration was varied in order to obtain TPA contents of 5%, 10%, 20%, and 30% w/w in the solid. The materials were characterized by N2 adsorption-desorption isotherms, XRD, FT-IR, 31P MAS-NMR, TGA-DSC, DRS-UV-Vis, and the acidic behavior was studied by potentiometric titration with n-butylamine. The BET surface area (SBET) decreased when the TPA content was raised as a result of zeolite pore blocking. The X-ray diffraction patterns of the solids modified with TPA only presented the characteristic peaks of NH4ZSM5 zeolites, and an additional set of peaks assigned to the presence of (NH4)3PW12O40. According to the Fourier transform infrared and 31P magic angle spinning-nuclear magnetic resonance spectra, the main species present in the samples was the [PW12O40]3- anion, which was partially transformed into the [P2W21O71]6- anion during the synthesis and drying steps. The thermal stability of the NH4ZSM5TPA materials was similar to that of their parent zeolites. Moreover, the samples with the highest TPA content exhibited band gap energy values similar to those reported for TiO2. The immobilization of TPA on NH4ZSM5 zeolite allowed the obtention of catalysts with high photocatalytic activity in the degradation of methyl orange dye (MO) in water, at 25 ºC. These can be reused at least three times without any significant decrease in degree of degradation.

Measurement and Improvement of Wet Paper Web Strength

Various strength properties of paper are measured to tell how well it resists breaks in a paper machine or in printing presses. The most often measured properties are dry tensile strength and dry tear strength. However, in many situations where paper breaks, it is not dry. For example, in web breaks after the wet pressing the dry matter content can be around 45%. Thus, wet-web strength is often a more critical paper property than dry strength. Both wet and dry strength properties of the samples were measured with a L&W tensile tester. Originally this device was not designed for the measurement of the wet web tensile strength, thus a new procedure to handle the wet samples was developed. The method was tested with Pine Kraft (never dried). The effect of different strength additives on the wet-web and dry paper tensile strength was studied. The polymers used in this experiment were aqueous solution of a cationic polyamidoamine-epichlorohydrin resin (PAE), cationic hydrophilised polyisocyanate and cationic polyvinylamine (PVAm). From all three used chemicals only Cationic PAE considerably increased the wet web strength. However it was noticed that at constant solids content all chemicals decreased the wet web tensile strength. So, since all chemicals enhanced solid content it can be concluded that they work as drainage aids, not as wet web strength additives. From all chemicals only PVAm increased the dry strength and two other chemicals even decreased the strength. As chemicals were used in strong diluted forms and were injected into the pulp slurry, not on the surface of the papersheets, changes in samples densities did not happen. Also it has to be noted that all these chemicals are mainly used to improve the wet strength after the drying of the web.

Design of Installation for Transport Measurements

In the present work the aim was to prepare an automatic installation for studies of galvanomagnetic effects in solids and to test it by calibration measurements. As a result required automatic installation was created in this work and test measurements were performed. Created setup automatically provides measurements of the magnetoresistance of the Hall effect with an accuracy of ± 2 µV in the temperature range 2 – 300 K and steady magnetic fields up to 6 T. The test measurements of the glassy carbon samples showed that the setup is reliable, has high sensitivity and is easy to use. The results obtained in the research process are pioneer and will be separately analyzed.

Magnetic, thermal and spectral characterization of 2,6-dimethoxybenzoates of Co(II), Ni(II) and Cu(II)

The complexes of 2,6-dimethoxybenzoic acid anion with ions of Co(II), Ni(II), and Cu(II) have been synthesized as polycrystalline solids, and characterized by elemental analysis, spectroscopy, magnetic studies, and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have following colours: pink for Co(II), green for Ni(II), and blue for Cu(II) compounds. The carboxylate group binds as monodentate, and bidentate bridging and chelating ligands. On heating in air to 1173 K the complexes decompose in four, three or two steps. At first, they dehydrate in one or two steps to anhydrous salts, that next decompose to oxides of the respective metals. The solubility of the investigated dimethoxybenzoates in water at 293 K is of the order of 10-2 mol/dm3. Their magnetic moments were determined in the temperature range of 76-303 K. The results reveal the compounds of Co(II) and Ni(II) to be high-spin complexes and that of Cu(II) to form dimer.

Puulevystä valmistettujen kalusteosien pintakäsittelyn kehittäminen UV-telalinjalla

Diplomityö tehtiin Kidex Oy:lle, joka on Kiteellä sijaitseva Martela-konsernin tytäryhtiö. Kidex Oy toimii sopimusvalmistajana Martelalle sekä muille valituille levykalusteasiakkaille, ja tuotteet ovat pääasiassa toimisto- ja keittiökalusteita. Kevättalvella 2008 yritykseen siirrettiin Nummelasta pintakäsittelyosasto, jolla on tehty petsaus- ja lakkaustöitä. Näiden lisäksi tehtaalla on pohdittu mahdollisuuksia maalaustöihin, jotta UV-telalinjan kapasiteetti saataisiin paremmin käyttöön Työssä selvitettiin, mitä muutoksia UV-kovettuvilla aineilla maalaaminen vaatii linjaan ja luotiin edellytykset maalaustoiminnan aloittamiselle. Muutokset pyrittiin pitämään niin vähäisinä kuin mahdollista. Lisäksi määritettiin maalattavien tuotteiden laadun kriteerit ja todennusmenetelmät, jotka voidaan viestiä asiakkaille väärinkäsitysten välttämiseksi. Laadun todentamista varten valmistettiin sarja koekappaleita, joista mitattiin asiakkaan kannalta tärkeimmät maalikalvon ominaisuudet. Työssä tarkasteltiin myös pintakäsittelylaitoksia koskevaa VOC-asetusta ja verrattiin liuottimien kulutusta asetuksen määrittämiin rajoihin. Puulevystä valmistettujen kalusteosien pintakäsittely UV-telalinjalla eroaa oleellisesti perinteisistä menetelmistä esimerkiksi tuotantonopeuden osalta, joka johtuu pääasiassa pinnoitekalvon hetkessä tapahtuvasta kovettumisesta UV-valon vaikutuksesta. UV-aineet ovat käytännössä täysin kiinteistä aineista koostuvia, eivätkä näin sisällä vaarallisia haihtuvia liuottimia. UV-kovettuvilla tuotteilla maalaaminen on viime vuosina runsaasti tutkittu alue, joka eroaa tietyiltä osin myös pintakäsittelystä UV-kirkaslakoilla. Pigmentoitujen kalvojen kovettuminen vaatii erilaista UV-säteilyä ja levitysmäärien seuranta on huomattavasti tarkempaa.

Magnetic, thermal and spectral characterization of 2,4-dimethoxybenzoates of Mn(II), Co(II) and Cu(II)

2,4 - Dimethoxybenzoates of Mn(II), Co(II) and Cu(II) have been synthesized as hydrated or anyhydrous polycrystalline solids and characterized by elemental analysis, IR spectroscopy, magnetic studies and X-ray diffraction measurements. They possess the following colours: Mn(II) - white, Co(II) - pink and Cu(II) - blue. The carboxylate groups bind as monodentate, or a symmetrical bidentate bridging ligands and tridentate. The thermal stabilities were determined in air at 293-1173K. When heated the hydrated complexes dehydrate to from anhydous salts which are decomposed to the oxides of respective metals. The magnetic susceptibilites of the 2,4-dimethoxybenzoates were measured over the range 76-303 K and their magnetic moments were calculated. The results reveal the complexes of Mn(II), Co(II) to be high-spin complexes and that of Cu(II) to form dimer.

Complexes of 3,4-dimethoxybenzoic acid anion with Cu(II), Co(II), La(III), and Nd(III)

Physico-chemical properties of 3,4-dimethoxybenzoates of Co(II), Cu(II), La(III) and Nd(III) were studied. The complexes were obtained as hydrated or anhydrous polycrystalline solids with a metal ion-ligand mole ratio of 1 : 2 for divalent ions and of 1 : 3 in the case of trivalent cations. Their colours depend on the kind of central ion: pink for Co(II) complex, blue for Cu(II), white for La(III) and violet for Nd(III) complexes. The carboxylate groups in these compounds are monodentate, bidentate bridging or chelating and tridentate ligands. Their thermal decomposition was studied in the range of 293-1173 K. Hydrated complexes lose crystallization water molecules in one step and form anhydrous compounds, that next decompose to the oxides of respective metals. 3,4 - Dimethoxybenzoates of Co(II) is directly decomposed to the appropriate oxide and that of Nd(III) is also ultimately decomposed to its oxide but with the intemediate formation of Nd2O2CO3.. The magnetic moment values of 3,4-dimethoxybenzoates determined in the range of 76-303 K change from 4.22 µB to 4.61 µB for Co(II) complex , from 0.49 µB to 1.17 µB for Cu(II) complex , and from 2.69 µB to 3.15 µB for Nd(III) complex.

The physico-chemical properties of 4-chlorophenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)

The complexes of 4-chlorophenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II) have been synthesized as polycrystalline solids, and characterized by elemental analysis, spectroscopy, magnetic studies and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have the following colours: pink for Co(II), green for Ni(II), blue for Cu(II) and a pale pink for Mn(II) compounds. The carboxylate group binds as monodentate and bidentate ligands. On heating to 1173K in air the complexes decompose in several steps. At first, they dehydrate in one step to anhydrous salts, that next decompose to the oxides of respective metals. Their magnetic moments were determined in the range of 76-303K. The results reveal them to be high-spin complexes of weak ligand fields.

CFD Simulation of Two-phase and Three-phase Flows in Internal-loop Airlift

Airlift reactors are pneumatically agitated reactors that have been widely used in chemical, petrochemical, and bioprocess industries, such as fermentation and wastewater treatment. Computational Fluid Dynamics (CFD) has become more popular approach for design, scale-up and performance evaluation of such reactors. In the present work numerical simulations for internal-loop airlift reactors were performed using the transient Eulerian model with CFD package, ANSYS Fluent 12.1. The turbulence in the liquid phase is described using κ- ε the model. Global hydrodynamic parameters like gas holdup, gas velocity and liquid velocity have been investigated for a range of superficial gas velocities, both with 2D and 3D simulations. Moreover, the study of geometry and scale influence on the reactor have been considered. The results suggest that both, geometry and scale have significant effects on the hydrodynamic parameters, which may have substantial effects on the reactor performance. Grid refinement and time-step size effect have been discussed. Numerical calculations with gas-liquid-solid three-phase flow system have been carried out to investigate the effect of solid loading, solid particle size and solid density on the hydrodynamic characteristics of internal loop airlift reactor with different superficial gas velocities. It was observed that averaged gas holdup is significantly decreased with increasing slurry concentration. Simulations show that the riser gas holdup decreases with increase in solid particle diameter. In addition, it was found that the averaged solid holdup increases in the riser section with the increase of solid density. These produced results reveal that CFD have excellent potential to simulate two-phase and three-phase flow system.

Complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III)

The complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) have been synthesized as polycrystalline hydrated solids, and characterized by elemental analysis, spectroscopy, magnetic studies and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have the following colours: violet for Nd(III), white for Gd(III) and cream for Ho(III) compounds. The carboxylate groups bind as bidentate chelating (Ho) or bridging ligands (Nd, Gd). On heating to 1173K in air the complexes decompose in several steps. At first, they dehydrate in one step to form anhydrous salts, that next decompose to the oxides of respective metals. The gaseous products of their thermal decomposition in nitrogen were also determined and the magnetic susceptibilites were measured over the temperature range of 76-303K and the magnetic moments were calculated. The results show that 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) are high-spin complexes with weak ligand fields. The solubility value in water at 293K for analysed 4-chlorophenoxyacetates is in the order of 10-4mol/dm³.

Assessment of hydrochemical quality of ground water under some urban areas within sana'a secreteriat

Groundwater from nine wells of three different districts, located at Sana'a secretariat was analyzed for hydrochemical quality assessment. Measurements of water quality parameters including pH, EC, CO3(2-), HCO3-, Cl-, NO3-, SO4(2-), Ca2+, Mg2+, Fe3+, K+, and Na+ were carried out . Classification of the groundwater samples according to Cl, SO4(2-), CO3(2-) and HCO3-, hardness (H), total dissolved solids (TDS), base-exchange, and meteoric genesis was demonstrated. Suitability of ground water samples for irrigation and industrial uses according to sodium adsorption ration (SAR), ratio of dissolved sodium (RDS), residual sodium carbonate (RSC) and saturation index (SI) was also investigated. The results of this study showed that almost all ground water samples were of good quality that makes them suitable for drinking and domestic uses. Results also indicated that even though some of the ground water samples were suitable for irrigation purposes, almost all of them were found not be good for industrial uses. Despite all drawbacks of the sewerage system built around Sana'a secretariat at the beginning of the first decade of the third millennium, the results of this study indicate that there is scope of significant improvement in Sana'a secretariat ground water quality.