Comparabilidade energética entre sistemas de ciclo de 1 andar e de 2 andares

Este trabalho faz uma análise comparativa do desempenho termodinâmico, num mesmo fluído frigorigéneo, de ciclos frigoríficos em diferentes regimes térmicos, de modo a avaliar as vantagens na utilização da compressão em dois andares sobre a compressão em andar único, para as mesmas temperaturas de evaporação e condensação, nos respectivos permutadores de calor. No estudo o escoamento do fluído é considerado sem perdas de carga, as expansões isentálpicas e as compressões isentrópicas. Os vários rendimentos têm valor unitário de modo a não particularizar o resultado. As temperaturas de regime neste trabalho são -40ºC para a evaporação do fluído e de 40ºC para a sua condensação. As temperaturas intermédias estão no intervalo situado entre -20ºC e 8ºC, com intervalos de 1ºC entre si. Os processos alvo de observação são arrefecimento intermédio (intercooler), remoção do título de vapor à pressão intermédia (flash gas removal), e a combinação dos dois num único processo, com a injecção total de fluído, para o mesmo fluído refrigerante, o NH3 Seguidamente foi analisada a opção em cascata para NH. Foram quantificados valores de COP utilizando compressão seca e compressão húmida. 3/NH3 e em dois fluidos, NH3/CO2 Constatou-se que o processo intercooler e flash gas removal em sistema combinado em compressão seca tem desempenho cerca de 15,5% superior ao ciclo de compressão num só andar, e que a compressão húmida tem melhor desempenho do que a compressão seca, nomeadamente o melhor desempenho na compressão húmida é 11,7% superior ao melhor desempenho na compressão seca.

Projecto de entreposto frigorífico a R-744/R-717 para produtos congelados

Pretende-se com este trabalho de Projecto de Mestrado conceber uma câmara frigorífica de 20000 m3 para armazenar produtos congelados e estudar um sistema frigorífico com dois fluidos frigorigénios que serão o CO2 (R-744) e o NH3 (R-717) O trabalho inicia-se com a definição dos objectivos principais para o projecto de um sistema frigorífico deste tipo. Após a definição dos objectivos, o projecto propõe um estudo termodinâmico do CO2 (R-744) como fluido frigorigénio, definindo se o seu historial de utilização, características principais, diagrama pressão-entalpia com a distinção das diversas fases do fluído, comparação em diversos parâmetros com outros fluidos, o porquê da utilização deste fluído, problemas comuns em sistemas com a presença deste fluído, entre outros parâmetros de estudo. De seguida será feito o dimensionamento de uma câmara frigorífica de 20000 m3 para armazenar produtos congelados paletizados através de um balanço térmico manual e um balanço térmico informático através do programa da Centauro comparando no final o resultado dos dois métodos. Será feito uma descrição das características básicas da câmara frigorífica com um esquema simples do edifício. Será abordado de seguida o sistema frigorífico a CO2 (R-744) e a NH3 (R-717) nas suas diversas características, nomeadamente no cálculo de caudais, diagrama pressão-entalpia, dimensionamento de tubagens e finalmente selecção de equipamento. Procede-se assim também ao estudo um sistema apenas a NH3 (R-717) com as suas diversas características nomeadamente no cálculo de caudais, diagrama pressão-entalpia, dimensionamento de tubagens e finalmente selecção dos equipamentos mais importantes, para que desta forma se proceda à comparação dos dois sistemas a nível energético, consumo eléctrico e manutenção de equipamentos. Finalmente proceder-se-á interpretação de resultados com o objectivo final de escolher a melhor solução nos vários parâmetros de comparação, para o esquema em questão.

Coordination Chemistry of the (eta(6)-p-Cymene)ruthenium(II) Fragment with Bis-, Tris-, andTetrakis(pyrazol-1-yl)borate Ligands: Synthesis, Structural, Electrochemical, and CatalyticDiastereoselective Nitroaldol Reaction Studies

Novel [Ru(eta(6)-p-cymene)(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O complexes (L = bis-, tris-, or tetrakis-pyrazolylborate; X = Cl, N-3, PF6, or CF3SO3) are prepared by treatment of [Ru(eta(6)-p-cymene)Cl-2](2) with poly-(pyrazolyl)borate derivatives [M(L)] (L in general; in detail L = Ph(2)Bp = diphenylbis-(pyrazol-1-yl)borate; L = Tp = hydrotris(pyrazol-1-yl)borate; L = pzTp = tetrakis(pyrazol-1-yl)borate; L = Tp(4Bo) = hydrotris(indazol-1-yl)borate, L = T-p4Bo,T-5Me = (5-methylindazol-1-yl)borate; L = Tp(Bn,4Ph) = hydrotris(3-benzyl-4-phenylpyrazol-1-yl)borate; M = Na, K, or TI) and characterized by analytical and spectral data (IR, ESIMS, H-1 and C-13 NMR). The structures of [Ru(eta(6)-p-cymene)(Ph(2)Bp)Cl] (1) and [Ru(eta(6)-p-cymene)(Tp)Cl] (3) have been established by single-crystal X-ray diffraction analysis. Electrochemical studies allowed comparing the electron-donor characters of Tp and related ligands and estimating the corresponding values of the Lever E-L ligand parameter. The complexes [Ru(eta(6)-p-cymene)-(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O act as catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehyde and nitroethane to the corresponding beta-nitroalkanol (up to 82% yield, at room temperature) with diastereoselectivity toward the formation of the threo isomer.

Evaluation of intermolecular interactions in thioxanthone derivatives: substituent effect on crystal diversity

A family of 9H-thioxanthen-9-one derivatives and two precursors, 2-[(4-bromophenyl) sulfanyl]-5-nitrobenzoic acid and 2-[(4-aminophenyl) sulfanyl]-5-nitrobenzoic acid, were synthesized and studied in order to assess the role of the different substituent groups in determining the supramolecular motifs. From our results we can conclude that Etter's rules are obeyed: whenever present the -COOH head to head strong hydrogen bonding dimer, R-2(2)(8) synthon, prevails as the dominant interaction. As for -NH2, the best donor when present also follows the expected hierarchy, an NH center dot center dot center dot O(COOH) was formed in the acid precursor (2) and an NH center dot center dot center dot O(C=O) in the thioxanthone (4). The main role played by weaker hydrogen bonds such as CH center dot center dot center dot O, and other intermolecular interactions, pi-pi and Br center dot center dot center dot O, as well as the geometric restraints of packing patterns shows the energetic interplay governing crystal packing. A common feature is the relation between the p-p stacking and the unit cell dimensions. A new synthon notation, R`, introduced in this paper, refers to the possibility of accounting for intra- and intermolecular interactions into recognizable and recurring aggregate patterns.

Nanofiltration for the treatment of coke plant ammoniacal wastewaters

This work addresses the treatment by nanofiltration (NF) of solutions containing NaCN and NH(4)Cl at various pH values. The NF experiments are carried out in a Lab-Unit equipped with NF-270 membranes for model solutions that are surrogates of industrial ammoniacal wastewaters generated in the coke-making processes. The applied pressure is 30 bar. The main objective is the separation of the compounds NaCN and NH(4)Cl and the optimization of this separation as a function of the pH. Membrane performance is highly dependent on solution composition and characteristics, namely on the pH. In fact, the rejection coefficients for the binary model solution containing sodium cyanide are always higher than the rejections coefficients for the ammonium chloride model solution. For ternary solutions (cyanide/ammonium/water) it was observed that for pH values lower than 9 the rejection coefficients to ammonium are well above the ones observed for the cyanides, but for pH values higher than 9.5 there is a drastic decrease in the ammonium rejection coefficients with the increase of the pH. These results take into account the changes that occur in solution, namely, the solute species that are predominant, with the increase of the pH. The fluxes of the model solutions decreased with increased pH. (C) 2010 Elsevier B.V. All rights reserved.

Halogen-bonded tris (2,4-Bis(trichloromethyl)-1,3,5,triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

One-pot template condensation of CCl3C=N with ammonia on a metal source [MnCl2 center dot 4H(2)O, FeCl3 center dot 6H(2)O or Co(CH3COO)(2)center dot 4H(2)O] in DMSO led to the formation of tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) complexes, [M(NH=C(CCl3)NC(CCl3)=-NH}(3)]center dot n(CH3)(2)SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)1, which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1-3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) < 69 (Fe) < 72 (Mn), pm] are related to the corresponding Cl center dot center dot center dot Cl distances [3.178 (3) > 3.155 (2) > 3.133 (1) Al. Compounds 1-3 and the related di(triazapentadienato)-Cu(v) complex [Cu(NH=C(CCl3)NC(CCl3)=NH}2]center dot 2(CH3)(2)SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 x 10(3) after 1 h of low power (10 W) MW irradiation.

Reactivity of bulky tris(Phenylpyrazolyl) methanesulfonate copper(I) complexes towards small unsaturated molecules

Reaction of the tris(3-phenylpyrazolyl)methane sulfonate species (Tpms(Ph))Li with the copper(I) complex [Cu(MeCN)(4)][PF6] affords [Cu(Tpms(Ph))(MeCN)] 1. The latter, upon reaction with equimolar amounts of cyclohexyl-(CyNC) or 2,6-dimethylphenyl (XylNC) isocyanides, or excess CO, furnishes the corresponding Cu(I)complexes [Cu(Tpms(Ph))(CNR)] (R = Cy 2, Xyl 3) or [Cu(Tpms(Ph))(CO)] 4. The ligated isocyanide in 2 or 3 (or the acetonitrile ligand in 1)is displaced by 3-iminoisoindolin-1-one to afford 5, the first copper(I) complex containing an 3-iminoisoindolin-1-one ligand. The ligated acetonitrile in 1 undergoes nucleophilic attack by methylamine to give the amidine complex [Cu(Tpms(Ph)){MeC(NH)NHMe}] 6, whereas only the starting materials were recovered from the attempted corresponding reactions of 2 and 3 with methylamine. Complexes 1 or 6 form the trinuclear hydroxo-copper(II)species [(mu-Cu){Cu(mu-OH) (2)(Tpms(Ph))}(2)] 7 upon air oxidation in moist methanol. In all the complexes the scorpionate ligand facially caps the metal in the N,N,O-coordination mode.

Redox-active cytotoxic diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes: Reduction behaviour and theoretical interpretation

Two series of new diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), formulated as the mononuclear [R2Sn(HL)(2)] (1:2) (a, R=Bu-n and Ph) and the polymeric [R2SnL](n) (1:1) (b, R=Bu-n) compounds, were prepared and fully characterized. Single crystal X-ray diffraction for [(Bu2Sn)-Bu-n{C5H9C(O)NHO}(2)] (3a) discloses the cis geometry and strong intermolecular NH center dot center dot center dot O interactions. The in vitro cytotoxic activities of the complexes were evaluated against HL-60, Bel-7402, BGC-823 and KB human tumour cell lines, the greater activity concerning [(Bu2Sn)-Bu-n(HL)(2)] [HL=C3H5C(O)NHO (1a), C6H11C(O)NHO (4a)] towards BGC-823. The complexes undergo, by cyclic voltammetry and controlled-potential electrolysis, one irreversible overall two-electron cathodic process at a reduction potential that does not appear to correlate with the antitumour activity. The electrochemical behaviour of [R2Sn(C5H9C(O)NHO)(2)] [R=Bu-n (3a), Ph (7a)] was also investigated using density functional theory (DFT) methods, showing that the ultimate complex structure and the mechanism of its formation are R dependent: for the aromatic (R = Ph) complex, the initial reduction step is centred on the phenyl ligands and at the metal, being followed by a second reduction with Sn-O and Sn-C ruptures, whereas for the alkyl (R=Bu-n) complex the first reduction step is centred on one of the hydroxamate ligands and is followed by a second reduction with Sn-O bond cleavages and preservation of the alkyl ligands. In both cases, the final complexes are highly coordinative unsaturated Sn-II species with the cis geometry, features that can be of biological significance.

Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols

A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity.

Selenium in dysphagic patients who underwent endoscopic gastrostomy for long term enteral feeding

Background and aims - Endoscopic gastrostomy (PEG) patients usually present protein-energy malnutrition, but little is known about selenium deficiency. We aimed to assess serum selenium evolution when patients underwent PEG, after 4 and 12 weeks. We also evaluated the evolution of albumin, transferrin and Body Mass Index and the influence of the nature of the underlying disease. Methods - A blood sample was obtained before PEG (T0), after 4 (T1) and 12 (T3) weeks. Selenium was assayed using GFAAS (Furnace Atomic Absorption Spectroscopy). The PEG patients were fed through homemade meals. Patients were studied as a whole and divided into two groups: head and neck cancer (HNC) and neurological dysphagia (ND). Results - We assessed 146 patients (89 males), between 21-95 years old: HNC-56; ND-90. Normal values of selenium in 79% (n=115); low albumin in 77, low transferrin in 94, low values for both serum proteins in 66. Low BMI in 78. Selenium has slow evolution, with most patients still displaying normal Selenium at T3 (82%). Serum protein levels increase from T0 to T3, most patients reaching normal values. The nature of the underlying disease is associated with serum proteins but not with selenium. Conclusions - Low serum selenium is uncommon when PEG is performed, after 4 and 12 weeks of enteral feeding and cannot be related with serum proteins levels or dysphagia cause. Enteral nutrition using customized homemade kitchen meals is satisfactory to prevent or correct Selenium deficiency in the majority of PEG patients.