Flow injection analysis (FIA) is a continuous flow technique developed in the early 1970's. FIA is based on reproducible sample injection, accurate timing and controlled dispersion. This technique is very versatile due to the control of the variables and can easily be automated. This technique is very suitable for routine laboratory analysis. By introducing various sample modifying techniques in tandem with the FIA system, samples can easily be modified. Some modifying techniques are analyte pre-concentration, sample dilution and sample cleanup. Passive dialysis can be used very successfully for sample dilution and cleanup. Problems arise when samples with low analyte concentration have to be analysed. For this reason an electrodialyser unit, equipped with a passive membrane, was developed. The history, development and theory of membranes and membrane processes are discussed. A study of the movement of ions, in solution and across a passive membrane, under the influence of an applied d.c. electrical potential is given. Passive membranes were evaluated for use in the proposed system. The following factors influencing the efficiency of electrodialysis in the F1 system were studies. The flow rate of the donor and acceptor channels; the applied d.c. electrical potential; injection loop volumes; flow direction in the electrodialyser unit. An investigation was done into on-line analyte pre-concentration and regulated dilution probabilities of the electrodialysis system. Systems that were evaluated are the following: The determination of chloride in water effluents; the determination of copper and zinc in pharmaceuticals; the direct and indirect determination of phosphate in fertilizers. A comparative study between the advantages and disadvantages of the passive dialysis and electrodialysis system is given. / Thesis (PhD (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

A derivatization reaction, based on a copulation reaction of diazonium salt of an analyte with a reagent (1-aminonaphthalene or NEDA) producing colour, spectrophotometrically detectable product, has been used for determination of two analytes (procain hydrochloride, sulfamethoxazole) containing amino group in the molecule. The conditions of batch spectrophotometric determination were studied. It was found, that the batch determination is applicable only for procain hydrochloride analysis, because sulfamethoxazole gives time-unstable colour product. FIA arrangement was proposed and effects of selected parameters were optimized using two levels factorial design. The calibration dependences were measured for both analysis with both reagents, and subsequently were applied on determination of analytes in medical forms. Key words: diazotization, flow injection analysis, procaine, spectrophotometry, sulfamethoxazole

The electrochemical oxidation of CoCl2(PPh3)2 was investigated in a mixture of acetonitrile and pentanol (1:1) at a platinum disk working electrode using Cyclic Voltammetry (CV) and Chronoamperometry. Elemental Analysis and Infrared Spectroscopy were used to characterise the synthesized compounds i.e. CoCl2(PPh3)2 and CoCl(PPh3)3. Cyclic Voltammetry was utilised for the examination of different working electrode materials that could be used for the anodic voltammetric studies of CoCl2 (PPh3)2, to characterise the reactants and products of each electrode reaction, to investigate the chloride binding ability to a CoCl(PPh3)3 complex, and to evaluate the electrocatalytic substitution of chloride by PPh3 from the complex CoCl2(PPh3)2. Use of ferrocene as an internal standard during the anodic studies of CoCl2(PPh3)2 was also evaluated. The number of electron involved in the electrode process, CoII to CoIII from CoCl2(PPh3)2 and diffusion coefficient of ferrocene in a mixture of acetonitrile and pentanol (1:1) were determined using Chronoamperometry. Ultraviolet-Visible (UV-Vis) and 31P Nuclear Magnetic Resonance (31P NMR) spectra were used to assist with the characterisation of the electrode reactions involved during oxidation of CoCl2(PPh3)2. / Dissertation (MSc (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted

A three-dimensional CFD program was used to predict the flow field that would enter a downstream fan or compressor rotor under the influence of an upstream thermal distortion. Two distortion generation techniques were implemented in the model; (1) a thermal source and (2) a heated flow injection method. Results from the investigation indicate that both total pressure and velocity boundary conditions at the compressor face are made non-uniform by the upstream thermal distortion, while static pressure remains nearly constant. Total pressure at the compressor face was found to vary on the order of 10%, while velocity varies from 50-65%. Therefore, in modeling such flows, neither of these latter two boundary conditions can be assumed constant under these conditions. The computational model results for the two distortion generation techniques were compared to one another and evaluations of the physical practicality of the thermal distortion generation methods are presented. Both thermal distortion methods create total temperature distortion magnitudes at the compressor face that may affect rotor blade vibration. Both analyses show that holding static pressure constant is an appropriate boundary condition for flow modeling at the compressor inlet. The analyses indicate that in addition to the introduction of a thermal distortion, there is a potential to generate distortion in total pressure, Mach number, and velocity. Depending on the method of thermally distorting the inlet flow, the flow entering the compressor face may be significantly non-uniform. The compressor face boundary condition results are compared to the assumptions of a previous analysis (Kenyon et al., 2004) in which a 25 R total temperature distortion was applied to a computational fluid dynamics (CFD) model of a fan geometry to obtain unsteady blade pressure loading. Results from the present CFD analyses predict similar total temperature distortion magnitudes corresponding to the total temperature variation used in the Kenyon analyses. However, the results indicate that the total pressure and circumferential velocity boundary conditions assumed uniform in the Kenyon analyses could vary by the order of 2% in total pressure and approximately 8% in velocity distortion. This supports the previously stated finding that assuming a uniform total pressure profile at the compressor inlet may be an appropriate approximation with the presence of a weak thermal distortion, while assuming a constant circumferential velocity boundary condition is likely not sufficiently accurate for any thermal distortion. In this work, the referenced Kenyon investigation and others related to the investigation of distortion-induced aeromechanical effects in this compressor rotor have assumed no aerodynamic coupling between the duct flow and the rotor. A full computational model incorporating the interaction between the duct flow and the fan rotor would serve to alleviate the need for assuming boundary conditions at the compressor inlet. / Master of Science

No description available.

No description available.

O presente trabalho apresenta estudos da reação de autoxidação de Ni(II)/tetraglicina ou Cu(II)/tetraglicina induzida por S(IV). Estudos espectrofotométricos enfocaram a formação do respectivo íon metálico no estado de oxidação 3+. Verificou-se que S(IV) acelera a autoxidação de Ni(II)/tetraglicina em pH=9,2 (tampão borato), com a determinação de alguns parâmetros cinéticos desta reação. A autoxidação de Cu(II)/tetraglicina induzida por S(IV), caracterizada por efeito sinérgico positivo de Ni(II), foi empregada no desenvolvimento de método analítico para S(IV) na faixa de (0-0,12) milimolar. Este método foi utilizado para estudo da autoxidação de S(IV) catalisada por traços de íons metálicos de transição, em meio não-complexante. Estudos por quimiluminescência abordaram a interação das espécies geradas na autoxidação de Ni(II)/tetraglicina e Cu(II)/tetraglicina induzida por S(IV) com o íon tris-bipiridil-2,2´-rutênio(II). Foi avaliado o efeito de intensificação da radiação emitida, causado por tensoativos ou adições sucessivas de S(IV). A interação das espécies produzidas na autoxidação de Ni(II)/tetraglicina induzida por S(IV) com luminol foi aproveitada para desenvolvimento de método quimiluminescente para determinação de sulfito. O método proposto foi aplicado para determinação de S(IV) livre em amostras de bebidas, açúcar e água de chuva (limite de detecção 0,28 nanomolar). / The current work shows studies concerning the sulfite induced Ni(II)/tetraglycine (NiIIG4) and Cu(II)/tetraglycine (CuIIG4) autoxidation reaction in aqueous medium. Spectrophotometric studies focused on the formation of the correspondent metallic ion in the 3+ oxidation state. It was found that S(IV) accelerates NiIIG4 autoxidation at pH = 9.2 (borate buffer). Some kinetic parameters of this reaction have been successfully determined. S(IV) induced CuIIG4 autoxidation, which is characterized by the remarkable positive synergistic effect of Ni(II), was used in the development of a S(IV) analytical method in the range of (0-12)x10-5 mol L-1. This method was used to study the S(IV) catalyzed autoxidation of metallic transition ions, in non-complexing medium. Chemiluminescence studies approached the interaction between Ru(II)/bipy (tris-bipyridil-2,2´-ruthenium(II) ion) and the species generated in the S(IV) induced NiIIG4 autoxidation. The emitted radiation intensifying effect, which is caused by the presence of certain surfactants or consecutive additions of S(IV), was evaluated. The interaction between the species generated in the S(IV) induced NiIIG4 autoxidation and luminol was used in the development of a sulfite determination method by chemiluminescence. A flow system containing a gas-diffusion unit was used to separate S(IV) from the matrix. Free sulfite was determined in beverages, sugar and rainwater samples, with a detection limit of 2,8 x 10-8 mol L-1.

Procedimentos analíticos baseados em medidas de quimiluminescência caracterizam-se por apresentar alta sensibilidade, baixos limites de detecção, ampla faixa de resposta linear e instrumentação simples. Uma das principais dificuldades relacionadas a este tipo de medida é maximizar a quantidade de radiação detectada, já que a emissão ocorre em todas as direções, o que dificulta o posicionamento adequado da cela de medida em relação ao sistema de detecção. Uma alternativa consiste na utilização de guias de ondas, que são dispositivos que conduzem a radiação emitida, minimizando perdas durante o transporte, tal como ocorre nos cabos de fibras ópticas. O acoplamento de sistemas de análises em fluxo com detecção por quimiluminescência é bastante conveniente, já que a mistura entre amostras a reagentes precisa ser rápida e altamente reprodutível, além de ser realizada a uma distância muito pequena do sistema de detecção, devido ao curto tempo de vida dos intermediários no estado excitado. Neste trabalho, é apresentada a avaliação de uma cela constituída por um guia de ondas para medidas de quimiluminescência. Estas ferramentas foram aplicadas à determinação de hipoclorito em amostras de líquido de Dakin por quimiluminescência empregando a reação de oxidação do luminol por hipoclorito. Também foi desenvolvido um procedimento analítico para a determinação de salbutamol, explorando a inibição da quimiluminescência da reação de oxidação de luminol por hipoclorito, caracterizando-se como uma alternativa promissora para a quantificação do fármaco. Em ambas as aplicações, os resultados foram concordantes com os obtidos por procedimentos de referência a nível de confiança de 95% / Analytical procedures based on chemiluminescence are characterized by high sensitivity, low detection limits, wide linear response ranges and simple instrumentation. One of the main troubles is to increase the amount of detected radiation, because emission occurs in all directions, making difficulty the positioning of the measurement cell in relation to the detection system. An alternative consists in the use of liquid-core waveguides, devices that constrain the emitted radiation, minimizing losses during the transport, in a similar way to optical fibers. Coupling flow analysis to chemiluminescence is attractive, because sample and reagents mixing needs to be fast, highly reproducible and accomplished close to the detector, in view of the short lifetime of the intermediates in the excited state. In this work, a cell constituted by a liquid-core waveguide was evaluated for chemiluminescence measurements. These tools were applied to the determination of hypochlorite in Dakin solution samples by chemiluminescence exploiting the oxidation of luminol by hypochlorite. An analytical procedure for salbutamol determination, exploiting the inhibition of chemiluminescence of luminol oxidation by hypochlorite, was developed, characterizing as a promising alternative for the quantification of this pharmaceutical substance. In both applications, results were in agreement to those obtained by reference procedures at the 95% confidence level

Polímeros molecularmente impressos (MIPs) se afiguram como materiais promissores a serem empregados em extração em fase sólida devido à boa seletividade apresentada por eles. A seletividade dos MIPs está diretamente relacionada ao reconhecimento pelo polímero de uma molécula de interesse, a qual foi empregada previamente como molde no processo de sua síntese. MIPs apresentam como características o fácil preparo, o baixo custo, a possibilidade de síntese em ambientes adversos, e a resistência química na presença de ácidos, bases, íons metálicos, solventes orgânicos bem como resistência física a altas temperaturas e pressões. Neste trabalho, a exploração de MIPs como extratores para separação em fase sólida (SPE) em sistemas de análises em fluxo foi realizada, sendo suas características e desempenho avaliados em relação às determinações espectrofotométricas de catecol, ácico ascórbico e atrazina em amostras de relevãncia ambiental, farmacológica e alimentícia. A possibilidade de separação quiral foi também investigada em relação D e L-ácido ascórbico. Potencialidades e limitações quanto ao emprego dos mesmos em sistemas de análises em fluxo foram observadas e enfatizadas / Molecularly imprinted polymers (MIPs) are promising as material to be used in solid phase extractions due to their high selectivity. MIPs selectivity is directly related to the recognition of a molecule of interest, which was previously employed as template in the synthesis process. The main favorable characteristics of MIPs are the easy preparation, low cost, possibility of synthesis in adverse environments, and chemical resistance in the presence of acids, bases, metal ions, organic solvents as well as the physical resistance to high temperatures and pressures. In the present work, flow systems with molecularly imprinted polymers as in-line solid phase extractors were designed, and their characteristics and efficiencies were assessed in relation to the spectrophotometric determinations of the catechol, ascorbic acid and atrazine in environmental, pharmacological and food samples. Moreover, the feasibility of chiral separation was investigated in relation to D and L-ascorbic acid. Potentialities and limitations of implementing MIPs in flow analysis were highlighted

"Neste trabalho, propõe-se o desenvolvimento de instrumentação e procedimentos analíticos automáticos para a determinação de tensoativos em águas empregando o conceito de multicomutação em fluxo. Visando a miniaturização do sistema, a minimização do consumo de reagentes, e da geração de efluentes foram utilizadas mini-bombas solenóide para a propulsão dos fluidos e válvulas solenóide de estrangulamento para controlar a manipulação das soluções. Estes dispositivos foram controlados por um microcomputador equipado com uma interface eletrônica baseada no circuito integrado ULN2803A a qual foi acoplada à saída da impressora. Como sistema de detecção foram empregados um espectrofotômetro HP8452A, um espectrofotômetro multicanal com arranjo linear de fotodetectores do tipo CCD e um fotômetro baseado em dois LEDs (azul e vermelho) como fonte de radiação e um fotodiodo de silício (IPL10530DAL) como detector. A aquisição dos dados do fotômetro foi realizada com um multímetro digital com saída serial RS232, empregando um programa escrito em linguagem VISUAL BASIC 3.0. No mesmo programa foram incluídas rotinas para controle do módulo de análise. Primeiramente, foram desenvolvidos a instrumentação e os procedimentos analíticos para a determinação independente de tensoativos aniônicos e catiônicos em águas. O mesmo módulo de análises foi utilizado para os dois tensoativos e foi constituído de quatro mini-bombas solenóide. O procedimento proposto para a determinação de tensoativos aniônicos foi baseado na substituição do reagente cromogênico alaranjado de metila (MO) pelo tensoativo aniônico dodecilbenzeno sulfonato de sódio (DBS), formando o par-iônico com o tensoativo catiônico cloreto de cetilpiridino (CPC) em pH 5,0. A instrumentação proposta possibilitou a obtenção de resposta linear entre 1,4 x 10-6 mol L-1 e 1,4 x 10-5 mol L-1 (0,5 - 5 mg L-1) (R = 0,997, n = 7), limite de detecção de 9,8 x 10-8 mol L-1 (0,034 mg L-1), e freqüência de amostragem de 60 determinações por hora. O desvio padrão relativo foi estimado em 0,8 % (n = 11) usando uma solução de referência contendo 5,7 x 10-6 mol L-1 (2 mg L-1) de DBS. Os resultados obtidos pelo método proposto processando amostras de efluentes domésticos e industriais foram comparados com os obtidos empregando-se o método de referência, e não foi observada diferença significativa em nível de confiança de 95 %. Para a determinação de tensoativos catiônicos em águas foi desenvolvido um procedimento baseado na formação do complexo ternário entre tensoativo catiônico CPC, Fe (III) e cromazurol S (CAS) em pH 4,5. Com o sistema proposto, utilizando-se uma cela de detecção de 40 mm de comprimento, obteve-se resposta linear entre 0,1 x 10-5 mol L-1 e 3,0 x 10-5 mol L-1 (0,34 - 10,2 mg L-1) (R = 0,999, n = 9), limite de detecção estimado em 1,0 x 10-7 mol L-1 (0,035 mg L-1), desvio padrão relativo de 0,6 % (n = 11) empregando uma solução de referência contendo 1,0 x 10-5 mol L-1 (3,4 mg L-1) de CPC, e freqüência de amostragem de 72 determinações por hora. O procedimento foi aplicado em amostras de águas coletadas no rio Piracicaba. Empregando-se teste de adição e recuperação foi observada recuperação entre 91 % e 106 %. O módulo de análise para a determinação seqüencial de tensoativos aniônicos e catiônicos foi constituído de duas mini-bombas solenóide e seis válvulas solenóide de estrangulamento. Com o sistema proposto, as características analíticas para os tensoativos aniônicos foram: resposta linear entre 0,1 x 10-5 mol L-1 e 3,0 x 10-5 mol L-1 (0,35 - 10,5 mg L-1) (R = 0,9992, n = 7); limite de detecção estimado em 1,6 x 10-7 mol L-1 (0,056 mg L-1); desvio padrão relativo de 0,6 % (n = 11) usando uma solução de referência contendo 1,0 x 10-5 mol L-1 (3,5 mg L-1) de DBS. Para os tensoativos catiônicos obteve-se resposta linear entre 0,1 x 10-5 mol L-1 e 3,0 x 10?5 mol L-1 (0,34 - 10,2 mg L-1) (R = 0,9992, n = 7); limite de detecção estimado em 1,4 x 10-7 mol L-1 (0,05 mg L-1); desvio padrão relativo de 0,5 % (n = 11) usando uma solução de referência contendo 1,0 x 10-5 mol L-1 (3,4 mg L-1) de CPC. O consumo das soluções de reagentes e de amostra foram de 400 mL e 200 mL, respectivamente, e freqüência de amostragem de 60 determinações por hora, para ambos tensoativos. O sistema foi aplicado em amostras de águas coletadas no rio Corumbataí, e os resultados obtidos com testes de adição e recuperação variaram entre 91 % e 105 %. Aplicando-se teste-t entre os resultados obtidos pelo procedimento proposto e pelos métodos de referência (aniônicos) e de validação (catiônicos), os resultados foram concordantes em nível de 95 % de confiança." / "In this work, development of the instrumentation and automatic analytical procedures for spectrophotometric determination of surfactants in waters employing the multicommutation concept were proposed. Aiming to system miniaturization, reduction of reagents consumption and effluents generation, solenoids micro-pump and solenoids pinch valves were used for the fluids propulsion and for solutions management, respectively. These devices were controlled by a microcomputer equipped with an electronic interface based on the integrate circuit ULN2803A that was coupled to the printer output. As system detection was employed an spectrophotometer model HP8452A, a multichannel spectrophotometer with CCD array linear arrangement of photodetectors and a homemade LED based photometer comprising two LEDs (blue and red) as radiation source and a photodiode (IPL10530DAL) as detector. In this case, the data acquisition was accomplished with a digital multimeter with serial out put RS232 employing a software wrote in VISUAL BASIC 3.0. The software comprised also routines to control the analysis module. Firstly, instrumentation and analytical procedures for independent determination of anionic and cationic surfactants in waters were developed. The same flow system comprised of four solenoid micro-pumps and it was employed for both surfactants. The procedure proposed for the determination of anionic surfactant was based on the substitution reaction of orange methyl (MO) by anionic surfactant (sodium dodecylbenzene sulfonate - DBS) to form an ion-pair with the cetyl pyridine (CPC) at pH 5.0. The proposed instrumentation allowed the achievement of a lineal response range between 1.4 x 10-6 mol L-1 and 1.4 x 10-5 mol L-1 (0.5 – 5.0 mg L-1) (R = 0.997, n = 7), a detection limit of 9.8 x 10-8 mol L-1 (0.034 mg L-1), a relative standard deviation of 0.8% (n = 11) for a reference solution containing 5.7 x 10-6 mol L-1 (2.0 mg L-1) DBS and sampling throughput of 60 determinations per hour. Results obtained applying the proposed procedure for domestic and industrial effluent samples were compared with those obtained using reference method and no significant differences at the 95 % confidence level was observed. For the determination of cationic surfactant in waters the procedure was developed based on the ternary complex formation between CPC, Fe (III) and chromazurol S at pH 4.5. The proposed system comprised a flow cell device with 40 mm optical path-length presented the following features: a linear response range between 0.1 x 10-5 mol L-1 e 3.0 x 10-5 mol L-1 (0.34 – 10.2 mg L-1) (R = 0.999, n = 9); a detection limit of 1.0 x 10-7 mol L-1 (0.035 mg L-1); a relative standard deviation of 0.6 % (n = 11) for a reference solution containing 1.0 x 10-5 mol L-1 (3.4 mg L-1) CPC; and a sampling throughput of 72 determinations per hour. The procedure was applied to samples waters collected in the Piracicaba River. Using standard addition test recoveries between 91 % and 106 % were observed. The flow network for the sequential determination of anionic and cationic surfactants comprised two solenoid micro-pumps and six solenoid pinch valves. Employing the system proposed for the determination of anionic surfactants the folowing analytical characteristics: linear response range between 0.1 x 10-5 mol L-1 e 3.0 x 10-5 mol L-1 (0.35 – 10.5 mg L-1) (R = 0.9992, n = 7); a detection limit of 1.6 x 10-7 mol L-1 (0.056 mg L-1); a relative standard deviation of 0.6 % (n = 11) for a reference solution containing 1.0 x 10-5 mol L-1 (3.5 mg L-1) DBS were observed. For cationic surfactants a linear response range between 0.1 x 10-5 mol L-1 e 3.0 x 10?5 mol L-1 (0.34 - 10.2 mg L-1) (R = 0.9992, n = 7), a detection limit of 1.4 x 10-7 mol L-1 (0.05 mg L-1), a relative standard deviation of 0.5 % (n = 11) for a reference solution containing 1.0 x 10-5 mol L-1 (3.4 mg L-1) CPC were observed. In both cases, the reagents and sample consumption were 400 mL and 200 mL, respectively. The sampling throughput of 60 determinations per hour was achieved for both surfactants. The system was applied to waters samples from the Corumbataí River. The results obtained using the standard addition test presented recoveries between 91 % and 105 %. Applying t-test between the results obtained by the proposed procedures and those obtained using reference procedures showed that for anionic and cationic surfactants, the results were concordant at 95% confidence level."