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No presente trabalho comprova-se o efeito prejudicial do oxalato, utilizado para a separação prévia de cálcio e magnésio, na determinação complexométrica deste último com EDTA em águas, usando-se em titulação visual o indicador Negro de Eriocromo T e, em titulação potenciométrica, o sistema indicador Hg/Hg-EDTA. Comprovou-se, também, a viabilidade de se usar como titulante uma solução de EDTA \"tetraneutralizado\", em titulações potenciométricas com medidas de pH através de eletrodo de vidro combinado. Neste caso o ponto final é obtido através da hidrólise da espécie Y4-, após o ponto de equivalência. Assim evidenciou-se a viabilidade de um novo método para a determinação da mistura de cálcio e magnésio, pelo uso EDTA \"tetraneutralizado\" e separação prévia dos dois cátions através da adição de oxalato. A detecção do ponto final nestas titulações com EDTA \"tetraneutralizado\" pode também ser feita visualmente com fenolftaleína. O efeito de volume em titulações potenciométricas em geral, num certo nível de concentração, foi objeto de análises diversas inclusive por cálculo computacional de curvas derivativas. Comprovou-se que quanto menor o volume do titulado maior é o salto potenciométrico obtido, caracterizando-se o que se denominou de \"paradoxo potenciométrico\", pois uma menor massa de substância pode ser titulada com, teoricamente, o mesmo erro relativo que para uma massa maior de substância. / Alternative method for the complexometric determination of magnesium. Influence of volume on potentiometric titrations. Keywords: Potentiometry, Magnesium, EDTA. Present paper has been found the negative effect of oxalate, used to the previous separation of calcium and magnesium in a complexometric determination of this last with EDTA in waters, using at visual titration Eriochrome black T as indicator and at potentiometric titration the indicator system Hg/Hg-EDTA. It has been found, also, the viability in the use as titrant a \"tetraneutralized\" EDTA solution, in potentiometric titration with measurements of pH with the glass electrode. In this case the end point is obtained on basis of hydrolysis of Y4- species, after the equivalent point. So it has been displayed the viability of a new method to the determination of the mixture calcium and magnesium by the use of \"tetraneutralized\" EDTA and previous separation of both cations by addition of oxalate. The end point detection can be visually found, in these titrations with \"tetraneutralized\" EDTA, by using of phenolphthalein. The effect of volume in potentiometric titration in general, at a defined concentration level, was subject of several analysis incluse using the compute calculation of derivative curves. It has been found that as smaller volume of titrated performes a higher potentiometric jump, this effect was called for us \"potentiometric paradox\", since an smaller weight of substance can be titrated, with theoretically, the same relative error that to a greater weight of substance.

O presente estudo procura dar continuidade a um dos ramos de pesquisa desenvolvidos na área de Analítica do Instituto de Química da USP, onde se procura estudar a química de complexos formados entre diferentes metais e o ânion azoteto, N-3. O cátion índio(III), à semelhança do que ocorre com o ferro (III), complexa com o ânion azoteto em meio aquoso. Este poder de complexação foi constatado em estudos polarográficos do sistema In N3+ / N-3 ora em desenvolvimento. A obtenção das constantes de estabilidade dos complexos formados entre o In3+ e o ligante azoteto, por via potenciométrica, baseia-se na alteração do pH do tampão formado por N-3 e o ácido fraco HN3, quando se adicionam íons In3+. O acompanhamento da variação da concentração hidrogeniônica foi f.eito com o auxílio do eletrodo de vidro combinado. A concentração de N-3 de equilíbrio variou de valores próximos de zero a 90 mM, para que se obtivessem dados na mais larga faixa de concentraç6es de ligante. Manteve-se a força iônica das soluções em 2,00OM (NaCI04) e trabalhou-se a 25,0οC. A análise dos dados experimentais e tratamento matemático dos mesmos, evidenciaram a formação de complexos mononucleares e os valores das constantes globais encontrados foram: β1 = (2,0 ± 0,1) x 103M-1 β2 = (7 ± 3) x 105M-2 β3 = (5 ± 1) x 107M-3 β4 = (7 ± 3) x 108M-4 / The present study is a branch of the main work concerned with the complex formation between several metal cations and azide anion in aqueous media. Indium (III) was selected, in analogy to iron (III), because forms complexes with azide in aqueous media. Polarographic studies in development showed the tendency of these complexation. To determine the stability constants of complexes was used potentiometric method using glass e1ectrode. The main advantage is based on pH modification of the buffer solution constituted by azide and hidrazoic acid (N-3;/HN3) when indium (III) cations are added in the buffer. The azide concentration was a1tered from near zero to 90 mM, the ionic strenght he1d at 2,000 M with sodium perchlorate and the temperature kept constant at 25,0°C. The evaluation of experimental data shawed mononuclear species and the global constants found were: β1 = (2,0 ± 0,1) x 103M-1 β2 = (7 ± 3) x 105M-2 β3 = (5 ± 1) x 107M-3 β4 = (7 ± 3) x 108M-4

1. Abstract Charles University in Prague Faculty of Pharmacy in Hradec Kralove Department of Biophysics and Physical Chemistry Candidate: Miroslav Suchy Supervisor: Ing. Vladimir Kubicek, CSc. Title of Diploma Thesis: Physico-Chemical properties of drugs To test physico-chemical properties of new molecules is necessary during drug development. It could be helpful to understand or predict the pharmacokinetic parametres of a new drug in vivo/in vitro experiments. One of this parameters is a dissociation constant (pK). Dissociation constant is defined as " Number on pH scale, wherein is just fifty percent of molecule in a ionization condition". In real case this number can help us to know where in the gastro-intestinal tract (GIT) the drug will be absorbed. In GIT only molecules exhibiting pK from 3 to 11 could be absorbed. Out of this range it is not possible. In this work I would like to introduce the ways of experimental measurement of pK values. I was working with two methods to measure the pK values of water-soluble compounds. The spectrophotometric method and the potentiometric one. I had to find out, that potentiometric titration is primary method which gets us good and accurate results. Based on my measurement I evaluated the spectrophotometric method as the secondary method. Spectrophotometric method...

Faculty of Science School of Chemistry 0204045a tspmkwi@hotmail.com / New possibilities in collection of polarographic and potentiometric experimental data in studies of metal–ligand systems by automated instrumental methods, and subsequent treatment of the polarographic data, whereby the degree of reversibility of the electrode processes varies, have been investigated in this work. An automated instrumental set–up was developed for applications in studies of metal–ligand solution equilibria by potentiometry and sampled Direct Current Polarography (DCP). The new set–up was designed based on virtual instrumentation principles whereby several commercially– available hardware units as well as custom–built electronic components, were interfaced to a personal computer that was equipped with appropriate hardware and control programs. The instrumental set–up was tested and validated by studying the protonation equilibria of the ligand glycine by Glass Electrode Potentiometry (GEP) as well as the complexation of the ligand glycine with Cd2+ by GEP and DCP. The new set–up provides increased versatility, accuracy and convenience in obtaining large numbers of experimental points in solution equilibria studies by DCP and GEP as opposed to the use of tedious and time–consuming manual methods. Nonlinear curve–fitting procedures, based on closed–form models that were derived here from suitable theoretical equations identified from literature, have been investigated in this work for applications in analysis of DC curves recorded on metal–ligand systems with variation in electrochemical reversibility. The applicability and limitations of the curve–fitting procedures developed have been tested in analysis of the DCP data collected on several metal–ligand systems involving Cd2+, Pb2+, Zn2+ and the ligands glycine and sarcosine, whereby the DCP studies of these systems exhibited reversible, quasi–reversible or irreversible electrochemical processes. Information on applicability and limitations of the proposed methods investigated in this work was derived by comparison of the results obtained from DCP, using the proposed methods, with either reported literature data and/or results obtained in this work by the independent analytical technique of GEP, which was deployed wherever it was found to be applicable to study the metal–ligand systems considered.

A construção de sensor potenciométrico, utilizando Nióbio acoplado a eletrodo de referência de prata/cloreto de prata num mesmo instrumento, possibilita o acompanhamento da variação de potencial que ocorre durante uma reação ácido-base em meio aquoso. Foi utilizado eletrodo de vidro combinado, cuja membrana de vidro foi danificada fisicamente, porém com sua referência interna em pleno funcionamento. O eletrodo de Nióbio foi confeccionado com metal polido ou então com a superfície modificada com óxido eletrodepositado. O crescimento de óxido sobre o Nióbio foi obtido por eletrólise em meio a H3PO4 diluído. O metal ou o par metal/óxido foi fixado no eletrodo de vidro contendo uma solução eletrolítica. O eletrodo de Nióbio não apresenta boa sensibilidade quando utilizado como indicador em potenciometria direta, mas é sensível às variações de potenciais que ocorrem em titulações ácido-base. O eletrodo de Nióbio metálico pode substituir o eletrodo de vidro combinado na determinação do teor de acidez de vinagres. / The construction of potentiometric sensors, using Niobium combined with the reference electrode silver / silver chloride in a single instrument, allows the variation of potential monitoring that occurs during an acid-base reaction in aqueous media. It was used a combined electrode glass, whose glass membrane was damaged physically, but with the internal reference in full operation. The Niobium electrode was made with polished metal or with the surface modified by electrodeposited oxide. The oxide growth was obtained by electrolysis in the H3PO4 diluted media. The metal or metal/oxide was fixed in glass electrode containing a electrolyte solution. The Niobium electrode doesn\'t show sensitivity when used as an indicator in direct potentiometry, but is sensitive to changes of potential that occur in acid-base titrations. The electrode of Niobium metal can replace the glass electrode combined in determining the level of acidity of vinegar.

A construção de sensor potenciométrico, utilizando Nióbio acoplado a eletrodo de referência de prata/cloreto de prata num mesmo instrumento, possibilita o acompanhamento da variação de potencial que ocorre durante uma reação ácido-base em meio aquoso. Foi utilizado eletrodo de vidro combinado, cuja membrana de vidro foi danificada fisicamente, porém com sua referência interna em pleno funcionamento. O eletrodo de Nióbio foi confeccionado com metal polido ou então com a superfície modificada com óxido eletrodepositado. O crescimento de óxido sobre o Nióbio foi obtido por eletrólise em meio a H3PO4 diluído. O metal ou o par metal/óxido foi fixado no eletrodo de vidro contendo uma solução eletrolítica. O eletrodo de Nióbio não apresenta boa sensibilidade quando utilizado como indicador em potenciometria direta, mas é sensível às variações de potenciais que ocorrem em titulações ácido-base. O eletrodo de Nióbio metálico pode substituir o eletrodo de vidro combinado na determinação do teor de acidez de vinagres. / The construction of potentiometric sensors, using Niobium combined with the reference electrode silver / silver chloride in a single instrument, allows the variation of potential monitoring that occurs during an acid-base reaction in aqueous media. It was used a combined electrode glass, whose glass membrane was damaged physically, but with the internal reference in full operation. The Niobium electrode was made with polished metal or with the surface modified by electrodeposited oxide. The oxide growth was obtained by electrolysis in the H3PO4 diluted media. The metal or metal/oxide was fixed in glass electrode containing a electrolyte solution. The Niobium electrode doesn\'t show sensitivity when used as an indicator in direct potentiometry, but is sensitive to changes of potential that occur in acid-base titrations. The electrode of Niobium metal can replace the glass electrode combined in determining the level of acidity of vinegar.