Complexometric titration with potenciometric indicator to determination of calcium and magnesium in soil extracts¹

This study proposes a method of direct and simultaneous determination of the amount of Ca2+ and Mg2+ present in soil extracts using a Calcium Ion-Selective Electrode and by Complexometric Titration (ISE-CT). The results were compared to those obtained by conventional analytical techniques of Complexometric Titration (CT) and Flame Atomic Absorption Spectrometry (FAAS). There were no significant differences in the determination of Ca2+ and Mg2+ in comparison with CT and FAAS, at a 95 % confidence level. Additionally, results of this method were more precise and accurate than of the Interlaboratorial Control (IC).

Predicting the physicochemical profile of diastereoisomeric histidine-containing dipeptides by property space analysis.

OBJECTIVES: This study aimed at measuring the lipophilicity and ionization constants of diastereoisomeric dipeptides, interpreting them in terms of conformational behavior, and developing statistical models to predict them. METHODS: A series of 20 dipeptides of general structure NH(2) -L-X-(L or D)-His-OMe was designed and synthetized. Their experimental ionization constants (pK(1) , pK(2) and pK(3) ) and lipophilicity parameters (log P(N) and log D(7.4) ) were measured by potentiometry. Molecular modeling in three media (vacuum, water, and chloroform) was used to explore and sample their conformational space, and for each stored conformer to calculate their radius of gyration, virtual log P (preferably written as log P(MLP) , meaning obtained by the molecular lipophilicity potential (MLP) method) and polar surface area (PSA). Means and ranges were calculated for these properties, as was their sensitivity (i.e., the ratio between property range and number of rotatable bonds). RESULTS: Marked differences between diastereoisomers were seen in their experimental ionization constants and lipophilicity parameters. These differences are explained by molecular flexibility, configuration-dependent differences in intramolecular interactions, and accessibility of functional groups. Multiple linear equations correlated experimental lipophilicity parameters and ionization constants with PSA range and other calculated parameters. CONCLUSION: This study documents the differences in lipophilicity and ionization constants between diastereoisomeric dipeptides. Such configuration-dependent differences are shown to depend markedly on differences in conformational behavior and to be amenable to multiple linear regression. Chirality 24:566-576, 2012. © 2012 Wiley Periodicals, Inc.

Investigation of defect formation and electronic transport in microcrystalline silicon deposited by hot-wire CVD

We have investigated doped and undoped layers of microcrystalline silicon prepared by hot-wire chemical vapour deposition optically, electrically and by means of transmission electron microscopy. Besides needle-like crystals grown perpendicular to the substrate's surface, all of the layers contained a noncrystalline phase with a volume fraction between 4% and 25%. A high oxygen content of several per cent in the porous phase was detected by electron energy loss spectrometry. Deep-level transient spectroscopy of the crystals suggests that the concentration of electrically active defects is less than 1% of the undoped background concentration of typically 10^17 cm -3. Frequency-dependent measurements of the conductance and capacitance perpendicular to the substrate surface showed that a hopping process takes place within the noncrystalline phase parallel to the conduction in the crystals. The parasitic contribution to the electrical circuit arising from the porous phase is believed to be an important loss mechanism in the output of a pin-structured photovoltaic solar cell deposited by hot-wire CVD.

Utilização de eletrodos potenciométricos de amálgama em estudos de complexação de substâncias húmicas

Potentiometric amalgam electrodes of lead, cadmium, and zinc are proposed to study the complexation properties of commercial and river sediment humic acids. The copper complexation properties of both humic acids were studied in parallel using the solid membrane copper ion-selective electrode (Cu-ISE). The complexing capacity and the averaged conditional stability constants were determined at pH 6.00 ± 0.05 in medium of 2x10-2 mol L-1 sodium nitrate, using the Scatchard method. The lead and cadmium amalgam electrodes presented a Nernstian behavior from 1x10-5 to 1x10-3 moles L-1 of total metal concentration, permitting to perform the complexation studies using humic acid concentrations around of 20 to 30 mg L-1, that avoids colloidal aggregation. The zinc amalgam electrode showed a subnernstian linear response in the same range of metal concentrations. The Scatchard graphs for both humic acids suggested two classes of binding sites for lead and copper and one class of binding site for zinc and cadmium.

Detectores potenciométricos para sistemas de análise por injecção em fluxo, evolução e aplicação

The field of flow injection potentiometry (FIP) is reviewed and its current status assessed. The research development and application of electrodes in flow injection systems are presented and discussed.

Ion-selective electrodes: historical, mechanism of response, selectivity and concept review

This paper presents a review of the concepts involved in the working mechanism of the ion-selective electrodes, searching a historical overview, moreover to describe the new advances in the area.

Determinação potenciométrica em fluxo de cloreto de cetilpiridinio em desinfectantes bucais

The work describes a new procedure for cetylpyridinium chloride determination in oral disinfectants, based on a flow-injection system with potentiometric detection. The determination was based on the measurement of picrate concentration decrease as result of ion-pair reaction with the analyte present in the injected sample. In the optimised set-up the sample injection volume was kept at 400 µL and merged downstream with the reagent solution containing 1,0 x10-5 mol/L of picrate adjusted to pH 5.0 with citrate/citric acid buffer. The flow rate was fixed at 8 mL/min and the reactor length at 40 cm. The proposed procedure enables the determination of cetylpyridinium in the analytical range of 5,0x10-6 - 7,5x10-5 mol/L at a sampling rate of 60/h. The results for real samples had a precision better than 3% and were comparable to the labelled values.

Aplicações eletroanalíticas com eletrodos de prata confeccionados a partir de CDs graváveis

This paper presents a new way for the construction of silver electrodes utilizing recordable CDs. The new electrodes were explored for the quantification of chloride (by potentiometry/FIA), cyanide (by amperometry/FIA) and for lead analysis (by square wave voltammetry). For the flowing measurements, a digital multimeter, connected to a microcomputer (via RS 232 interface) was used to collect directly the potential signal (for Cl- measurements) or to take the output signal from a potentiostat (for CN- measurements). The square wave voltammetry analysis was performed in a commercial instrument. The results shown good performance of the new electrodes and the detection limit (s/n = 3) attained for these three analytes were: 0.2, 50, and 200 µg L-1 for Pb2+, Cl-, and CN- respectively.

Eletrodo íon-seletivo para determinação potenciométrica de alumínio(III) em meio de fluoreto

The construction and analytical evaluation of a coated graphite Al(III) ion-selective electrode, based on the ionic pair formed between the Al(F)n3-n anion and tricaprylylmethylammonium cation (Aliquat 336S) incorporated on a poly(vinylchloride) (PVC) matrix membrane are described. A thin membrane film of this ionic pair and dibutylphthalate (DBPh) in PVC was deposited directly on a cylindric graphite rod (2 cm length x 0.5 cm diameter) attached to the end of a glass tube using epoxy resin. The membrane solution was prepared by dissolving 40% (m/m) of PVC in 10 mL of tetrahydrofuran following addition of 45% (m/m) of DBPh and 15% (m/m) of the ionic pair. The effect of membrane composition, fluoride concentration, and several concomitants as potential interferences on the electrode response were investigated. The aluminium(III) ion-selective electrode showed a linear response ranging from 1.4 x 10-4 to 1.0 x 10-2 mol L-1, a detection limit of 4.0 x 10-5 mol L-1, aslope of -54.3±0.2mV dec-1 and a lifetime of more than 1 year (over 3000 determinations for each membrane). The slope indicates that the ion-selective electrode responds preferentially to the Al(F)4- species. Application of this electrode for the aluminium(III) determination in stomach anti-acid samples is reported.

Emprego do sal di-sódico de edta como padrão no preparo de soluções

The hydrated sodium salt of EDTA, Na2H2Y·2H2O, cannot be used as a primary standard for titrations due to uncertainties in the water content. An alkalimetric titration of the homogenized solid in the presence of a small excess of BaCl2·2H2O allows one to titrate quantitatively the released two hydrogen cations with end-point indication by phenolphthalein or potentiometry. This leads one to calculate the average molar mass of the reagent and its water content, allowing to use it to prepare EDTA standard solutions. One titrated sample led to the formula Na2H2Y·1.876 H2O, and 370.01 g.mol-1 for the average molar mass.

Determinação de ascarel em óleo isolante de transformadores

The contamination level of silicon oil used as insulation liquid in high-voltage transformers by ascarel (PCBs) is above those permitted by the Brazilian law. Thus new techniques able to detect ascarel, with low operational costs, are very attractive. The present work proposes an analysis of the contamination levels of silicon oil using the following techniques: naphthalene anion radical reaction for ascarel dechlorination; and potentiometry with an ion-selective electrode for chloride ion determination. The data obtained with the proposed methodology agree well with those from the official methodology, (method IEC 61619).

Titulações potenciométricas de cátions metálicos tendo como eletrodo indicador o sistema Cu/Cu(II)-EDTA

In potentiometric titrations of metal cations with EDTA the Hg/HgY2- system is usually used to detect the end point. However, the use of mercury has been discouraged in analytical procedures due to its toxicity. In this work the Cu/CuY2- system was used as indicator electrode for potentiometric titrations of some metal cations with EDTA. The solutions of Cu2+, Cd2+, Mn2+, Co2+ and Zn2+ were titrated with Na2EDTA solution in the presence of a small concentration of the CuY2- complex using a copper wire as indicator electrode. The potentiometric titrations with the Cu/CuY2- system showed good correlation when compared with an Hg/HgY2- system.

Determinação potenciométrica da concentração micelar crítica de surfactantes: uma nova aplicação metodológica no ensino de Química

The participation of the students in the planning, execution and discussion of experimental results is important for the valuation of the role of them in the construction of the chemical knowledge implicited in the approach between education and research. This work relates either the construction of selective membrane electrodes for surfactants and its application in the potenciometric determination of the critical micellar concentration of the sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) surfactants. In adition it´s possible to discuss the potenciometric results in matching with the data valued for the tensiometric and condutimetric traditionally used in the physical-chemistry lessons.

Preparo de amostras de combustíveis fósseis por piroidrólise para a determinação de flúor e cloro

Pyrohydrolysis is proposed for fossil fuels sample preparation for further fluorine and chlorine determination. Samples were heated during 10 min at temperatures up to 1000 °C. Water vapor was passed through the reactor and the volatile products were condensed and collected in NH4OH solution. Fluoride was determined by potentiometry using an ion selective electrode (ISE) and Cl by ICP OES and DRC-ICP-MS. The results are in good agreement with certified values and the precision is better than 10% (n = 4). Sample preparation by means of pyrohydrolysis is relatively simple, whereas chlorine and fluorine can be determined at low concentrations.

Controle da qualidade na determinação potenciométrica de sulfetos volatilizáveis por acidificação (SVA) utilizando adições de padrão

This paper presents a quality assurance and quality control protocol in order to ensure the reliability of analytical results for the determination of acid volatile sulfides in environmental samples by potentiometry. The monitoring of the ion selective sensor readings must be realized continually and particularly in this situation where the analyte is susceptible to transformation and volatilization. Potentiometry with the standard addition was presented as a rapid, accurate, precise, feasible as well as a low cost technique. Concentrations of the analyte in the range of 0.49 to 1.02 mg L-1 were tested with percentage recoveries varying from 89 to 113%.