Thin mercury film electrodes in dynamic speciation studies of metals

No presente trabalho, foi avaliado o desempenho e a aplicabilidade do eléctrodo de filme fino de mercúrio, em estudos de especiação dinâmica de metais vestigiais. Para tal, foram utilizadas duas técnicas electroanalíticas de redissolução: a clássica Voltametria de Redissolução Anódica (ASV) e a recentemente desenvolvida, Cronopotenciometria de Redissolução com varrimento do potencial de deposição (SSCP). As propriedades de troca-iónica e de transporte de massa de películas mistas preparadas a partir de dois polímeros com características distintas, o Nafion (NA) e o 4-Poliestireno sulfonato de sódio (PSS), foram avaliadas, antes da sua aplicação no âmbito da especiação de metais. Estas películas de NA-PSS demonstraram uma elevada sensibilidade, reprodutibilidade, estabilidade mecânica, bem como, propriedades de anti-bloqueio adequadas na modificação química do eléctrodo de filme fino de mercúrio (TMFE) e, na sua aplicação na determinação de catiões metálicos vestigiais em amostras complexas, por ASV. Para além disso, o desempenho de membranas do polielectrólito PSS em estudos de voltametria de troca-iónica (IEV) foi estudado. O objectivo desta investigação foi reunir as condições ideais na preparação de películas de PSS estáveis e com uma densidade de carga negativa elevada, de modo a aumentar a acumulação electrostática de catiões metálicos no filme polimérico e por conseguinte, conseguir incrementos no sinal voltamétrico. O desempenho e aplicabilidade do TMFE em estudos de especiação de metais vestigiais foram extendidos à SSCP como técnica analítica. Dada a elevada sensibilidade e resolução evidenciada pelo TMFE, este revelou ser uma alternativa adequada aos eléctrodos de mercúrio convencionais, podendo ser utilizado durante um dia de trabalho, sem degradação aparente do sinal analítico de SCP. As curvas de SSCP obtidas experimentalmente utilizando o TMFE estavam em concordância com aquelas previstas pela teoria. Para além disso, a constante de estabilidade (K) calculada a partir do desvio do potencial de meia-onda, para dois sistemas metal-complexo lábeis, aproxima-se não só do valor teórico, como também daquele obtido utilizando o eléctrodo de mercúrio de gota suspensa (HMDE). Adicionalmente, o critério experimental de labilidade inerente a esta técnica foi validado e o grau de labilidade para um dado sistema metal-complexo foi determinado, utilizando o filme fino de mercúrio depositado sob um eléctrodo rotativo (TMF-RDE). Este eléctrodo é muito útil na determinação de parâmetros cinéticos, como é o caso da constante de velocidade de associação (ka), uma vez que as condições hidrodinâmicas, durante a etapa de deposição, se encontram bem definidas.

Adsorptive stripping voltammetric determination of venlafaxine in urine with a mercury film microelectrode

An adsorptive stripping voltammetric procedure for the determination of the antidepressant venlafaxine in urine using a mercury film microelectrode wasdeveloped. The method is based on controlled adsorptive accumulation of the drug at the potential of 1.00V (vs. Ag/AgCl) in the presence of 1.25 x10 -2 molL- 1 borate buffer (pH 8.7). Urine samples were analyzed directly after performing a ten-fold dilution with the supporting electrolyte but without other pretreatment. The limit of detection obtained for a 30 s collection time was 0.693x 10- 6 mol L -1. Recovery experimentsgave good results at the 10 -6 mol L- 1 level (bias less 5% were obtained).

Determination of lead in the absence of supporting electrolyte using carbon fiber ultramicroelectrode without mercury film

The determination of lead ions directly in water, for application in analysis of samples of environmental interest, was studied by electroanalytical techniques. Linear sweep anodic stripping voltammetry with a carbon fiber disk ultramicroelectrode (7.0 mu m in diameter), without mercury film, has been used for lead determination, by standard addition, in purified water in the absence of supporting electrolyte. The response was linear in the range from 10.0 to 50.0 mu g L-1, with a detection limit of 0.8 mu g L-1, for 300 s preconcentration time, at -1.2 V and 1.0 V s(-1) scan rate. The reliability of the analytical procedure was evaluated by precision using relative standard deviations (5.6%, for three repetitive stripping current measurements of solution with 10.0 mu g L-1 lead ions) and by the accuracy with recovery experiments (mean of 110.8%) for the same concentration.

Determination of sulfur compounds in gasoline using mercury film electrode by square wave voltammetry

A sensitive method based on square wave voltammetry is described for the quantitative determination of elemental sulfur, disulfide and mercaptan in gasoline using a mercury film electrode. These sulfur compounds can be quantified by direct dissolution of gasoline in a supporting electrolyte followed by subsequent voltammetric measurement. The supporting electrolyte is 1.4 mol L-1 sodium acetate and No acetic acid in methanol. Chemical and optimum operational conditions for the formation of the mercury film were analyzed in this study. The values obtained were a 4.3 mu m thickness for the mercury film, a 1000 rpm rotation frequency, -0.9 V applied potential and 600 s depositing time. Voltammetric measurements were obtained using square wave voltammetry with detection limits of the 3.0 x 10(-9), 1.6 x 10(-7) and 4.9 x 10(-7) mol L-1 for elemental sulfur, disulfide and mercaptan, respectively. (C) 2007 Elsevier Ltd. All rights reserved.

Simultaneous determination of zinc, copper, lead, and cadmium in fuel ethanol by anodic stripping voltammetry using a glassy carbon-mercury-film electrode

A new, versatile, and simple method for quantitative analysis of zinc, copper, lead, and cadmium in fuel ethanol by anodic stripping voltammetry is described. These metals can be quantified by direct dissolution of fuel ethanol in water and subsequent voltammetric measurement after the accumulation step. A maximum limit of 20% (v/v) ethanol in water solution was obtained for voltammetric measurements without loss of sensitivity for metal species. Chemical and operational optimum conditions were analyzed in this study; the values obtained were pH 2.9, a 4.7-mum thickness mercury film, a 1,000-rpm rotation frequency of the working electrode, and a 600-s pre-concentration time. Voltammetric measurements were obtained using linear scan (LSV), differential pulse (DPV), and square wave (SWV) modes and detection limits were in the range 10(-9)-10(-8) mol L-1 for these metal species. The proposed method was compared with a traditional analytical technique, flame atomic absorption spectrometry (FAAS), for quantification of these metal species in commercial fuel ethanol samples.

Determination of Mg (II) in biodiesel by adsorptive stripping voltammetry at a mercury film electrode in the presence of sodium thiopentone

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Direct simultaneous determination of Pb(II) and Cu(II) in biodiesel by anodic stripping voltammetry at a mercury-film electrode using microemulsions

A mercury film electrode was used to determine direct and simultaneously Pb(II) (at -410 mV) and Cu(II) (at -100 mV) in biodiesel by anodic stripping voltammetry. A linear response was obtained for Pb(II) and Cu(II) in the 2.00 × 10-8-1.00 × 10-7 mol L-1 concentration range and detection limits were 2.91 × 10-9 mol L-1 and 4.69 × 10-9 mol L-1 for Pb(II) and Cu(II), respectively, with recovery around of 100.0%. © 2012 Elsevier Ltd. All rights reserved.

Simple, Direct and Simultaneous Stripping Voltammetric Determination of Lead and Copper in Gasoline Using an In Situ Mercury Film Electrode

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Measurement of aqueous film thickness between charged mercury and mica surfaces : a direct experimental probe of the Poisson-Boltzmann distribution

A stable aqueous electrolyte film is formed between a mercury drop and a flat mica surface due to electrical double-layer repulsion when a negative potential is applied to the mercury. Film thickness has been measured as a function of applied potential while keeping the film pressure constant. By making measurements in this way, it is possible to map the data directly according to the Poisson-Boltzmann equation. An excellent fit to the data is obtained, providing direct evidence for this classical equation and its use as the basis of the Gouy-Chapman model of the diffuse double layer in electrolyte solutions.

Nafion-graphene nanocomposite film as enhanced sensing platform for ultrasensitive determination of cadmium

In this work, an ultrasensitive platform for the detection of cadmium (Cd2+) combining the nafion-graphene nanocomposite film with differential pulse anodic stripping voltammetry (DPASV) analysis was presented. It is found that this sensing platform exhibits enhanced response to the determination of the Cd2+ and has been used to determine the Cd2+ in real sample with good recovery.

POLYANILINE-DISPERSED MERCURY-ELECTRODE FOR THE DETECTION OF MONOCHLORAMINE AND DICHLORAMINE

A novel type of electrochemical detector based on a polyaniline-dispersed mercury-coated glassy carbon chemically modified electrode was investigated for the detection of monochloramine and dichloramine. A polyaniline dispersed-mercury modified electrode, which was prepared by coating polyaniline on a thin mercury film electrode using fast-sweep voltammetry, was developed. The selectivity could be altered using various counter ions incorporated into the polymer. The results indicated that the use of a conducting polymer-based electrochemical sensor for the selective determination of chloramine is a feasible approach.

Electrodeposited thin mercury films on Pt-Ir alloy electrodes

Mercury thin films prepared by electrochemical deposition on Pt-Ir alloy and after partial removing of mercury at different temperatures were studied by means of an interferometric surface mapping microscope and by X-ray photoelectronic spectroscopy. Mercury film samples having mercury partially removed by anodic stripping at a potential more positive than the corresponding peak in the voltammogram were also studied using the same techniques. For blank samples the surface topographic studies showed well defined grain boundaries. Mercury film samples when heated up to different temperatures showed as material is removed and that the surface roughness decreases as the temperature increases. For samples heated up to 800 degrees C the surface roughness is approximately the same that for the blank. A model for the interphase of volumetric mercury electrodeposited on a Pt-Ir alloy has been proposed using samples both electrochemically and thermally removed of their Hg coatings. The model includes a layered three-region structure, containing at least two Pt-Hg intermetallics: PtHg4 and PtHg2. A substrate modified region, iridium rich, has also been detected. (C) 1999 Elsevier B.V. S.A. All rights reserved.

Solid-state reactions of mercury with pure noble metals - Part 2. Mercury-iridium system

Thermogravimetry, cyclic voltammetry and other analytical techniques were used to study the reactions of mercury with pure iridium. The results allowed to suggest when subjected to heat or anodic stripping voltammetry an electrodeposited mercury film reacts with Ir substrate and at least three mass loss steps and three peaks appear in the mercury desorption process. The first two were attributed to Hg(0) species removal like a mercury bulk and a mercury monolayer. The last can be ascribed to the mercury removal from a solid solution with iridium.

Scanned stripping chronopotentiometry at bismuth film rotating disc electrodes: a method for quantitative dynamic metal speciation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Stripping voltammetric determination of Pb(II) and Cd(II) based on the multiwalled carbon nanotubes-Nafion-bismuth modified glassy carbon electrodes

In this work, a new method for the simultaneous determination of Pb(II) and Cd(II) on the multiwalled carbon nanotubes (MWNT)-Nafion-bismuth modified glassy carbon electrode (GCE) using square-wave anodic stripping voltammetry has been studied. Scanning electron microscopy was used to investigate the characteristics of the MWNT-Nafion-bismuth modified GCE.