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.

Cathodic stripping voltammetric determination of ceftazidime in urine at a hanging mercury drop electrode

A method was developed for the differential-pulse cathodic stripping voltammetric determination of ceftazidime with a hanging mercury drop electrode using its reduction peak at -0.43 V in Britton-Robinson buffer pH 4.0. The optimum accumulation potential and time were -0.15 V and up to 60 s, respectively. Linear calibration graphs were obtained from 1 x 10(-8) M and 1.5 x 10(-7) M. The limit of determination was calculated to be 5 x 10(-9) M. The coefficient of variation was 4% (n = 7) at 1 x 10(-7) M ceftazidime. The effect of various components of urine on the voltammetric response was studied, and creatinine, uric acid, urea, and glucose were shown to interfere in the method. Ceftazidime bound to human albumin gives a unique stripping peak at -0.48 V. Recoveries of 87% +/- 2% of the ceftazidime (n = 5) were obtained from urine spiked with 1.27 mu g ml(-1) using C-18 solid phase extraction cartridges. (C) 1997 Academic Press.

Cathodic stripping voltammetric detection and determination at a hanging mercury-drop electrode of dye contaminants in purified biomaterials: study of the human serum albumin and reactive dye 120 system

Procion red HE-3B (RR120) is an example of dye currently used in affinity purification. A method is described for determining trace amounts of RR120 dye contaminant in human serum albumin by cathodic stripping voltammetry. The method is based on a measure of a well-defined peak at -0.58 V, obtained when samples of HSA protein (0.01-2% w/v) containing dye concentrations are submitted to a heating time of 330 min at 80degreesC in NaOH, pH 12.0 and the samples are removed to a solution containing Britton-Robinson buffer, pH 4.0. Using an optimum accumulation potential and tune of 0 V and 240 s, respectively, linear calibration curves were obtained from 1.0 X 10(-9) to 1.0 X 10(-8) mol 1(-1) for RR120 dye. Leakage/hydrolysis of reactive red 120 from an agarose support (e.g. at pH 2 or 12) can also be conveniently determined at very low levels (sub-mug ml(-1)) by means of cathodic stripping voltammetry, which involves adsorptive accumulation of the dye onto the hanging mercury-drop electrode. (C) 2002 Elsevier B.V. B.V. All rights reserved.

DEVELOPMENT OF A CHEMICALLY MODIFIED ELECTRODE BASED ON CARBON PASTE AND FUNCTIONALIZED SILICA-GEL FOR PRECONCENTRATION AND VOLTAMMETRIC DETERMINATION OF MERCURY(II)

A mercury-sensitive chemically modified electrode (CME) based on modified silica gel-containing carbon paste was developed. The functional group attached to the silica gel surface was 3-(2-thiobenzimidazolyl)propyl, which is able to complex mercury ions. This electrode was applied to the determination of mercury(II) ions in aqueous solution. The mercury was chemically preconcentrated on the CME prior to voltammetric determination by anodic stripping in the differential-pulse mode. A calibration graph covering the concentration range from 0.08 to 2 mg l-1 was constructed. The precision for six determinations of 0.122 and 0.312 mg l-1 Hg(II) was 3.2 and 2.9% (relative standard deviation), respectively. The detection limit for a 5-min preconcentration period was 0.013 mg l-1. A study for foreign ions was also made.

Cathodic stripping voltammetric determination of ceftazidime with reactive accumulation at a poly-L-lysine modified hanging mercury drop electrode

Ceftazidime is hydrolysed only slowly at pH 10 at room temperature. This is indicated by a small cathodic stripping voltammetric peak obtained at pH 10 at a hanging mercury drop electrode at about -0.6 V which corresponds to the reduction of the hydrolysis product. This peak is enhanced more than tenfold by the addition of poly-L-lysine (PLL) to the electrolyte solution. The optimum accumulation potential is between 0 and -0.1 V: the size of the peak decreases steadily, however, as the accumulation potential is moved to more negative potentials and is about one-sixth the size for accumulation at -0.4 V. Existing knowledge of the organic chemistry of cephalosporins indicates that the accumulation must involve an aminolysis reaction of the unprotonated PLL with the beta-lactam ring of the ceftazidime. The limit of detection (3 sigma) in standard solutions was calculated to be 1 x 10(-10) mol l(-1). The detection limit in buffer solution containing 1% of urine was calculated to be 5 x 10(-9) mol l(-1), i.e. 5 x 10(-6) mol l(-1) in the urine. (C) 1999 Elsevier B.V. B.V. AU 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.

Aspects of cathodic stripping voltammetry at the hanging mercury drop electrode and in non-mercury disposable sensors

Cathodic stripping voltammetry (CSV) and accumulation at the hanging mercury drop electrode are reviewed briefly. Proposals in a recent IUPAC technical report are considered. Three recent developments in CSV are discussed: the adaptation of CSV methods developed for use with the hanging mercury drop electrode for use with screen-printed carbon electrodes in disposable sensors, the use of reactive accumulation, and the chemometric use of kinetic methods of determination with pulse methods in CSV.

Preconcentration and determination of mercury(II) at a chemically modified electrode containing 3-(2-thioimidazolyl)propyl silica gel

A mercury-sensitive chemically modified graphite paste electrode was constructed by incorporating modified silica gel into a conventional graphite paste electrode. The functional group attached to the (3-chloropropyl) silica gel surface was 2-mercaptoimidazole, giving a new product denoted by 3-(2-thioimidazolyl)propyl silica gel, which is able to complex mercury ions. Mercury was chemically adsorbed on the modified graphite paste electrode containing 3-(2-thioimidazolyl)propyl silica (TIPSG GPE) by immersion in a Hg(II) solution, and the resultant surface was characterized by cyclic and differential pulse anodic stripping voltammetry. One cathodic peak at 0.1 V and other anodic peak at 0.34 V were observed on scanning the potential from -0.1 to 0.8 V (0.01 M KNO3; ν = 2.0 mV s-1 νs. Ag/AgCl). The anodic peak at 0.34 V show an excellent sensitivity for Hg(II) ions in the presence of several foreign ions. A calibration graph covering the concentration range from 0.02 to 2 mg L-1 was obtained. The detection limit was estimated to be 5 μg L-1. The precision for six determinations of 0.05 and 0.26 mg L-1 Hg(II) was 3.0 and 2.5% (relative standard deviation), respectively. The method can be used to determine the concentration of mercury(II) in natural waters contaminated by this metal. 2005 © The Japan Society for Analytical Chemistry.

Voltammetry of mercury (II) based on an organo-clay modified graphite electrode

Organo-clay complex of ligand-hexadecyltrimethylammonium with montmorillonite was made for the purpose of application as a preconcentration agent in a chemically modified carbon paste electrode for determination of mercury (II) in aqueous solution. It was found out that the adsorption of Hg(II) by organo-clay complex is independent of the pH of the solution. It was also found out that the adsorption of the remaining metals Cd(II), Ps(II), Cu(II), Zn(II), and Ni(II) was dependent on the changes in pH solutions and increased when it varies from 1 to 8. The resultant material was characterized by cyclic and differential pulse anodic voltammetry using a modified graphite paste electrode in different supporting electrolytes. The mercury response was evaluated with respect to pH, electrode composition, preconcentration time, mercury concentration, possible interferences and other variables.

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)

Preparation of a clay-modified carbon paste electrode based on 2-thiazoline-2-thiol-hexadecylammonium sorption for the sensitive determination of mercury

A montmorillonite from Wyoming-USA was used to prepare an organo-clay complex, named 2-thiazoline-2-thiol-hexadecyltrimethylammonium-clay (TZT-HDTA-clay), for the purpose of the selective adsorption of the heavy metals ions and possible use as a chemically modified carbon paste electrode (CMCPE). Adsorption isotherms of Hg 2+, Pb 2+, Cd 2+, Cu 2+, and Zn 2+ from aqueous solutions as a function of the pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The organo-clay complex was very selective to Hg(II) in aqueous solution in which other metals and ions were also present. The accumulation voltammetry of Hg(II) was studied at a carbon paste electrode chemically modified with this material. The mercury response was evaluated with respect to the pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. A carbon paste electrode modified by TZT-HDTA-clay showed two peaks: one cathodic peak at about 0.0 V and an anodic peak at 0.25 V, scanning the potential from -0.2 to 0.8 V (0.05 M KNO 3 vs. Ag/AgCl). The anodic peak at 0.25 V presents excellent selectivity for Hg(II) ions in the presence of foreign ions. The detection limit was estimated as 0.1 μg L -1. The precision of determination was satisfactory for the respective concentration level. 2005 © The Japan Society for Analytical Chemistry.

Screen-printed electrode based electrochemical detector coupled with ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction for determination of mercury in water samples

A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid–liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbamate is extracted from sample solution into the water-immiscible IL formed in-situ. Then, an ultrasound-assisted procedure is employed to back-extract the mercury into 10 µL of a 4 M HCl aqueous solution, which is finally analyzed using SPCnAuEs. Sample preparation methodology was optimized using a multivariate optimization strategy. Under optimized conditions, a linear range between 0.5 and 10 µg L−1 was obtained with a correlation coefficient of 0.997 for six calibration points. The limit of detection obtained was 0.2 µg L−1, which is lower than the threshold value established by the Environmental Protection Agency and European Union (i.e., 2 µg L−1 and 1 µg L−1, respectively). The repeatability of the proposed method was evaluated at two different spiking levels (3 and 10 µg L−1) and a coefficient of variation of 13% was obtained in both cases. The performance of the proposed methodology was evaluated in real-world water samples including tap water, bottled water, river water and industrial wastewater. Relative recoveries between 95% and 108% were obtained.

Mercury selective electrochemical sensor based on a double armed crown ether as ionophore

PVC based membranes of a double armed crown ether, N, N'-dibenzyl, 1,4,10,13-tetraoxa-7, 16-diaza cyclooctadecane (I) as ionophore with sodium tetra phenyl borate (NaTPB) as anion excluder and with many plasticizing solvent mediators have been prepared and used for Hg(II) ion determination. The membrane with DBBP (dibutyl butyl phosphonate ) as plasticizer with various ingredients in the ratio PVC: I: NaTPB: DBBP (150: 12: 2: 100) shows the best results in terms of working concentration range (3.1x10-5-1.0x10-tM) with a Nernstian slope (29.0′0.5 mV/decade of activity). The electrode works in the pH range 2.1-4.5. The response time of the sensor is 15s and it can be used for about 4 months in aqueous as well as in non-aqueous medium. It has good stability and reproducibility. The potentiometric selectivity coefficient values for mono-, di-, and trivalent cations are tabulated. The sensor is highly selective for Hg2+ in the presence of normal interferents like cadmium, silver, sodium and iron.