A mercury(II) ion-selective electrode based on N,N-dimethylformamide-salicylacylhydrazone as a neutral carrier.

A new PVC membrane mercury(II) ion electrode based on N,N-dimethylformamide-salicylacylhydrazone (DMFAS) as an ionophore is described, which shows excellent potentiometric response characteristics and displays a linear log[Hg(2+)] versus EMF response over a wide concentration range between 6.2 x 10(-7) and 8.0 x 10(-2) M with a Nerstian slope of 29.6 mV per decade and a detection limit of 5.0 x 10(-7) M. The response time for the electrode is less than 30 s and the electrode can be used for more than 2 months with less than a 2 mV observed divergence in a potentials. The proposed electrode exhibits very good selectivity for mercury(II) ions over many cations in a wide pH range (pH 1 - 4). The electrode was also applied to the determination of a mercury(II) ion in vegetables and in Azolla filiculoides.     

Extraction of mercury(II) from aqueous thiocyanate solutions with 5-(4-pyridyl)nonane in benzene, and its subsequent atomic-absorption spectrometric determination

Tracer ( approximately 10(-8)M) mercury(II) can be quantitatively extracted with 5-(4-pyridyl)nonane in benzene from aqueous thiocyanate solutions that are up to 6M in HCl, 1M in H(2)SO(4) or 0.25M in HNO(3), in a single extraction. Optimal conditions for the extraction are given, based on a critical study of the relevant factors such as the effects of the acids, thiocyanate, salting-out and complexing agents and the reagent concentration. The mechanism underlying these extractions is discussed on the basis of the results obtained from partition and slope-analysis data. The extraction of the metal as Hg(PyN)(2)(SCN)(2) is indicated. The extracted mercury can be stripped from the non-aqueous layer with various aqueous solutions, including nitric acid (2M), sodium citrate ( 1M) and sodium thiosulphate (0.1 M). Common salts do not depress the extraction. Distribution coefficients and separation factors of several elements relative to mercury(II) are reported for media that contain the optimal concentrations of the mineral acids and are in 0.2M in potassium thiocyanate. The data have been applied for the determination of mercury in soil and water samples by atomic-absorption spectrometry.     

Differential pulse anodic stripping voltammetry of lead (lI) benzoylacetonate in chloroform: Application to the analysis of free-lead gasoline and gas oil samples

The voltammetric characteristics of lead(II) benzoylacetonate in chloroform at the mercury electrode are investigated. The conditions for nearly reversible reduction of lead(II) were optimized. Anodic stripping voltammetry for the determination of trace-lead was developed using differential pulse technique to strip amalgamed lead from hanging mercury drop electrode. The experimental conditions, such as scanning rate of electrode potential and deposition time of lead were optimized. The calibration graph was linear over concentration range 5x10(-8)-10(-6) M of lead(II). The detection limit was 2.5x10(-9) and the relative standard deviation for the determination of 4x10(-7) M Pb(II) was 2%. Preceded by decomposition of organolead compounds with concentrated nitric acid, then ashing at 300 degrees C and a solvent extraction of Pb(II) benzoylacetonate in chloroform, the suitability of the proposed method for the determination of lead in free-lead gasoline and gas oil was demonstrated as a typical example of application.     

A rapid spectrophotometric method for determination of zinc in milk

1-(2',3'-Dihydroxypyridyl-4'-azo)benzene-4-sulphonic acid and the corresponding 5'-chloro-substituted acid are proposed as sensitive reagents for zinc. Cyanide masking and selective demasking of zinc can be used to deal with the interference of many metal ions, cadmium can be masked with semithiocarbazide, and thiosulphate can be used for masking Hg(II), Pd(II) and Os(VIII). The molar absorptivities are about 1.3 x 10(5) 1.mole(-1).cm(-1). The method has been used for determinating zinc in milk.     

Spectrophotometric determination of mercury in soils with triphenyltetrazolium chloride

The formation of the acidocomplex of mercury(II) with triphenyl-tetrazolium chloride is studied spectrophotometrically in water-organic media. The composition of the complex is established as TTC:Hg:I = 1:1:1. The molar absorptivity (255) = (6.45 +/- 0.12) x 10(4) 1 mole(-1). cm(-1) is determined. The selectivity of the reaction is studied and the method for determination of mercury(II) 0.1-0.8 mug/ml is shown. Extraction investigations of the system discussed were carried out. The characteristic values for the extraction equilibrium and the equilibrium in the aqueous phase was determined: extraction constant K(ex) = 3.16 x 10(4), distribution constant K(D) = 20.67, and association constant = 1.53 x 10(3). 5 A rapid and sensitive extractive-photometric method for determination of mercury(II) in soil was developed. The determination was carried out without preliminary elimination of mercury.     

Kinetics and mechanism of mercury(II)-catalysed replacement of cyanide in hexacyanoferrate(II) by p-nitrosodiphenylamine

The mercury(II)-catalysed replacement of cyanide in hexacyanoferrate(II) by p-nitrosodiphenylamine (p-NDA) in aqueous solution has been investigated spectrophotometrically by measuring the change in absorbance of the green complex ion, [Fe(CN)(5).p-NDA](3-), at 640 nm. Activation parameters of the catalysed and uncatalysed reactions have been calculated. The effects of the dielectric constant and water content of the medium on reaction rates are used to explain the formation of a polar activated complex and suggest an I(d) mechanism for the catalysed reaction. The varying catalytic activity of Hg(II) as a function of concentration has been discussed.     

Flow-injection successive determination of cysteine and cystine in pharmaceutical preparations

A flow-injection configuration is proposed for the individual determination of cysteine and cystine and for the mixtures of both analytes. The procedure is based on the inhibitory effect of cysteine on the oxidation of thiamine to thiochrome by mercury(II). Linear calibration graphs were obtained between 1.0 x 10(-5) and 1.0 x 10(-4)M, with a sampling rate of 22 samples/hr and relative standard deviation of 1.14%. The inclusion of a selecting valve in the configuration, to pump water or hydroxylamine, allows the successive determination of these two analytes. The applicability of the method to the determination of cysteine and cystine in pharmaceutical preparations was demonstrated by investigating the effect of potential interferences and by the analysis of commercial preparations.     

Flotation-spectrophotometric determination of mercury in water samples using iodide and ferroin.

This paper describes a simple and highly selective method for separation, preconcentration and spectrophotometric determination of trace amounts of mercury. The method is based on the flotation of an ion-associate of HgI4(2-) and ferroin between aqueous and n-heptane interface at pH 5. The ion-associate was then separated and dissolved in acetonitrile to measure its absorbance. Quantitative flotation of the ion-associate was achieved when the volume of the water sample containing Hg(II) was varied over 50 - 800 ml. Beer's law was obeyed over the concentration range of 3.2 x 10(-8) - 9.5 x 10(-7) mol l(-1) with an apparent molar absorptivity of 1 x 10(6) l mol(-1) cm(-1) for a 500 ml aliquot of the water sample. The detection limit (n = 25) was 6.2 x 10(-9) mol l(-1), and the RSD (n = 5) for 3.19 x 10(-7) mol l(-1) of Hg(II) was 1.9%. A notable advantage of the method is that the determination of Hg(II) is free from the interference of the almost all cations and anions found in the environmental and waste water samples. The determination of Hg(II) in tap, synthetic waste, and seawater samples was carried out by the present method and a well-established method of extraction with dithizone. The results were satisfactorily comparable so that the applicability of the proposed method was confirmed in encountering with real samples.     

Voltammetric study of the redox behaviour of the Hg(II)/Hg(I)/Hg system at a rotating metal-ring/glassy-carbon disc electrode

The reduction of Hg(II) at a glassy-carbon electrode in various electrolytes has been studied by rotating ring-disc voltammetry. Reduction proceeds directly to metallic mercury in a single 2-electron step. However, at the foot of the wave, and only during the first reduction sweep after pretreatment of the electrode surface, a small amount of Hg(I) species is detected at the ring. The appearance of an Hg(I) intermediate is most pronounced in sulphuric acid solution. The reduction of Hg(II) is found to proceed irreversibly and to be of first order. At sufficiently negative potentials the reduction is convective-diffusion controlled. Stripping voltammetric experiments indicate that the dissolution of mercury gives Hg(II) in complexing electrolytes. In non-complexing electrolytes the initially formed Hg(II) reacts with mercury atoms on the electrode surface to give Hg(I). During electrodissolution, two stripping peaks may be observed as a result of underpotential adsorption of mercury on glassy carbon. The difference in peak potential between the adsorption (mono) layer peak and the bulk mercury peak has been related to the difference in work functions of the deposit (mercury) and substrate (carbon). A rotating glassy-carbon electrode has been used for the anodic stripping determination of mercury. When an appropriate amount of a cation such as cadmium(II) or copper(II) is added to the test solution, mercury down to 2 x 10(-9)M (0.4 ng ml ) can be determined in acidified thiocyanate electrolyte with a relative standard deviation of about 22%.     

Applications of enzyme-catalysed reactions in trace analysis--I. Determination of mercury and silver by their inhibition of invertase

Procedures are described for the accurate determination of silver (2-10 x 10(-7)M) and mercury(II) (2-10 x 10(-7)M) in the presence of each other and of most other metals. The methods are based on the inhibition by these metals of invertase catalysis of the hydrolysis of sucrose.     

Flow-injection determination of ascorbic acid and cysteine simultaneously with spectrofluorometric detection.

A simple and sensitive spectrofluorometric method was developed for the simultaneous determination of ascorbic acid and cysteine by a flow-injection system. This method is based on the reduction of Tl(III) with ascorbic acid or cysteine in acidic media, producing fluorescence reagent, TlCl3(2-) (lambdaex = 227 nm, lambdaem = 419 nm). The injected sample solution was divided into two separate streams. The first stream was treated with Tl(III) at pH 3.0 and then passed through a 270 cm reaction coil to the flow cell of the spectrofluorometer, where the fluorescence intensity was measured. This signal is related to ascorbic acid and cysteine concentration. The second part of the injected sample solution was treated with Tl(III) in HCl solution and then passed through a 50 cm reaction coil to the flow cell and the fluorescence intensity was measured. This signal is related only to cysteine. Thus, the ascorbic acid content was determined directly by the difference according to the calibration curve. Ascorbic acid and cysteine can be determined in the range of 1 x 10(-6) to 5.0 x 10(-5) M, at a rate of 16 samples per hour. The limits of detection (S/N = 3) were 8 x 10(-7) M for ascorbic acid and 7 x 10(-7) M for cysteine. The influence of potential interfering substances was studied. The proposed method was successfully applied to the simultaneous determination of both analytes in real samples.     

Anodic stripping voltammetric determination of mercury by use of a sodium montmorillonite-modified carbon-paste electrode

A sodium montmorillonite (SWy-2)-modified carbon-paste electrode has been examined for determination of trace levels of mercury. Because of its strong cation-exchange and adsorptive characteristics, SWy-2 greatly improves the sensitivity of determination of Hg(2+). Hg(2+) is preconcentrated and reduced on the modified electrode surface at -0.40 V and then stripped from the electrode surface during the positive potential sweep. The conditions used for determination, e.g. supporting electrolyte, pH, amount of SWy-2, accumulation potential, and accumulation time, were optimized. The peak current was linearly dependent on the concentration of mercury from 1 x 10(-9) to 5 x 10(-7) mol L(-1). The detection limit (signal-to-noise ratio=3) was 1 x 10(-10) mol L(-1) after accumulation for 6 min. When the SWy-2-modified carbon-paste electrode was used to detect mercury in water samples the average recovery was 101.11%.     

A simple spectrophotometric determination of trace level mercury using 1,5-diphenylthiocarbazone solubilized in micelle.

A very simple, ultra-sensitive and fairly selective non-extractive spectrophotmetric method is presented for the rapid determination of mercury(II) at ultra-trace level using 1,5-diphenylthiocarbazone (dithizone) as a new micellar spectrophotometric reagent (lambdamax = 490 nm) in a slightly acidic (0.07 - 0.17 M H2SO4) aqueous solution. The presence of a micellar system avoids the previous steps of solvent extraction and reduces the cost, toxicity while enhancing the sensitivity, selectivity and the molar absorptivity. The reaction is instantaneous and the absorbance remains stable for over 24 h. The average molar absorption coefficient and Sandell's sensitivity were found to be 5.02 x 10(4) L mol(-1) cm(-1) and 10 ng cm(-2) of Hg, respectively. Linear calibration graphs were obtained for 0.05 - 10 mg L(-1) of Hg; the stoichiometric composition of the chelate is 1:2 (Hg:dithizone). The method is characterized by a detection limit of 1 microg L(-1) of Hg. Large excesses of over 60 cations, anions and complexing agents (e.g. EDTA, tartrate, oxalate, citrate, phosphate, thiourea, azide, SCN-) do not interfere in the determination. The method was successfully applied to a number of environmental water samples (potable and polluted), biological samples (human blood and urine; milk and fish) and soils; solutions contained both mercury(I) and mercury(II) as well as complex synthetic mixtures. The method has high precision and accuracy (s = +/-0.01 for 0.1 mg L(-1)).     

Coated-wire silver ion-selective electrode based on silver complex of cyclam.

A coated-wire ion-selective electrode (ISE) based on cyclam (1,4,8,11-tetraazacyclotetradecane) as a neutral carrier in a polyvinyl chloride (PVC) matrix was fabricated for the determination of Ag(I) ions. The coated-wire ISE exhibited a linear Nernstian response over the range 1 x 10(-1) to 1 x 10(-7) M with a slope of 59 +/- 2 mV per decade change and a detection limit of 5 x 10(-8) M. The ISE shows a greater preference for Ag over other cations with good precision. The electrode was selective towards Ag(I) ions in the presence of 13 different metal ions tested. The selectivity coefficients (K(ij)) were determined for Na(I), K(I), Mg(II), Ca(II), Ba(II), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II) and Hg(II). The selectivity coefficients of these cations are in the range of 10(-4) to 10(-2). This ISE was used for the determination of free silver and total silver in electroplating bath solutions, additives and brighteners.     

Spectrophotometric study of the mercury(II)-Xylenol Orange chelate

The reaction between mercury(II) and Xylenol Orange has been studied in aqueous hexamine medium. The chelate is 1:1 and has an apparent stability constant of 2.4 (+/-0.6) x 10(6) at pH 7 (2.9 M hexamine). Beer's law is obeyed over the concentration range 0.5-2.0 x 10(-5)M mercury(II) when the hexamine concentration is 2.9 M.     

Application of reverse pulse polarography to the determination of substances which form films electrochemically on the mercury electrode

The application of reverse pulse polarography to the determination of substances which form films electrochemically on the mercury electrode is illustrated with penicillamine and cysteine. The dependence of the peak current on several variables is reported and compared with theoretical predictions. It is shown that under optimal instrumental conditions (long drop times and short effective pulses) reverse pulse polarography compares favourably with both normal pulse polarography and differential pulse polarography for the determination of penicillamine and cysteine, concentrations of penicillanline as low as 5 x 10(-8)M being readily determined in the presence of copper(II).     

Catalytic effect of some inorganic ligands on a ligand substitution reaction involving mercury(II) and its application as a differential kinetic method of analysis

To design a sensitive and selective kinetic method for determining a catalyst, the kinetics of the ligand substitution reaction between the mercury(II)-4-(2-pyridylazo)resorcinol complex and 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid together with the catalytic effect of some inorganic ligands on this reaction were studied. The rate constant for a catalyzed reaction path was found to be linearly correlated with the electron donor constant of the catalyst. From this correlation, the difference in reactivity between sulfite or thiosulfate and sulfate was established. Under the selected conditions, sulfite up to 1.5 x 10(-6) M and thiosulfate up to 7 x 10(-7) M could be determined with detection limits of 3 x 10(-8) and 2 x 10(-8) M in the presence of 10 000 and 25 000-fold molar amounts of sulfate, respectively. The tolerance level in the determination of 1 x 10(-6) M of sulfite and 4 x 10(-7) M of thiosulfate was studied for 15 inorganic anions and 44 metal ions.     

Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 nanostructured silica in the simultaneous determination of divalent lead, copper and mercury ions

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol in the simultaneous determination of Pb(II), Cu(II) and Hg(II) ions in natural water and sugar cane spirit (cacha?a) is described. Pb(II), Cu(II) and Hg(II) were pre-concentrated on the surface of the modified electrode by complexing with 2-benzothiazolethiol and reduced at a negative potential (-0.80 V). Then the reduced products were oxidised by DPASV procedure. The fact that three stripping peaks appeared on the voltammograms at the potentials of -0.48 V (Pb2+), -0.03 V (Cu2+) and +0.36 V (Hg2+) in relation to the SCE, demonstrates the possibility of simultaneous determination of Pb2+, Cu2+ and Hg2+. The best results were obtained under the following optimised conditions: 100 mV pulse amplitude, 3 min accumulation time, 25 mV s(-1) scan rate in phosphate solution pH 3.0. Using such parameters, calibration graphs were linear in the concentration ranges of 3.00-70.0 x 10(-7) mol L(-1) (Pb2+), 8.00-100.0 x 10(-7) mol L(-1) (Cu2+) and 2.00-10.0 x 10(-6) mol L(-1) (Hg2+). Detection limits of 4.0 x 10(-8) mol L(-1) (Pb2+), 2.0 x 10(-7) mol L(-1) (Cu2+) and 4.0 x 10(-7) mol L(-1) (Hg2+) were obtained at the signal noise ratio (SNR) of 3. The results indicate that this electrode is sensitive and effective for simultaneous determination of Pb2+, Cu2+ and Hg2+ in the analysed samples.     

Differential pulse polarography of cadmium-and lead-urate and adsorptive stripping voltammetric determination of uric acid

The complex formation between uric acid and zinc, cadmium and lead ions has been investigated using differential pulse polarography in 0.01M NaNO(3). It is found that the complexes formed by Cd(II) and Pb(II) ions with uric acid have the stoichiometry of 1:2 and the logarithmic values of the apparent stability constant are 9.47 and 11.7, respectively. On the other hand, zinc(II) ions do not give any indication of complexation with uric acid. A sensitive voltammetric method is developed for the quantitative determination of uric acid. This method is based on controlled adsorptive preconcentration of uric acid on the hanging mercury drop electrode (HMDE), followed by tracing the voltammogram in the cathodic going potential scan. The modes used are direct current stripping voltammetry (DCSV) and differential pulse stripping voltammetry (DPSV). The detection limits found were 8 x 10(-9)M (quiescent period 15 sec) by DPSV and 1.6 x 10(-8)M by DCSV.     

A simple and rapid flow injection chemiluminescence determination of cysteine with Ru(phen)3(2+)-Ce(IV) system

A new chemiluminescence system was developed for the determination of cysteine by flow injection system. This method is based on the reaction of L-cysteine with Ru(phen)3(2+) and Ce(IV) to produce chemiluminescence. The calibration curve was linear over the range 8.0x10(-7) to 4.0x10(-5) and 4.0x10(-5) to 1.0x10(-3) M with a detection limit of 7.0x10(-7) M (S/N=3). The relative standard deviation of 4.0x10(-6) M cysteine was found 3.5% (n=10). The influence of potential interfering substances was studied. The proposed method was successfully applied for the flow injection determination of cysteine in the real samples with minimum sampling rate of 90 sample/h.