Trace determination of yttrium and some heavy rare-earths by adsorptive stripping voltammetry

The interfacial and redox behaviour of rare-earth chelates with Solochrome Violet RS are exploited for developing a sensitive adsorptive stripping procedure. Yttrium and heavy rare earths such as dysprosium, holmium and ytterbrium can thus be measured at ng ml levels and below, by controlled adsorptive accumulation of the metal chelate at the hanging mercury drop electrode, followed by voltammetric measurement of the surface species. With a 3-min preconcentration time, the detection limit ranges from 5 x 10(-10) to 1.4 x 10(-9)M. The relative standard deviation at the 7 ng ml level ranges from 4 to 7%. A separation method is required to differentiate between the individual rare-earth metals.     

Trace measurements of the antineoplastic agent methotrexate by adsorptive stripping voltammetry

An extremely sensitive voltammetric method is presented for trace measurement of the cancer chemotherapy drug methotrexate. The method is based on controlled adsorptive preconcentration of methotrexate on the hanging mercury-drop electrode, followed by voltammetric determination of the surface species. Cyclic voltammetry was used to explore the interfacial behaviour. The adsorptive stripping response was evaluated with respect to preconcentration time and potential, pH, concentration dependence, stripping mode, possible interferences, and other variables. The detection limit found was 2 x 10(-9)M (5-min preconcentration), the response was linear, and the relative standard deviation (at the 1.6 x 10(-7)M level) 2.2%. Sensitive adsorptive stripping measurements were also obtained by use of a carbon-paste disk electrode. Applicability to urine analysis is illustrated.     

Trace measurements of colchicine by adsorptive stripping voltammetry

A highly sensitive voltammetric method for trace measurements of the alkaloid colchicine is described. The method is based on the controlled adsorptive accumulation of the drug at the hanging mercury drop electrode, followed by voltammetric determination of the surface species. The adsorptive stripping response is evaluated with respect to preconcentration time and potential, solution pH, voltammetric waveform and other variables. With a 10-min preconcentration, a detection limit of 1.3 x 10(-10)M is obtained. The relative standard deviation (at the 1 x 10(-7)M level) is 1.1%. Applicability to urine analysis is illustrated.     

Ultrasensitive and selective measurements of tin by adsorptive stripping voltammetry of the tin-tropolone complex

Trace levels of tin can be determined by voltammetry after controlled adsorptive preconcentration of the tin-tropolone complex on a hanging mercury drop electrode. The resulting adsorptive stripping procedure offers better sensitivity and selectivity than conventional stripping methods for tin. Optimal conditions include 4 x 10(-6)M tropolone in a stirred acetate buffer (pH 4.0), a preconcentration potential of -0.40 V, and differential-pulse stripping. For an 8-min preconcentration period, the detection limit is 2.3 x 10(-10)M (28 ng/l.). Linear calibration plots of i(p)vs. C are obtained at low concentrations, with linear plots of 1/i(p)vs. 1/C at high concentrations. The relative standard deviation (at the 6-mug/1. level) is 2.6%. The response is not affected by the presence of lead, cadmium, indium and thallium, which commonly interfere severely in analogous anodic stripping measurements. Results are reported for river and orange-juice samples.     

Differential pulse anodic stripping voltammetric determination of lead(II) with a 1,4-bis(prop-2'-enyloxy)-9,10-anthraquinone modified carbon paste electrode

A sensitive and selective method for the determination of lead(II) with a 1,4-bis(prop-2'-enyloxy)-9,10-anthraquinone (AQ) modified carbon paste electrode has been developed. The method is based on non-electrolytic preconcentration via complex formation with modifier, followed by an accumulation period with a negative potential (-1.5 V), and then by a proper anodic stripping. The analytical performance was evaluated with respect to the quantity of modifier in the paste, concentration of electrolyte solution, preconcentration time, lead(II) concentration, and other variables. A linear calibration graph was obtained in the concentration range 2.00x10(-9)-1.06x10(-5) M Pb(II) (n=21, r=0.9999) with 30 s preconcentration time. The detection limit was found to be 1x10(-9) M. For eight preconcentration/determination cycles, the differential pulse voltammetric response was reproduced with 5.0 and 3.7% relative standard deviations at 2.00x10(-8) and 2.00x10(-6) M Pb(II), respectively. Rapid and convenient renewal of electrode surface allows the use of a single modified electrode surface in multiple analytical determinations over several weeks. Many coexisting metal ions had little or no effect on the determination of lead(II). The developed method was applied to lead determination in waste waters.     

Stripping voltammetric determination of traces of catechol compounds preceded by adsorptive accumulation of metal complexes

Catechol compounds are quantified by controlled adsorptive accumulation of their metal complexes onto a hanging mercury drop electrode followed by stripping voltammetry. By using tin(IV) as a redox marker for quantifying the surface-bound species, selectivity can be improved relative to conventional oxidative methods; dopamine can be quantified in the presence of ascorbic acid. The method allows measurements of micromolar levels of catechol, dopamine, l-dopa, 3,4-dihydroxyphenylacetic acid and caffeic acid. The adsorptive stripping response is evaluated with respect to preconcentration time and potential, tin(IV) and analyte concentrations, stripping mode, reproducibility and possible interferences. Analogously, solochrome violet RS and dimethylglyoxime can be quantified after accumulation of their iron(III) and nickel(II) complexes, respectively. Detection limits are 7×10^?9 M for solochrome violet RS and 5×10^?8 M for caffeic acid (1- and 5-min preconcentration, respectively).     

Determination of trace thorium using catalytic-adsorptive stripping voltammetry of the thorium-cupferron complex

A sensitive stripping voltammetric procedure for trace measurement of thorium, based on the catalytic-adsorptive peak of the thorium-cupferron complex, is reported. Optimal experimental conditions include the use of 1mM BES buffer solution (pH 5.5), containing 20muM cupferron, an accumulation potential of -0.80 V (vs. Ag/AgCl), and a differential pulse potential scan. The resulting stripping procedure offers improved sensitivity over a previous stripping scheme for thorium. The limit of detection after 5 min preconcentration is 50 ng/l. (2 x 10(-10)M), the response is linear up to 8 x 10(-8)M, and the relative standard deviation at the 2.1 x 10(-8)M level is 4.4%. Possible interferences are evaluated.     

Adsorption voltammetry of the scandium-alizarin red S complex onto a carbon paste electrode

For the first time, a new method is described for the determination of scandium based on the cathodic adsorptive stripping of the scandium-alizarin red S complex onto a carbon paste electrode. The second-order derivative linear scan voltammograms of the complex are recorded by use of model JP-303 polarographic analyzer from 0.0 to -1.0 V (versus SCE). Optimum conditions are found to be: an acetic acid (0.36 mol l(-1))-potassium biphthalate (0.064 mol l(-1)) buffer solution (pH 4.0) containing 2.0x10(-5) mol l(-1) alizarin red S, a preconcentration potential of 0.0 V, a preconcentration time of 60 s, a rest time of 10 s and a scan rate of 100 mV s(-1). The results show that the complex can be adsorbed on the surface of a carbon paste electrode, yielding one peak at -0.58 V, corresponding to the reduction of alizarin red S in the complex at the electrode. The detection limit is found to be 6.0x10(-10) mol l(-1) for 3 min of preconcentration time. The linear range is 1.0x10(-9) to 4.0x10(-7) mol l(-1). Application of the procedure to the determination of scandium in the ore samples gave good results.     

Investigations on adsorption potentiometry-part VIII. Determination of ultratrace copper in food by derivative adsorption chronopotentiometry

An electroanalytical method, based on derivative chronopotentiometry of the copper complex with 4-[(4-diethylamino-2-hydroxyphenyl) azo]-5-hydroxy-naphthalene-2,7-disulphonic acid (Beryllon III) accumulated on the surface of a hanging mercury drop electrode, for determining trace copper in food has been developed. The dependence of the peak height of reduction of the copper complex on the preconcentration time and preconcentration potential are discussed. Optimum experimental conditions include 0.01 M HOAc, 0.01M NaOAc, 1.0 x 10(-6) Beryllon III and a preconcentration potential of 0.10 V (vs. SCE). Under these conditions the detection limit and the linear range are 4 x 10(-11)M and 6 x 10(-11) -4 x 10(-7)M, respectively. The method was applied to samples of digested rice.     

Trace adsorptive voltammetric determination of antimony in hair

A very sensitive electrochemical procedure for trace determination of antimony is described. The complex of antimony with p-dimethyl-aminophenyl-fluorone (p-DMPF) is adsorbed on a hanging mercury drop electrode (HMDE), and the reduction current of the accumulated complex is measured by voltammetry. In linear sweep voltammetry, the reduction potential of the complex is more positive than that of the free dye. The peak height of the complex is proportional to the concentration of antimony in the range of 4.0 x 10(-9) to 4.0 x 10(-7) M, the detection limit is 1.0 x 10(-9) M Sb(III) for a 5 min preconcentration time. The relative standard error for the determination of 8.0 x 10(-8) M Sb(III) is 2.9%.     

Subtractive differential pulse voltammetry following adsorptive accumulation of organic compounds

Subtractive differential pulse voltammetry following adsorptive preconcentration of organic compounds at solid electrodes is described. Different preconcentration periods are used, and the difference between the oxidation (stripping) currents is recorded. Background currents which are independent of the preconcentration period cancel out. Combining the enhanced peak current, due to the preconcentration step, with the background current correction of the subtractive mode, gives improved sensitivity and/or allows the use of shorter preconcentration periods. Chlorpromazine and dopamine have been used as test systems. A detection limit of around 1 x 10(-9)M has been obtained for chlorpromazine with a 10-min preconcentration period. Applicability to clinical samples is illustrated by the determination of chlorpromazine in whole blood and urine.     

Trace measurement of dipyridamole by adsorptive stripping voltammetry

A sensitive adsorptive stripping voltammetric method for trace measurement of dipyridamole in alkaline solution is described. The method is based on the adsorptive accumulation of the drug at the hanging mercury drop electrode, followed by linear sweep voltammetric determination. The response is evaluated with respect to percentage of ethanol, preconcentration time and potential, and concentration of NaOH. The detection limit of 1.0 x 10(-9)M is obtained under optimized conditions with a 5-min preconcentration. Applicability to injection, tablets and urine analysis is illustrated.     

Adsorptive stripping voltammetry of a fentanyl derivative at a mercury electrode

In a supporting electrolyte of NaOH, a pair of cathodic and anodic peaks of N,N'-diphenyl-N,N'-bis(1-phenylmethyl-4-piperidinyl)-ethanediamide (DBPPE) is found by cyclic voltammetry at a Hg electrode. The cathodic and anodic peak potentials are -1.53 and -1.46 V (vs. Ag/AgCl), respectively. The cathodic peak shows adsorptive characteristics when the concentration of DBPPE is low and the preconcentration time is long. The adsorbed species is most probably the DBPPE neutral molecule. The method for measuring trace amount of DBPPE by adsorptive stripping voltammetry is established and the detection limit can reach 5 x 10(-9)M with a 6-min preconcentration.     

Functionalized HMS mesoporous silica as solid phase extractant for Pb(II) prior to its determination by flame atomic absorption spectrometry

In this work, a mesoporous silica has been chemically modified with 5-mercapto-1-methyl-1-H-tetrazol using the homogeneous route (MTTZ-HMS). This synthetic route involved the reaction of 5-mercapto-1-methyl-1-H-tetrazol with 3-chloropropyltriethoxysilane, prior to immobilization on the support. The resulting material has been characterized and employed as solid phase extractant for Pb(II). The effect of several variables (stirring time, pH, temperature, metal concentration, presence of other metals) has been studied using batch and column techniques. In batch experiments, 15 min stirring time, 55 degrees C and pH 8 were the optimal conditions for Pb(II) adsorption. In column experiments, sorption was quantitative for 1000 mL of 2.41 x 10(-4 )mM of Pb(II) solution and adsorbed ions were eluted out by 5 mL of 1 M HCl (preconcentration factor of 200). Spiked tap water was used for the preconcentration and determination of Pb(II) by flame atomic absorption spectrometry, and a 100% recovery was obtained. The LOD and LOQ values of the proposed method were found to be 3.52 x 10(-3) and 4.20 x 10(-3 )mM, respectively. The RSD for three preconcentration experiments was found to be 相似文献   

Trace measurements of rhodium by adsorptive stripping voltammetry

A sensitive stripping voltammetric procedure for quantifying rhodium is described. The complex of rhodium with chloride ions is adsorbed on the hanging mercury drop electrode, and the reduction current of the accumulated complex is measured during a negative-going scan. Cyclic voltammetry is used to characterize the interfacial and redox behaviors. The effect of pH, chloride concentration, accumulation potential and other variables is discussed. The detection limit is 1 x 10(-8)M ( approximately 1 ng/ml) with 5-min accumulation. A linear current-concentration relationship is observed up to 7 x 10(-7)M and the relative standard deviation (at the 2 x 10(-7)M level) is 3.0%. Possible interferences by co-existing metals are investigated.     

Voltammetric measurement of haloperidol following adsorptive accumulation at glassy-carbon electrodes

A sensitive stripping voltammetric method is reported for trace measurement of the psychotherapeutic drug haloperidol. The method is based on adsorptive preconcentration of haloperidol on the glassy-carbon electrode in an open circuit, followed by medium exchange and voltammetric determination of surface species. Cyclic voltammetry was used to explore the adsorptive behaviour and the results obtained suggest that the adsorption of haloperidol corresponds to the Frumkin-type isotherm. The adsorptive stripping response was evaluated with respect to stripping mode, electrolyte. pH, preconcentration time, concentration dependence, possible interference and other variables. The detection limit was 1.3 x 10(-9)M (10 min preconcentration) and the response was linear. The relative standard deviation (at the 1.3 x 10(-6)M level) was 2.3%. Applicability to a patient's urine sample is illustrated.     

Adsorptive stripping voltammetric properties of fentanyl at Hg electrode

Cyclic voltammetry shows that in a supporting electrolyte of NaOH, fentanyl (FENT) has a pair of cathodic and anodic peaks at Hg electrode. The peak potentials, E(pc) and E(pa), are -1.47 and -1.44 V (vs. Ag/AgCl), respectively. Fentanyl can be adsorbed on Hg surface, so the cathodic peak shows adsorptive properties. The adsorptive characteristics of fentanyl are explored in detail with various methods. The adsorbed species is considered to be fentanyl neutral molecule. The method for measuring trace amount of fentanyl by adsorptive stripping voltammetry is established. Under the optimised condition, the detection limit may reach 5 x 10(-8)M with a 10-min preconcentration.     

Spectrophotometric determination of bismuth and EDTA by means of the reaction of bismuth with pyrocatechol violet in the presence of septonex

The reaction of bismuth(III) with Pyrocatechol Violet in the presence of the cationic surfactant Septonex was studied and the optimal conditions for its analytical use were found (lambda = 612 nm, pH = 3.1, C(PV) = 4 x 10(-5)M, C(Sept), = 5 x 10(-4)M). The Lambert-Beer law is obeyed over the bismuth range 0.1-7.5 mug/ml. Decomposition of the Bi-PV-Septonex complex was utilized for indirect determination of ethylenediaminetetra-acetic acid at concentrations of 0.3-7.4 mug/ml.     

Voltammetric determination of methidathion insecticide

An electroanalytical method has been developed for the determination of methidathion by squarewave voltammetry on a Nafion®-coated glassy carbon electrode in aqueous solutions with 0.05 M acetate buffer as a supporting electrolyte. The best voltammetric conditions were found to be pH 4.0, a preconcentration potential of 0.45 V, and a preconcentration time of 60 s. The experimental parameters, such as pH, film thickness, preconcentration potential, preconcentration time, and square-wave voltammetric parameters, were optimized. Using this method, the calibration curve is linear in the range 5 × 10^?8?7 × 10^?7 M with a detection limit (S/N = 3) of 30 nM.     

Determination of iron(II) with chemically-modified carbon-paste electrodes

The utility of carbon-paste electrodes modified with 2,2'-bipyridyl and Nafion for the differential pulse voltammetric determination of iron(II) in aqueous medium is demonstrated. The method is based on formation of the 2,2'-bipyridyl complex of iron(II) and its accumulation by the Nafion. The differential pulse voltammetric response of the accumulated complex is used as the analytical signal. The response was evaluated with respect to carbon-paste composition, preconcentration time, pH, iron(II) concentration and other variables. A 3-min accumulation period permits measurement of iron(II) down to 10(-8)M, and a relative standard deviation of 3.8% for 2 x 10(-6)M iron(II). Rapid and convenient chemical renewal allows use of a single modified carbon-paste electrode in multiple analytical measurements over several days. The proposed procedure was applied to the determination of iron in certified standard reference materials and trace iron in natural waters.