Tibor Garai

Second harmonic a.c. anodic stripping voltammetry of metals at trace level: simultaneous determination of lead and thallium, and bismuth and antimony

Pairs of elements with very small differences in their half-wave potentials were determined at trace levels by second harmonic a.c. anodic stripping voltammetry. The simultaneous determination of lead and thallium as well as that of bismuth and antimony in 1M hydrochloric acid as supporting electrolyte was found to be possible in the range of concentration ratios: 7:1 > or = C(Pb):C(Tl) > or = 1:36 and 45:1 > or = C(Sb):C(Bi) > or = 1:35, with <5 % relative error due to mutual interference. The limit of detection was approximately 10(-8)M for all four elements, and the precision and error were 2-3%. The simultaneous determination of these metals in mixtures with concentration ratios outside the quoted ranges is still feasible by the standard-addition technique.

A Critical Comparison of Hanging Mercury Drop Electrode and Long Lasting Sessile Drop Mercury Electrode in A.C. Anodic Stripping Voltammerty

Abstract The hanging mercury drop electrode (HMDE) and the long lasting sessile drop mercury electrode (LLSDME) currently used in trace metal analysis are critically compared. Alternating current anodic stripping voltammetry (AC-ASV) and alternating current linear sweep voltammetry (AC-LSV) respectively are employed for the determination of Zn,Cd, Pb, Cu and Fe. The influence of the electrolysis time, stirring rate, a.c. amplitude, frequency and scan rate on the peak current is evaluated. Analytical measurements were carried out by the standard addition method, using 0.02 mol/l HClO4 + 0.1 mol/l NaClO4 (Zn, Cd, Pb, Cu) and 0.1 mol/l (COONa)2, (Fe), respectively as supporting electrolytes.

Analysis of metal alloys by second-harmonic phase-selective a.c. voltammetry

Second-harmonic phase-selective a.c. voltammetry and second-harmonic a.c. anodic stripping voltammetry are shown to be particularly suitable for simultaneous determinations of elements having very close half-wave potentials (differences of <50 mV). The technique are applied to real matrices. Samples of standard materials BCS 207/2 Gunmetal, SRM 631 SPectrographic Zinc Spelter and SRM 899 (Nickel-base High-temperature Alloy) were digested with a sulphuric acid/nitric acid mixture; after dissolution, the samples were taken up in hydrochloric acid. After adjustment to 1 mol l−1 HCl, the solutions were used directly for voltammetric measurements of Pb(II)/Sn (II), Sb(III)/Bi(III), Pb(II)/Tl(I) and In(III)/Cd(II) as appropriate. The confidence intervals of the experimental data were in agreement with the certified values for each element. Both the accuracy, expressed as percentage error, and precision, expressed as relative standard deviation, were better than 5%. The standard addition technique was found to improve the resolution of the a.c. voltammetric peaks even in the case of severe overlapping.

Trace-metal determination by second-harmonic alternating-current anodic stripping voltammetry

Second-harmonic alternating-current voltammetry can be used for the sequential determination of two electroactive species having very similar half-wave potentials (deltaE(1 2 ) < 50 mV). Since the concentrations of such metals in samples of special interest are often at trace levels, for their determination second-harmonic a.c. voltammetry (extremely selective but not sufficiently sensitive) can usefully be combined with the anodic stripping method, which has a very high analytical sensitivity. The determination of tin and lead as well as of indium and cadmium in 1M hydrochloric acid is described. The half-wave potentials are only 35 and 45 mV apart, respectively, for these systems. A three-electrode cell was used with a long-lasting sessile-drop mercury electrode as the working electrode, with a drop-time of 240-300 sec. The detection limit was found to be 10(-8)M for all four elements studied. The precision expressed as the relative standard deviation was 2-3% and the relative error was 1-2%.

Determination of metals by second-harmonic alternating-current voltammetry with a semi-stationary mercury electrode

The simultaneous determination of tin(II) and lead(II) as well as of indium(III) and cadmium(II) by second-harmonic a.c. voltanunetry using a semi-stationary mercury electrode with a drop-time of 240-300 sec (the long-lasting sessile-drop mercury electrode) has been investigated. Under the best experimental conditions, concentration ratios in the ranges l:12 c(Sn):c(Pb) 15:1 and 1:15 c(In):c(Cd) 15:1 can be determined.

Critical comparison of alternating current and differential pulse voltammetry in the determination of some heavy metals in sea-water

A critical comparison of phase-selective fundamental harmonic a.c. anodic stripping voltammetry and differential pulse anodic stripping voltammetry for the determination of Pb, Cd, Cu and Zn in sea-water is reported. Differential pulse anodic stripping voltammetry was found to be slightly more sensitive than the a.c. technique, but the effect of the charging current could be more effectively eliminated by the latter, especially in the determination of zinc(II) and copper(II). The detection limits for both techniques were found to be about 10−10-10−8M for all four elements. The precision, expressed as relative standard deviation, was of the order of 2–5% for the fundamental harmonic a.c. method and 5–8% for differential pulse voltammetry. The accuracy (expressed as recovery) was 95–105% for the former and 90–110% for the latter.