Anodic stripping copper

The concentration of copper in a sample of sea water is determined by anodic stripping voltammetry using the method of standard additions. When a 50.0-mL sample is analyzed, the peak current is 0.886 )J,A. A 5.00-)J,L spike of 10.0-ppm Cu + is added, giving a peak current of 2.52 )J,A. Calculate the parts per million of copper in the sample of sea water. 

Some electrodes are made of substances that participate in the redox reactions that transfer electrons. These are active electrodes. Other electrodes serve only to supply or accept electrons but are not part of the redox chemistry these are passive electrodes. In Figure 19-7. both metal strips are active electrodes. During the redox reaction, zinc metal dissolves from the anode while copper metal precipitates at the cathode. The reactions that take place at these active electrodes are conversions between the metals contained in the electrodes and their aqueous cations. 

Qin, W., Zhang, Z., and Liu, H., Chemiluminescence flow-through sensor for copper based on anodic stripping voltammetric flow cell and ion-exchange column with immobilized reagents., Anal. Chem., 70, 3579, 1998. 

Scarponi et al. [93] used anodic stripping voltammetry to investigate the contamination of seawater by cadmium, lead, and copper during filtration and storage of samples collected near an industrial area. Filtration was carried... 

Muzzarelli and Sipos [622] showed that a column of chitosan (15 x 10 mm) can be used to concentrate zinc from 3 litres of seawater before determination by anodic-stripping voltammetry with a composite mercury-graphite electrode. Zinc (and lead) are eluted from the column by 2 M ammonium acetate (50 ml), copper by 0.01 M EDTA (10 ml), and cadmium by 0.1 M potassium cyanide (3 ml). 

Brugmann et al. [680] compared three methods for the determination of copper, cadmium, lead, nickel, and zinc in North Sea and northeast Atlantic waters. Two methods consisted of atomic absorption spectroscopy but with preconcentration using either freon or methyl isobutyl ketone, and anodic stripping voltammetry was used for cadmium, copper, and lead only. Inexplicable discrepancies were found in almost all cases. The exceptions were the cadmium results by the two atomic absorption spectrometric methods, and the lead results from the freon with atomic absorption spectrometry and anodic scanning voltammetric methods. 

Scarponi et al. [781] studied the influence of an unwashed membrane filter (Millpore type HA, 47 mm diameter) on the cadmium, lead, and copper concentrations of filtered seawater. Direct simultaneous determination of the metals was achieved at natural pH by linear-sweep anodic stripping voltammetry at a mercury film electrode. These workers recommended that at least 1 litre of seawater be passed through uncleaned filters before aliquots for analysis are taken the same filter can be reused several times, and only the first 50-100 ml of filtrate need be discarded. Samples could be stored in polyethylene containers at 4 °C for three months without contamination, but losses of lead and copper occurred after five months of storage. 

Nygaard et al. [752] compared two methods for the determination of cadmium, lead, and copper in seawater. One method employs anodic stripping voltammetry at controlled pH (8.1,5.3 and 2.0) the other involves sample pretreatment with Chelex 100 resin before ASV analysis. Differences in the results are discussed in terms of the definition of available metal and differences in the analytical methods. 

Cuculic and Branica [788] applied differential pulse anodic stripping voltammetry to a study of the adsorption of cadmium, copper, and lead in seawater onto electrochemical glass vessels, quartz cells, and Nalgene sample bottles. Nalgene was best for sample storage and quartz was best for electroanalytical vessels. 

Batley [28] examined the techniques available for the in situ electrodeposition of lead and cadmium in estuary water. These included anodic stripping voltammetry at a glass carbon thin film electrode and the hanging drop mercury electrode in the presence of oxygen and in situ electrodeposition on mercury coated graphite tubes. Batley [28] found that in situ deposition of lead and cadmium on a mercury coated tube was the more versatile technique. The mercury film, deposited in the laboratory, is stable on the dried tubes which are used later for field electrodeposition. The deposited metals were then determined by electrothermal atomic absorption spectrometry, Hasle and Abdullah [29] used differential pulse anodic stripping voltammetry in speciation studies on dissolved copper, lead, and cadmium in coastal sea water. 

A kind of standard additions approach can also be used for the measurement of apparent complexing capacity. In this technique, labile copper is measured by differential pulse anodic stripping voltammetry after each of a number of spikes of ionic copper have been added to the sample [420]. 

The copper flow-through CL sensor comprised an anion-exchange column having luminol and cyanide coimmobilized on the resin, while copper was temporarily retained by electrochemical preconcentration on a Au electrode placed in an anodic stripping voltammetric cell [64], Injection of 0.1 mol/L NaOH through the column eluted the reagents, which then reacted with copper, stripped from the electrode to produce a CL signal. The response was linear in the 0.01-10-pg/L... 

The high current intensity associated with the return peak relative to the second reduction process is characteristic of the so-called anodic stripping, which originates from the fast reoxidation of the metallic copper deposited on the electrode surface during the Cu+/Cu° reduction. 

It displays two successive reductions, corresponding to the sequence Cu(II)/Cu(I)/Cu(0). The first step (E° = + 0.19 V) is chemically reversible (ipJipc = 1) but electrochemically quasireversible (A2sp = 145 mV, at 0.2 V s 1) the second step is irreversible ( p = -0.65 V). The appearance of peak C in the backscan reveals, by its characteristic pointed lineshape, the presence of a process known as anodic stripping . This consists of the sudden reoxidation of the metallic copper that has been deposited on the electrode surface during the Cu(I)/Cu(0) reduction. 

Electroanalytical application of hemispherical [35,36], cylindrical [37,38] and ring microelectrodes [39] has been described. A hemispherical iridium-based mercury ultramicroelectrode was formed by coulometric deposition at -0.2 V vs. SSCE in solution containing 8 x 10 M Hg(II) and 0.1M HCIO4 [35]. The radius of the iridium wire was 6.5 pm. The electrode was used for anodic stripping SWV determination of cadmium, lead and copper in unmodified drinking water, without any added electrolyte, deoxygenation, or forced convection. The effects of finite volume and sphericity of mercury drop elecPode in square-wave voltammetiy have been also studied [36]. 

Fig. 3.2 Sono-square-wave anodic stripping voltammetric traces for an insonated deposition of 60 s at —1.5 V. Traces show background corrected standard additions to sono-solvent extracted laked horse blood solution (test solution 0.05%, by volume-blood). Each 10 (tl addition corresponds to an increase in copper concentration of 0.22 pg/1. Calibration graph shown inset (R = 0.9972) gives concentration of 1.637 mg/1 (reprinted from [64] with permission)...

Lead in water may he analyzed very precisely at low concentrations hy anodic stripping voltametry using an electrochemical analyzer static or controlled growth mercury drop electrodes, reference calomel or silver-silver chloride electrodes and silica or TEE cells. Copper, silver, gold, and certain organic compounds may interfere in the test. (APHA, AWWA and WEE. 1998. Standard Methods for the Examination of Water and Wastewater, 20 ed. Washington, D.C. American Public Health Association.)... 

The determination of copper is also discussed under Multi-Metal Analysis of Soils in Sect. 2.55 (atomic absorption spectrometry), Sect. 2.55 (emission spectrometry), Sect. 2.55 (inductively coupled plasma atomic emission spectrometry), Sect. 2.55 (photon activation analysis), Sect. 2.55 (neutron activation analysis), Sect. 2.55 (electron probe microanalysis) and Sect. 2.55 (differential pulse anodic stripping voltammetry). 

Figure 8.3 Schematic representation of copper concentrations relevant to freshwater studies and analytical windows of several analytical techniques. ASV, anodic stripping voltammetry CSV, cathodic stripping voltammetry ISE, ion selective electrode SLM, supported liquid membrane SWASV, square wave anodic stripping voltammetry LC50, lethal concentration for 50% of the population [Cu]t, total metal concentration (adapted from Langford and Gutzman, 1992).

Deaver, E. and Rodgers, J.H. (1996) Measuring bioavailable copper using anodic stripping... 

Martinotti, W., Queirazza, G., Guarinoni, A. and Mori, G. (1995) In-flow speciation of copper, zinc, lead and cadmium in fresh waters by square wave anodic stripping voltammetry Part II. Optimization of measurement step. Anal. Chim. Acta, 305, 183-191. 

Plavsic, M., Krznaric, D. and Branica, M. (1982) Determination of the apparent copper complexing capacity of seawater by anodic stripping voltammetry. Mar. Chem., 11, 17-31. 

Lead and mercury are deposited as micron-sized clusters, predominantly at intercrystallite boundaries [105] so does lithium from the polyethylene oxide solid electrolyte. What is more, Li intercalates into the sp2-carbon [22, 138], Thus, observations on the Li intercalation and deintercalation enable one to detect non-diamond carbon on the diamond film surface. Copper is difficult to plate on diamond [139], There is indirect evidence that Cu electrodeposition, whose early stages proceed as underpotential deposition, also involves the intercrystallite boundaries [140], We note that diamond electrodes seem to be an appropriate tool for use in the well-known electroanalytical method of detection of traces of metal ions in solutions by their cathodic accumulation followed by anodic stripping. The same holds for anodic deposition, e.g. of, Pb as PbCh with subsequent cathodic reduction [141, 142], Figure 30 shows the voltammograms of anodic dissolution of Cd and Pb cathodically predeposited from their salt mixtures on diamond and glassy carbon electrodes. We see that the dissolution peaks are clearly resolved. The detection limit for Zn, Cd, and Pb is as low as a few ppb [143]. 

The four variations of this technique are to be found in Table 14.2. The schemes of operation are shown in Fig. 14.6. Important applications for trace metals are the use of anodic stripping voltammetry (ASV) to determine trace quantities of copper, cadmium, lead and zinc, and adsorptive stripping voltammetry (AdSV) of trace quantities of nickel and cobalt—pre-concentration by adsorption accumulation of the oxime complexes followed by reduction to the metal is employed, as reoxidation of these metals in ASV is kinetically slow and does not lead to well-defined stripping peaks. 

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