Stripping voltammetry cathodic

Cathodic stripping voltammetry (CSV) is the mirror image of ASV It involves anodic deposition of the analyte, followed by stripping in a negative-going potential scan  

FIGURE 3-17 Adsorptive stripping potentiogranis for 0.5 ppm calf-thymus DNA following different adsorption times of 1-150 s (curves a-f) (Reproduced with permission from reference 38.) 

Anions (e.g., halides) that form insoluble silver salts can be measured at a rotating silver disk electrode. In this, the deposition and stripping steps involve the reaction 

Copper-based electrodes can also be employed for the same task. 

Ag -F AgX -F e X = Cl, Br Copper-based eleetrodes ean also be employed for the same task. 

In another version of the technique, a thin film of organic ligand is collected on the working electrode, prior to sample introduction. Trace elements (in the sample) interact with the adsorbed ligand to form metal complexes. The electrode is then subjected to a cathodic sweep operation and reduction of the surface-active metal species (to form a metal amalgam) yields a current flow which is a sensitive measure of the initial trace element content. 

The determination of five selected elements is discussed below in detail to illustrate the procedures which are conunon for aU elements that can be determined by this technique. 

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The experimental design for cathodic stripping voltammetry is similar to that for anodic stripping voltammetry with two exceptions. First, the deposition step in-... 

Anodic Stripping Voltammetry Cathodic Stripping Voltammetry Absorptive Stripping Voltammetry... 

Table 11.11 lists several analytes that have been analyzed successfully by cathodic stripping voltammetry. 

This experiment describes the application of cathodic stripping voltammetry to the analysis of Ni and Co in fresh water and sea water. 

From the nature of the process described above it has been referred to as stripping polarography , but the term anodic stripping voltammetry is preferred. It is also possible to reverse the polarity of the two electrodes of the cell, thus leading to the technique of cathodic stripping voltammetry. 

Mattsson G, Nyholm L, Olin A (1994) Cathodic stripping voltammetry of HgSe. J Electroanal Chem 377 149-162... 

DPCSV Differential pulse cathodic stripping voltammetry... 

Ag(I). Ions in bold type are those that can also be determined using differential pulse anodic or cathodic stripping voltammetry. 

Van den Berg [131] used this technique to determine nanomolar levels of nitrate in seawater. Samples of seawater from the Menai Straits were filtered and nitrite present reacted with sulfanilamide and naphthyl-amine at pH 2.5. The pH was then adjusted to 8.4 with borate buffer, the solution de-aerated, and then subjected to absorptive cathodic stripping voltammetry. The concentration of dye was linearly related to the height of the reduction peak in the range 0.3-200 nM nitrate. The optimal concentrations of sulfanilamide and naphthyl-amine were 2 mM and 0.1 mM, respectively, at pH 2.5. The standard deviation of a determination of 4 nM nitrite was 2%. The detection was 0.3 nM for an adsorption time of 60 sec. The sensitivity of the method in seawater was the same as in fresh water. 

Absorptive cathodic stripping voltammetry has been used [151,152] to determine nanomolar levels of nitrite in seawater. The nitrite is derivatised by diazotisation with sulfanilamide and coupled with 1-naphthylamine to form an azo dye. The dye adsorbs onto a mercury drop electrode and its reduction is fully reversible. The concentration of dye is linearly related to concentration of nitrite in the range 0.3-200 nM. Down to 0.3 nM nitrite can be determined in seawater for an adsorption time of 60 seconds. 

Measurement techniques that can be employed for the determination of trace metals include atomic absorption spectrometry, anodic stripping voltammetry, differential pulse cathodic stripping voltammetry, inductively coupled plasma atomic emission spectrometry, liquid chromatography of the metal chelates with ultraviolet-visible absorption and, more recently, inductively coupled plasma mass spectrometry. 

Adsorptive cathodic stripping voltammetry has an advantage over graphite furnace atomic absorption spectrometry in that the metal preconcentration is performed in situ, hence reducing analysis time and risk of contamination. Additional advantages are low cost of instrumentation and maintenance, and the possibility to use adapted instrumentation for online and shipboard monitoring. 

Cathodic stripping voltammetry has been used to determine copper species in seawater [291,292],... 

Donat and Bruland [217] determined low levels of nickel and cobalt in seawater by a voltammetric technique, and the nioxime complexes of the two elements were concentrated on a hanging mercury drop electrode. The current resulting from the reduction of Co (II) and Ni (II) was measured by differential pulse cathodic stripping voltammetry. Detection limits are 6 pM (cobalt) and 0.45 nM (nickel). 

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