Electrochemical detection basic methods

Bond et al. [68] have described a method for the simultaneous determination of down to lmg L 1 free sulphide and cyanide by ion chromatography, with electrochemical detection. These workers carried out considerable exploratory work on the development of ion chromatographic conditions for separating sulphide and cyanide in a basic medium (to avoid losses of toxic hydrogen cyanide and hydrogen sulphide) and on the development of a suitable amperometric detector. 

The hydrodynamically well-defined conditions of flow systems are an ideal environment for electrochemical detectors, resulting in enhanced performance characteristics. The surface sensing properties of most electrochemical methods require particular attention in the construction of suitable flow-through cells. Efficient and repeatable mass transport toward the electrode surface is necessary, and dead volumes should be small. Various flow-through cells have been designed for electrochemical detection, all of which can be derived from the basic configurations depicted in Figure 4. 

To date, a few methods have been proposed for direct determination of trace iodide in seawater. The first involved the use of neutron activation analysis (NAA) [86], where iodide in seawater was concentrated by strongly basic anion-exchange column, eluted by sodium nitrate, and precipitated as palladium iodide. The second involved the use of automated electrochemical procedures [90] iodide was electrochemically oxidised to iodine and was concentrated on a carbon wool electrode. After removal of interference ions, the iodine was eluted with ascorbic acid and was determined by a polished Ag3SI electrode. The third method involved the use of cathodic stripping square wave voltammetry [92] (See Sect. 2.16.3). Iodine reacts with mercury in a one-electron process, and the sensitivity is increased remarkably by the addition of Triton X. The three methods have detection limits of 0.7 (250 ml seawater), 0.1 (50 ml), and 0.02 pg/l (10 ml), respectively, and could be applied to almost all the samples. However, NAA is not generally employed. The second electrochemical method uses an automated system but is a special apparatus just for determination of iodide. The first and third methods are time-consuming. 

Ion chromatographic methods have been described for the co-determination of anions and cations in rainwater. Thus Jones and Tarter [138], using the conditions given in Table 2.19 reported determinations down to lmg L 1 of anions (chloride, bromide and sulphate) and cations (sodium, potassium, magnesium and calcium) in rainwater without converting the cations to anion complexes prior to detection [139], The technique uses a cation separator column, a conductivity detector, an anion suppressor column, and either a second conductivity detector or an electrochemical detector in sequence. The use of different eluants provides a means for the detection of monovalent cations and anions and divalent cations and anions in each of the samples. Using an eluant with a basic pH, it is possible to separate simultaneously and detect the monovalent cations (with the exception of the ammonium ion) and anions, while an eluant with an acidic pH allows for the separation and detection of divalent cations and anions. 

On the other hand, detection difficulties are often experienced with basic drugs because their therapeutic levels are in the low ng ml" range. Some of the problems can be alleviated by employing either an electrochemical or fluorescence detector, since it is possible to achieve detection levels of sub-nanogram with these instruments, if operated under favourable conditions. Furthermore, both of these detection methods can enhance selectivity because analytes will only be detected if they contain an electrochemically active group or fluoresce. 

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