Stripping voltammetry anodic

Anodic stripping voltammetry (ASV) is the most widely used form of stripping analysis. In this case, the metals are being preconcentrated by electrodeposition into a small-volume mercury electrode (a thin mercury him or a hanging mercury drop). The preconcentration is done by cathodic deposition at a controlled time and potential. The deposition potential is usually 0.3-0.5 V more negative than E° for the least easily reduced metal ion to be determined. The metal ions reach the mercury electrode by diffusion and convection, where they are reduced and concentrated as amalgams  

The voltammetric peak reflects the time-dependent concentration gradient of the metal in the mercury electrode during the potential scan. Peak potentials serve to identify the metals in the sample. The peak current depends on various parameters of the deposition and stripping steps, as well as on the characteristics of the metal ion and the electrode geometry. For example, for a mercury film electrode, the peak current is given by 

The major types of interferences in ASV procedures are overlapping stripping peaks caused by a similarity in the oxidation potentials (e.g., of the Pb, Tl, Cd, Sn or Bi, Cu, Sb groups), the presence of surface-active organic compounds that adsorb on the mercury electrode and inhibit the metal deposition, and the formation of intermetallic compounds (e.g., Cu-Zn), which affects the peak size and position. Knowledge of these interferences can lead to their prevention, through adequate attention to key operations. 

Improved signal-to-background characteristics can be achieved using dualworking electrode techniques, such as ASV with collection or subtractive ASV (but at the expense of more complex instrumentation). 

Other versions of stripping analysis, including potentiometric stripping, adsorptive stripping, and cathodic stripping schemes, have been developed to further expand its scope and power. 

FIGURE 3-12 Anodic shipping voltammetry the potential-time waveform (a), along with die resulting voltammogram b). 

FIGURE 3-13 Concentration gradient of the metal in the merciuy film electrode and nearhy solntion dining the stripping step. 

FIGURE 3-14 Stripping voltammograms for 2 x 10 M Cu +, Pb +, In + and Cd + at the mercmy film (A) and hanging mercmy drop (B) electrodes. (Reproduced with permission from reference 21.) 

The sensitivity of the ASV technique allows detection of a limited number of trace elements at their natural concentration levels (e.g. in seawater many species of interest occur at concentrations of 10 9moldm 3). This technique is especially useful for monitoring elements of particular environmental concern, for example, Cu, Pb, Cd, Zn. 

The electro-chemical response (i.e. peak area values) reflects the hydrated metal ion content, and contributions from any labile complexes present. The size of the peak can be affected by experimental parameters such as the deposition potential used, the rate of stirring, the mercury drop diameter, the pulse frequency, the stripping solution composition, the system pH and the temperature. The size and position of the ASV peak can also be influenced by the chemical nature of the original test sample through processes such as 

In speciation studies ASV has been used in three different ways  

The position of the ASV peak on the voltage scan reflects the nature of the ion being reduced, and for complex ions the peak position moves to more negative potentials as stability increases. In some cases formation of intermediate valency states (e.g. in chloride solution, Cu2+ — Cu+ — Cu°) results in split peaks. Adsorption of species (e.g. colloidal particles, surfactants) on the mercury electrode also causes peak movement (generally in an anodic direction). 

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Albery W J and Brett C M A 1983 The wall-]et ring disc electrode. 2. Collection efficiency, titration curves and anodic stripping voltammetry J. Electroanal. Chem. 148 201... 

Anodic stripping voltammetry consists of two steps (Figure 11.37). The first is a controlled potential electrolysis in which the working electrode, usually a hanging mercury drop or mercury film, is held at a cathodic potential sufficient to deposit the metal ion on the electrode. For example, with Cu + the deposition reaction is... 

Potential-excitation signal and voltammogram for anodic stripping voltammetry at a hanging mercury drop electrode. 

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... 

When either pulse polarography or anodic stripping voltammetry can be used, the selection is often based on the analyte s expected concentration and the desired... 

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. 

Peak currents in anodic stripping voltammetry are a linear function of concentration... 

Wang, J. Anodic Stripping Voltammetry, /. Chem. Educ. 1983, 60, 1074-1075. 

The application of anodic stripping voltammetry for the quantitative analysis of Cd, Pb, and Cu in natural waters is described in this experiment. 

Anodic stripping voltammetry at a mercury film electrode can be used to determine whether an individual has recently fired a gun by looking for traces of antimony in residue collected from the individual s hands, fn a typical analysis a sample is collected with a cotton-tipped swab that had been wetted with 5% v/v HNO3. When returned to the lab, the swab is placed in a vial containing 5.00 mb of 4 M HCl that is 0.02 M in hydrazine sulfate. After allowing the swab to soak overnight,... 

X f0 ppb Sb was added, anodic stripping voltammetry is repeated, giving a peak current of f.i4 pA. How many nanograms of Sb is collected from the individual s hand ... 

The speciation scheme of Batley and Florence requires eight measurements on four samples. After removing insoluble particulates by filtration, the solution is analyzed for the concentration of anodic stripping voltammetry (ASV) labile metal and the total concentration of metal. A portion of the filtered solution is passed through an ion-exchange column, and the concentrations of ASV metal and total metal are determined. A second portion of the filtered solution is irradiated with UV light, and the concentrations of ASV metal... 

The methods of investigation of metal species in natural waters must possess by well dividing ability and high sensitivity and selectivity to determination of several metal forms. The catalytic including chemiluminescent (CL) techniques and anodic stripping voltammetry (ASV) are the most useful to determination of trace metals and their forms. The methods considered ai e characterized by a low detection limits. Moreover, they allow detection of the most toxic form of metals, that is, metal free ions and labile complexes. 

Pretreatment of the collected particulate matter may be required for chemical analysis. Pretreatment generally involves extraction of the particulate matter into a liquid. The solution may be further treated to transform the material into a form suitable for analysis. Trace metals may be determined by atomic absorption spectroscopy (AA), emission spectroscopy, polarogra-phy, and anodic stripping voltammetry. Analysis of anions is possible by colorimetric techniques and ion chromatography. Sulfate (S04 ), sulfite (SO-, ), nitrate (NO3 ), chloride Cl ), and fluoride (F ) may be determined by ion chromatography (15). 

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. 

Storage of solutions for titrimetry 108 Stripping analysis see Anodic stripping voltammetry... 

Describe clearly the principle and operation of potentiometric stripping analysis (PSA). How it is differed from anodic stripping voltammetry (ASV) What is the quantitative signal What is its advantage over ASV ... 

Whang, C. W., Page, J. A., vanLoon, G., and Griffin, M. R, Modified Standard Additions Calibration for Anodic Stripping Voltammetry, Anal. Chem. 56, 1984, 539-542. 

Anodic stripping voltammetry (ASV) has been used extensively for the determination of heavy metals in samples of biological origin, such as lead in blood. ASV has the lowest detection limit of the commonly used electroanalytical techniques. Analyte concentrations as low as 10 M have been determined. Figure 16 illustrates ASV for the determination of Pb at a mercury electrode. The technique consists of two steps. The potential of the electrode is first held at a negative value for several minutes to concentrate some of the Pb " from the solution into the mercury electrode as Pb. The electrode process is... 

DPASV Differential pulse anodic stripping voltammetry... 

Fig. 3.64. Idealized picture (by Barendrecht) of anodic stripping voltammetry. 

We shall now consider the electrochemical apparatus used (electrodes and electrolytic cell) and the three steps in its procedure more closely, especially for anodic stripping voltammetry (ASV) as most important application. 

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