Mercury dropping

It is to be noted that not only is the correction quite large, but for a given tip radius it depends on the nature of the liquid. It is thus incorrect to assume that the drop weights for two liquids are in the ratio of the respective surface tensions when the same size tip is used. Finally, correction factors for r/V < 0.3 have been determined, using mercury drops [37],... 

If, on the other hand, the thermometer has previously been used at some temperature below the freezing-point of benzene, when the bulb is originally placed in the beaker of water at 7-8 C., the mercury will rise in the capillary and ultimately collect in the upper part of the reservoir at a. When the expansion is complete, again tap the thermometer sharply at R so that this excess of mercury drops down into b, and then as before check the success of the setting by placing the thermometer m some partly frozen benzene. In either case, if the adjustment is not complete, repeat the operations, making a further small adjustment, until a satisfactory result is obtained. 

Mercury electrodes (a) hanging mercury drop electrode (b) dropping mercury electrode (c) static mercury drop electrode. 

A form of voltammetry using a dropping mercury electrode or a static mercury drop electrode. 

In hydrodynamic voltammetry current is measured as a function of the potential applied to a solid working electrode. The same potential profiles used for polarography, such as a linear scan or a differential pulse, are used in hydrodynamic voltammetry. The resulting voltammograms are identical to those for polarography, except for the lack of current oscillations resulting from the growth of the mercury drops. Because hydrodynamic voltammetry is not limited to Hg electrodes, it is useful for the analysis of analytes that are reduced or oxidized at more positive potentials. 

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. 

Faraday s law (p. 496) galvanostat (p. 464) glass electrode (p. 477) hanging mercury drop electrode (p. 509) hydrodynamic voltammetry (p. 513) indicator electrode (p. 462) ionophore (p. 482) ion-selective electrode (p. 475) liquid-based ion-selective electrode (p. 482) liquid junction potential (p. 470) mass transport (p. 511) mediator (p. 500) membrane potential (p. 475) migration (p. 512) nonfaradaic current (p. 512)... 

Here Ee is the standard potential of the reaction against the reference electrode used to measure the potential of the dropping electrode, and the potential E refers to the average value during the life of a mercury drop. Before the commencement of the polarographic wave only a small residual current flows, and the concentration of any electro-active substance must be the same at the electrode interface as in the bulk of the solution. As soon as the decomposition potential is exceeded, some of the reducible substance (oxidant) at the interface is reduced, and must be replenished from the body of the solution by means of diffusion. The reduction product (reductant) does not accumulate at the interface, but diffuses away from it into the solution or into the electrode material. If the applied potential is increased to a value at which all the oxidant reaching the interface is reduced, only the newly formed reductant will be present the current then flowing will be the diffusion current. The current / at any point... 

The mercury reservoir is then lowered until the mercury flow just ceases (not further) and the electrode is allowed to stand in the air. It is good technique, at the beginning of each period of use, to immerse the capillary for ca 1 min. in 1 1-nitric acid while mercury is flowing, then wash it well with distilled water a further precaution is to allow the mercury drops to form in distilled water for about 15 minutes. 

As already indicated, quantitative conventional d.c. polarography is limited at best to solutions with electrolytes at concentrations greater than 10-5M, and two different ions can only be investigated when their half-wave potentials differ by at least 0.2 V. These limitations are largely due to the condenser current associated with the charging of each mercury drop as it forms, and various procedures have been devised to overcome this problem. These include ... 

Barker and Jenkins45 attempted to solve the problem by application of the polarising current in a series of pulses one pulse of approximately 0.05 second duration being applied during the growth of a mercury drop, and at a fixed point near the end of the life of the drop. Two different procedures may, however, be employed (a) pulses of increasing amplitude may be superimposed upon a constant d.c. potential, or (b) pulses of constant amplitude may be applied to a steadily increasing d,c. potential. 

An important feature of pulse polarography is the sampling of the current at definite points in the lifetime of the mercury drop, and it is essential to... 

When the adjustment has been completed, rinse the capillary well with a stream of distilled water from a wash bottle and then dry by blotting with filter paper. Insert the capillary through an inverted cone of quantitative filter paper and clamp vertically over a small beaker. Lower the levelling bulb until the mercury drops just cease to flow,... 

Now commence the voltage sweep using a scan rate of 5 mV per second, or with a manual polarograph, increase the voltage in steps of 0.05 V. The recorder plot will take the form shown in Fig. 16.4 if a manual instrument is used, then since the current oscillates as mercury drops grow and then fall away, the plot will have a saw-tooth appearance, and for measurement purposes a smooth curve must be drawn through the midpoint of the peaks of the plot. 

Electrodes. The Hanging Mercury Drop Electrode is traditionally associated with the technique of stripping voltammetry and its capabilities were investigated by Kemula and Kublik.51 In view of the importance of drop size it is essential to be able to set up exactly reproducible drops, and this can be done as explained in Section 16.8 for the S.M.D.E. 

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