Polarography VOLUME

Figure 26.8 (A) Suction equipment for TLC. (B) Equipment for polarography of small volumes 1, upper part of ground joint 2, mantle of the ground joint 3, electrolysis cell 4, water container sealing the inner space. [From Ref. 84.]...

Table VII is an index to the techniques employed. For the sake of brevity polarography is excluded from It, as pure water Is from Table VI and as the dropping mercury electrode is from Table VIII, but for each of the other fifty-odd techniques that are included in this volume an entry like...

The majority of controlled-potential electrochemistry has been carried out at mercury-pool electrodes. This is because of the vast amount of reference data available from polarography. Furthermore, the uniform and reproducible surface, and the high voltage for solvent reduction make the mercury pool particularly attractive relative to solid electrodes. As with electrodeposition, controlled-potential electrolysis rates are dependent on electrode area, stirring rates, solution volume, solution temperature, and supporting electrolyte. If the diffusion layer is uniform and the applied potential is such that one is on the diffusion plateau, the electrolysis obeys the relation... 

Lingane was a leader in the field of - electro analytical chemistry and wrote, with Kolthoff, the definitive, two volume monograph, Polarography [i] that remains a useful reference work. He also helped develop other electroanalytical techniques, like controlled potential electrolysis, -> coulometry, -> coulometric titrations, and developed an early electromechanical (Lingane-Jones) potentiostat, He wrote the widely-used monograph in this field, Electroanalytical Chemistry (1st edn., 1953 2nd edn., 1958). Lingane received a number of awards, including the Analytical Chemistry (Fisher) Award of the American Chemical Society in 1958. Many of his Ph.D. students, e.g., -> Meites, Fred Anson, Allen Bard, Dennis Peters, and Dennis Evans, went on to academic careers in electrochemistry. 

Heyrovsky, M. and Hyerovska, R. Surface and volume redox processes difference between potentiofnetry and polarography. J. Electroanal. Chem. 52, 141-143 (1974). 

The kinetics of the hydrolysis reactions (43) and (44) was studied in detail by means of polarography [158], and the respective pseudo-first-order rate constants and k2 were determined. In 0.2M KOH at 75°C, the rate constants were k = 3.2 x 10 s and At2 = 1.43 X 10 s , indicating that the second step of hydrolysis (44) is nearly 500 times faster than the first step (43). For this reason, the efficiency of borohydride in enhancing the plating reaction is very low, typically on the order of a few %, and most borohydride is lost by hydrolysis. (The actual efficiency depends on the ratio of substrate area to bath volume, i.e., the loading factor.)... 

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