Stationary electrode polarography

Bard AJ, Faulkner LR (1980) Electrochemical Methods. John Wiley Sons, New York. Nicholson RS, Shain I (1964) Theory of Stationary Electrode Polarography. Anal Chem 36 706-723. 

Sybrandt LB, Perone SP (1972) Computerized pattern classification of strongly overlapped peaks in stationary electrode polarography. Anal Chem 44 2331-2339. 

This technique was originally called Stationary Electrode Polarography [9, 10]. 

Mann, C. K. Stationary Electrode Polarography with a Staircase Voltage... 

Nicholson, R.S., and Shain, 1. 1964. Theory of stationary electrode polarography. Analytical Chemistry 36, 706-723. 

This method has also been called stationary electrode polarography however, we will adhere to the recommended practice of reserving the term polarography for voltammetric measurements at the DME. 

Recently, stationary electrode polarography has been used to study the electrode kinetics of several metal-ion systems on mercury in DMSO solutions. In cadmium discharge, the rate-determining step was believed to be a chemical reaction, the loss of molecules of solvation from the reactant ion, preceding a reversible charge transfer. The sensitivity of the rate towards the electrolyte cation suggests that the slow step is essentially confined to the double layer. 

R. S. Nicholson and 1. Shain. Theory of stationary electrode polarography. Single scan and cychc methods applied to reversible, irreversible, and kinetic systems. Anal. Chem. 36, 706-23 (1964). 

Reinmuth has examined chronopotentiometric potential-time curves and proposed diagnostic criteria for their interpretation. His treatment applies to the very limited cases with conditions of semi-infinite linear diffusion to a plane electrode, where only one electrode process is possible and where both oxidized and reduced forms of the electroactive species are soluble in solution. This approach is further restricted in application, in many cases, to electrode processes whose rates are mass-transport controlled. Nicholson and Shain have examined in some detail the theory of stationary electrode polarography for single-scan and cyclic methods applied to reversible and irreversible systems. However, since in kinetic studies it is preferable to avoid diffusion control which obscures the reaction kinetics, such methods are not well suited for the general study of the mechanism of electrochemical organic oxidation. The relatively few studies which have attempted to analyze the mechanisms of electrochemical organic oxidation reactions will be discussed in detail in a following section. 

Nicholson, R. S. and 1. Shain. 1964. Stationary electrode polarography. Analytical Chemistry, 36, 706-723. 

Polcyn, D.S. and Shain, I. (1966) Multistep charge transfers in stationary electrode polarography. Analyt. Chem., 38 (3), 370-375. 

Both linear sweep voltammetry (oscillographic polarography, stationary electrode polarography, chronoamperometry with linear sweep) and chrono-potentiometry have been extensively applied for studies in molten salts. The advantages of linear sweep voltammetry include (1) extensively developed theory enabling the experimentalist to interpret the mechanisms of relatively complex electrode reactions (2) well-defined mass transfer conditions, particularly when faster scan rates ( 1 V/sec) are employed (3) the decrease of the faradaic charge with the square root of the scan rate and the resulting decrease of any modifications of the solid electrode caused by the faradaic process. Chronopotentiometry, 29) related electroanalytical... 

---