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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 11, Number 6
BKCSDE 11(6)
June 20, 1990 

 
Title
Evaluation of the Function exp(x2)erfc(x) to Higher Precisions for Higher Order Derivative Polarography of CE-type Electrode Process
Author
Myung-Hoon Kim*, Veriti P. Smith, Tae-Kee Hong
Keywords
Abstract
The function exp(x2)erfc(x), which is often encountered in studies of electrode kinetics, is evaluated to an extended precision with 32 significant decimal digits in order to find theoretical relationships used in derivative polarography/voltammetry for a chemically-coupled electrode process. Computations with a lower precision are not successful. Evaluation of the function is accomplished by using three types of expansions for the function. Best ranges of arguments are selected for each equation for particular precisions for efficiencies. The method is successfully applied to calculate higher-order derivatives of the current potential curves in all potential ranges for a reversible electron transfer reaction coupled with a prior chemical equilibrium (i.e., a CE type process). Various parameters that characterize the peak asymmetry (such as ratios of peak-heights, ratios of half-peak-widths, and separations in peak-potentials) are analyzed to find how kinetic and thermodynamic parameters influence shapes of the derivatives. The results from the CE process is compared with those from an EC process in which a reversible electron transfer is coupled with a follow-up homogeneous chemical reaction. The two processes exibit quite contrasting differences for values of the parameters.
Page
497 - 505
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