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By Ronald G. Larson

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Response curves of current (/) in an electrolytic cell containing a planar working electrode can be obtained when the potential {E) is varied linearly with time. 3) result. These conditions can be 39 B. Examples of Model Types 100 3 o 0 30 60 90 - E , mV Figure 3 . 3 Sigmoid-shaped steady state voltammogram with background. achieved by stirring the solution, by rotating the electrode, or by using very tiny electrodes. These sigmoid curve shapes are therefore found in the electrochemical techniques of polarography, normal pulse voltammetry, rotating disk voltammetry, and slow scan voltammetry using disk "ultramicroelectrodes" with radii less than about 20 /xm.

It is intuitive that the number of degrees of freedom should be significantly larger than 1. Although it might be acceptable to use a 5-parameter model to analyze a set of 6 data points, better accuracy and precision of the parameters would probably be obtained with 10 or 20 data points. On the other hand, there is usually an upper Hmit on the number of degrees of freedom needed to provide parameters of the required accuracy and precision. This can be tested for a given analysis by using data for a standard system with known parameters or theoretical data with a realistic amount of error added to it.

299-385. 8. J. F. Rusling, in S. J. ), Practical Guide to Chemometrics, pp. 151-179. New York: Marcel Dekker, 1992. 9. S. N. Deming and S. L. Morgan, Anal Chem. 45 (1973), p. 278A. 10. K. J. Johnson, Numerical Methods in Chemistry, pp. 282-303. New York: Marcel Dekker, 1980. Chapter 3 Building Models for Experimental Data A. Sources of Data and Background Contributions We can envision at least two different sources of data that could be analyzed by nonlinear regression. One type of data is a typical response curve from a single instrumental experiment.

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