Decision-theoretical formulation of the calibration problem

Abstract

The choice of calibration policy is of basic importance in analytical chemistry. A prototype of the practical calibration problem is formulated as a mathematical task and a Bayesian solution of the resulting decision problem is presented. The optimum feedback calibration policy can then be found by dynamic programming. The underlying parameter estimation and filtering are solved by updating relevant conditional distributions. In this way: the necessary information is specified (for instance, the need for knowledge of the probability distribution of unknown samples is clearly recognized as the conceptually unavoidable informational source); the relationship of the information gained from a calibration experiment to the ultimate goal of calibration, i.e., to the estimation of unknown samples, is explained; an ideal solution is given which can serve for comparing various ways of calibration; and a consistent and conceptually simple guideline is given for using decision theory when solving problems of analytical chemistry containing uncertain data. The abstract formulation is systematically illustrated by an example taken from gas chromatography.