Dean's Analytical Chemistry Handbook, Second Edition

Section 3: STATISTICS IN CHEMICAL ANALYSIS

3.1 INTRODUCTION

Each observation in any branch of scientific investigation is inaccurate to some degree. Often the accurate value for the concentration of some particular constituent in the analyte cannot be determined. However, it is reasonable to assume the accurate value exists, and it is important to estimate the limits between which this value lies. It must be understood that the statistical approach is concerned with the appraisal of experimental design and data. Statistical techniques can neither detect nor evaluate constant errors (bias); the detection and elimination of inaccuracy are analytical problems. Nevertheless, statistical techniques can assist considerably in determining whether or not inaccuracies exist and in indicating when procedural modifications have reduced them.

By proper design of experiments, guided by a statistical approach, the effects of experimental variables may be found more efficiently than by the traditional approach of holding all variables constant but one and systematically investigating each variable in turn. Trends in data may be sought to track down nonrandom sources of error.

3.1.1 Errors in Quantitative Analysis

Two broad classes of errors may be recognized. The first class, determinate or systematic errors, is composed of errors that can be assigned to definite causes, even though the cause may not have been located. Such errors are characterized by being unidirectional. The magnitude may be constant from sample to sample, proportional to sample size, or variable in a more complex way. An example is the error caused by weighing a hygroscopic sample. This error is always...

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