Uncertainty due to volumetric operations is often underestimated

Fifteen international titration standards were evaluated to determine minimum and maximum combined standard uncertainties. Assuming most thorough performance of the analyses revealed minimum values, whereas maximum values of uncertainty were obtained assuming that the analyses had been done under high time pressure. Minimum and maximum uncertainties were compared with the corresponding reproducibility standard deviations. Since the combined standard uncertainty is expected to lie between the reproducibility standard deviation and the maximum combined standard uncertainty, realistic standard uncertainties of individual influence quantities of volumetric and weighing procedures could be calculated. This top-down approach revealed up to 4 times higher uncertainties for volumetric operations compared to the bottom-up approach according to the current literature. Hence, uncertainty due to volumetric operations is obviously strongly underestimated. The present study additionally contains a ranking of the contributions to the uncertainty of titrimetric results.