Abstract
Thermodynamic data are suitable subject for investigating strategies and concepts for the evaluation of complete measurement uncertainty budgets in situations where the measurand cannot be expressed in a mathematical formula. Some suitable approaches are the various forms of Monte Carlo simulations in combination with computer-intensive statistical methods that are directed to an evaluation of empirical distribution curves for the uncertainty budget. Basis of the analysis is a cause-and-effect diagram. Some experience is available with cause-and-effect analysis of thermodynamic data derived from spectrophotometric data. Another important technique for the evaluation of thermodynamic data is glass-electrode potentiometry. On basis of a newly derived cause-and-effect diagram, a complete measurement uncertainty budget for the determination of the acidity constants of phosphoric acid by glass-electrode potentiometry is derived. A combination of Monte Carlo and bootstrap methods is applied in conjunction with the commercially available code SUPERQUAD. The results suggest that glass-electrode potentiometry may achieve a high within-laboratory precision because major uncertainty contributions become evident via interlaboratory comparisons. This finding is further underscored by analysing available literature data.
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A. Kufelnicki and M. Świątek acknowledge financial support from the Medical University of Łódź under project 503-314-2.
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Meinrath, G., Kufelnicki, A. & Świątek, M. Approach to accuracy assessment of the glass-electrode potentiometric determination of acid-base properties. Accred Qual Assur 10, 494–500 (2006). https://doi.org/10.1007/s00769-005-0030-7
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DOI: https://doi.org/10.1007/s00769-005-0030-7