Uncertainty analysis of the diffusion rate in the dynamic generation of volatile organic compound mixtures

The measurement of volatile organic compound (VOC) concentration changes, in the range of 10 ppt–1ppb, is essential in several applications. The World Meteorological Organization has identified a set of VOCs that are critical because of their long-term instability. The measurement of such changes demands generation of reference mixtures at a high accuracy and stability level. The dynamic preparation of gas mixtures based on diffusion is a suitable way of generating accurate reference mixtures, particularly of unstable VOCs. Diffusion rate and dilution gas flow rate uncertainties are the main contributors to the overall VOC concentration uncertainty. This paper presents a comprehensive overview of the uncertainty of the diffusion rate. Stress is laid on the advantages offered by a modified measurand equation. The validity of this analysis and the modified equation has been confirmed experimentally. Temperature variability and mass difference uncertainty make the main contributions to the uncertainty: a 0.01 ◦C variability results in a 0.2% uncertainty. The new measurand equation provides both a better indication of the systematic effects at a narrow temperature variability and a more realistic calculation of the uncertainty. The modified equation enhances calculation of uncertainty at the low diffusion rates needed to generate very low VOC concentration mixtures.