Development of a primary diffusion source of organic vapors for gas analyzer calibration

Abstract

The generation of reference mixtures of volatile organic compounds (VOCs) at trace levels (10 ppt–10 ppb) is a challenge for both environmental and clinical measurements. The calibration of gas analyzers for trace VOC measurements requires a stable and accurate source of the compound of interest. The dynamic preparation of gas mixtures by diffusion is a suitable method for fulfilling these requirements. The estimation of the uncertainty of the molar fraction of the VOC in the mixture is a key step in the metrological characterization of a dynamic generator. The performance of a dynamic generator was monitored over a wide range of operating conditions. The generation system was simulated by a model developed with computational fluid dynamics and validated against experimental data. The vapor pressure of the VOC was found to be one of the main contributors to the uncertainty of the diffusion rate and its influence at 10–70 kPa was analyzed and discussed. The air buoyancy effect and perturbations due to the weighing duration were studied. The gas carrier flow rate and the amount of liquid in the vial were found to play a role in limiting the diffusion rate. The results of sensitivity analyses were reported through an uncertainty budget for the diffusion rate. The roles of each influence quantity were discussed. A set of criteria to minimize the uncertainty contribution to the primary diffusion source (25 µg min−1) were estimated: carrier gas flow rate higher than 37.7 sml min−1, a maximum VOC liquid mass decrease in the vial of 4.8 g, a minimum residual mass of 1 g and vial weighing times of 1–3 min. With this procedure a limit uncertainty of 0.5% in the diffusion rate can be obtained for VOC mixtures at trace levels (10 ppt–10 ppb), making the developed diffusion vials a primary diffusion source with potential to become a new reference material for trace VOC analysis.

Uncertainty evaluation of thermodynamic properties estimated with online data tools: vapor pressure as case study

“…In this work, these issues are explored trough a case study: the vapor pressure; a property that is common ground for many engineering problems where the coexistence of two or more fluid phases in equilibrium is involved. In the field of metrology, the vapor pressure is particularly important when designing devices for gas standards generation [3,6]. For the case study, the model of Antoine equation is considered, in both linearized and non-linearized form.…”