Dong Min Moon

Final report on international key comparison CCQM-K53: Oxygen in nitrogen

Gravimetry is used as the primary method for the preparation of primary standard gas mixtures in most national metrology institutes, and it requires the combined abilities of purity assessment, weighing technique and analytical skills. At the CCQM GAWG meeting in October 2005, it was agreed that KRISS should coordinate a key comparison, CCQM-K53, on the gravimetric preparation of gas, at a level of 100 ?mol/mol of oxygen in nitrogen. KRISS compared the gravimetric value of each cylinder with an analytical instrument. A preparation for oxygen gas standard mixture requires particular care to be accurate, because oxygen is a major component of the atmosphere. Key issues for this comparison are related to (1) the gravimetric technique which needs at least two steps for dilution, (2) oxygen impurity in nitrogen, and (3) argon impurity in nitrogen. The key comparison reference value is obtained from the linear regression line (with origin) of a selected set of participants. The KCRV subset, except one, agree with each other. The standard deviation of the x-residuals of this group (which consists of NMIJ, VSL, NIST, NPL, BAM, KRISS and CENAM) is 0.056 ?mol/mol and consistent with the uncertainties given to their standard mixtures. The standard deviation of the residuals of all participating laboratory is 0.182 ?mol/mol. With respect to impurity analysis, overall argon amounts of the cylinders are in the region of about 3 ?mol/mol; however; four cylinders showed an argon amount fraction over 10 ?mol/mol. Two of these are inconsistent with the KCRV subset. The explicit separation between two peaks of oxygen and argon in the GC chromatogram is essential to maintain analytical capability. Additionally oxygen impurity analysis in nitrogen is indispensable to ensure the preparative capability. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

Effect of variation in argon content of calibration gases on determination of atmospheric carbon dioxide.

Carbon dioxide (CO(2)) is a greenhouse gas that makes by far the largest contribution to the global warming of the Earths atmosphere. For the measurements of atmospheric CO(2) a non-dispersive infrared analyzer (NDIR) and gas chromatography are conventionally being used. We explored whether and to what degree argon content can influence the determination of atmospheric CO(2) using the comparison of CO(2) concentrations between the sample gas mixtures with varying Ar amounts at 0 and 18.6 mmol mol(-1) and the calibration gas mixtures with Ar at 8.4, 9.1, and 9.3 mmol mol(-1). We newly discovered that variation of Ar content in calibration gas mixtures could undermine accuracy for precise and accurate determination of atmospheric CO(2) in background air. The differences in CO(2) concentration due to the variation of Ar content in the calibration gas mixtures were negligible (<+/-0.03 micromol mol(-1)) for NDIR systems whereas they noticeably increased (<+/-1.09 micromol mol(-1)) especially for the modified GC systems to enhance instrumental sensitivity. We found that the thermal mass flow controller is the main source of the differences although such differences appeared only in the presence of a flow restrictor in GC systems. For reliable monitoring of real atmospheric CO(2) samples, one should use calibration gas mixtures that contain Ar content close to the level (9.332 mmol mol(-1)) in the ambient air as possible. Practical guidelines were highlighted relating to selection of appropriate analytical approaches for the accurate and precise measurements of atmospheric CO(2). In addition, theoretical implications from the findings were addressed.

International comparison CCQM-K46: Ammonia in nitrogen

Ammonia is an important compound in the chemical industry. It is widely used and is the basis for producing other compounds containing nitrogen. Ammonia is also very hazardous, and consequently emissions of ammonia need be controlled and monitored. In the past years, several national metrology institutes have developed facilities for the preparation of Primary Standard gas Mixtures (PSMs), dynamically generated ammonia mixtures and facilities for comparing and certifying gas mixtures containing ammonia. The amount-of-substance fraction level of ammonia chosen for this key comparison is 30–50 µmol/mol. The results of this key comparison revealed that there is at present no consensus among static and dynamic techniques for gas mixture preparation for this component in this range. As key comparison reference value (KCRV), the mean of the three methods is used. In its uncertainty, no allowance is made for the observed biases. With respect to the KCRV, only two laboratories report consistent results. When grouped in accordance with the employed methods, the results are consistent. Further experimental work is needed. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

International Comparison CCQM-K15: Emission level of CF4 and SF6

CF4 and SF6 are the global warming chemicals that are used in semiconductor companies. In the Kyoto protocol on climate change in 1997, those chemicals were included in the items for which quantified emission limitation and reduction commitments were required. Accordingly for the measurement of these gases, it is necessary that measurement results are accurate and traceable, in particular because of the fact that CF4 and SF6 are global warming source gases. This part of the project focuses on a comparison of measurement capability for measuring CF4 and SF6 at emission level. This key comparison will cover the comparability of the gas CRMs at the emission level (10 × 10-6 mol/mol – 100 mmol/mol in nitrogen or air) of the following chemicals: CF4, C2F6, CHF3, SF6 and NF3. There is good agreement between the results of the key comparison participants in this comparison for both CF4 and SF6. The results for CF4 agree within 0.5% relative, and for SF6 they agree within 0.1% relative. Even though the concentration is as low as 100 µmol/mol, the comparability between participants on gravimetric preparation plus comparison analysis is excellent for the laboratories that are participating in this key comparison. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM.

Analysis of trace impurities in neon by a customized gas chromatography.

Excimer lasers, widely used in the semiconductor industry, are crucial for analyzing the purity of premix laser gases for the purpose of controlling stable laser output power. In this study, we designed a system for analyzing impurities in pure neon (Ne) base gas by customized GC. Impurities in pure neon (H2 and He), which cannot be analyzed at the sub-μmol/mol level using commercial GC detectors, were analyzed by a customized pulsed-discharge Ne ionization detector (PDNeD) and a pressurized injection thermal conductivity detector using Ne as the carrier gas (Pres. Inj. Ne-TCD). From the results, trace species in Ne were identified with the following detection limits: H2, 0.378μmol/mol; O2, 0.119μmol/mol; CH4, 0.880μmol/mol; CO, 0.263μmol/mol; CO2, 0.162μmol/mol (PDNeD); and He, 0.190μmol/mol (Pres. Inj. Ne-TCD). This PDNeD and pressurized injection Ne-TCD technique thus developed permit the quantification of trace impurities present in high-purity Ne.