Jin Seog Kim

Improving acoustic determinations of the Boltzmann constant with mass spectrometer measurements of the molar mass of argon

We determined accurate values of ratios among the average molar masses MAr of 9 argon samples using two completely-independent techniques: (1) mass spectrometry and (2) measured ratios of acoustic resonance frequencies. The two techniques yielded mutually consistent ratios (RMS deviation of 0.16 × 10−6 MAr from the expected correlation) for the 9 samples of highly-purified, commercially-purchased argon with values of MAr spanning a range of 2 × 10−6 MAr. Among the 9 argon samples, two were traceable to recent, accurate, argon-based measurements of the Boltzmann constant kB using primary acoustic gas thermometers (AGT). Additionally we determined our absolute values of MAr traceable to two, completely-independent, isotopic-reference standards; one standard was prepared gravimetrically at KRISS in 2006; the other standard was isotopically-enriched 40Ar that was used during NISTs 1988 measurement of kB and was sent to NIM for this research. The absolute values of MAr determined using the KRISS standard have the relative standard uncertainty ur(MAr) = 0.70 × 10−6 (Uncertainties here are one standard uncertainty.); they agree with values of MAr determined at NIM using an AGT within the uncertainty of the comparison ur(MAr) = 0.93 × 10−6. If our measurements of MAr are accepted, the difference between two, recent, argon-based, AGT measurements of kB decreases from (2.77 ± 1.43) × 10−6 kB to (0.16 ± 1.28) × 10−6 kB. This decrease enables the calculation of a meaningful, weighted average value of kB with a uncertainty ur(kB) ≈ 0.6 × 10−6.

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).

Final report on international comparison CCQM-K68: Nitrous oxide in synthetic air

Nitrous oxide (N2O) is one of six greenhouse gases that are regulated by the Kyoto Protocol and has a Global Warming Potential (GWP) that is 296 times that of carbon dioxide. Global levels of nitrous oxide have increased at a rate of 0.25%/yr (0.8 ppb/yr) during the last ten years. In order to monitor levels of nitrous oxide in the atmosphere, it is necessary to use measurement standards with demonstrated equivalence at the highest level of accuracy. This report describes the results of a key comparison of standard gas mixtures of nitrous oxide in synthetic air at an amount fraction of 320 nmol/mol. This key comparison is part of the programme of the Gas Analysis Working Group (GAWG) of the CCQM to demonstrate the equivalence of the standards and measurement capabilities of the NMIs for greenhouse gases. It will support the development of measurement capability at the NMIs for nitrous oxide with uncertainties within the target set by the Global Atmospheric Watch (GAW) programme of the WMO for its global monitoring networks. 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-K54: Primary standard gas mixtures of hexane in methane

The aim of this comparison is to evaluate the gravimetry and purity verification of gas mixtures prepared by introducing a liquid into a gas cylinder. This type of preparation is well known from, e.g., ethanol in nitrogen/air (CCQM-K4), and n-hexane in synthetic natural gas (CCQM-K16). The choice for n-hexane in methane is based on the relevance of natural gas primary standard mixtures and higher hydrocarbons in synthetic natural gas (for, e.g., dew point calibrations). Furthermore, n-hexane is relatively straightforward to analyse using a GC/FID (gas chromatograph equipped with a flame ionisation detector) with good repeatability. Eight laboratories participated. After the data evaluation, the result of one laboratory was eliminated to arrive at a consistent subset. The quality of the fitted line was not overly good, leading to small discrepancies in the degrees-of-equivalence calculated for three other laboratories. Only four laboratories are consistent with the KCRV. 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 K23b-Natural gas type II

At the highest metrological level, natural gas standards are commonly prepared gravimetrically as PSMs (Primary Standard Mixtures). This international key comparison is a repeat of CCQM-K1e-g. The mixtures concerned contain nitrogen, carbon dioxide and the alkanes up to butane. The only difference from CCQM-K1e-g is the addition of iso-butane to the list. The agreement of the results in this key comparison is very good. For all parameters, with a few exceptions, the results agree within 0.5% (or better) with the key comparison reference value. For methane, the results are generally within 0.1% (or better) of the KCRV. 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).

Gravimetric standard gas mixtures for global monitoring of atmospheric SF6

In this study, standard gas mixtures of SF6 in synthetic air were gravimetrically developed as a suite consisting of 6 mixtures with mole fractions of SF6 ranging from 5 to 15 pmol/mol. For precision in weighing the gas fills, an automatic weighing system coupled with a high sensitivity mass balance was used and a gravimetry precision of 3 mg (2σ) was achieved. Impurity profiles of the raw gases were determined by various analyzers. In particular, sub pmol/mol levels of SF6 in the matrix components (N2, O2, and Ar) were carefully measured, since the mole fraction of SF6 in the final step can be significantly biased by this trace amount of SF6 in the raw gases of the matrix components. Gravimetric dilution of SF6 by purity-assessed N2 was performed in 6 steps to achieve a mole fraction of 440 pmol/mol. In the final step, O2 and Ar were added to mimic the atmospheric composition. Gravimetric fractions of SF6 and the associated standard uncertainty in each step were computed according to the ISO 6142 and JCGM 100:2008, respectively, and validated experimentally. Eventually, the SF6 fraction uncertainty of the standard gas mixtures combined by uncertainties of gravimetric preparation and verification measurements were found to be nominally 0.08% at a 95% confidence interval. A comparison with independent calibration standards from NOAA shows agreement within 0.49%, satisfying the extended WMO compatibility goal, 0.05 ppt.

Roles of chemical metrology in electronics industry and associated environment in Korea: A tutorial

Chemical metrology is gaining importance in electronics industry that manufactures semiconductors, electronic displays, and microelectronics. Extensive and growing needs from this industry have raised the significance of accurate measurements of the amount of substances and material properties. For the first time, this paper presents information on how chemical metrology is being applied to meet a variety of needs in the aspects of quality control of electronics products and environmental regulations closely associated with electronics industry. For a better understanding of the roles of the chemical metrology within electronics industry, the recent research activities and results in chemical metrology are presented using typical examples in Korea where electronic industry is leading a national economy. Particular attention is paid to the applications of chemical metrology for advancing emerging electronics technology developments. Such examples are a novel technique for the accurate quantification of gas composition at nano-liter levels within a MEMS package, the surface chemical analysis of a semiconductor device. Typical metrological tools are also presented for the development of certified reference materials for fluorinated greenhouse gases and proficiency testing schemes for heavy metals and chlorinated toxic gas in order to cope properly with environmental issues within electronics industry. In addition, a recent technique is presented for the accurate measurement of the destruction and removal efficiency of a typical greenhouse gas scrubber.

Final report on CCQM-P151: Halocarbons in dry whole air

The growing awareness of climate change/global warming and continuing concerns regarding stratospheric ozone depletion will require future measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track and control the emissions of these species globally in the atmosphere, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. This report describes the results of a pilot study between National Metrology Institutes and atmospheric research laboratories for several of the more important halocarbons at atmospheric concentration levels. The comparison includes the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC 12), trichlorofluoromethane (CFC 11), and 1,1,2-trichlorotrifluoroethane (CFC 113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC 22) and 1-chloro-1,1-difluoroethane (HCFC 142b); and the hydrofluorocarbon (HFC) 1,1,1,2-tetrafluoroethane (HFC 134a), all in a dried whole air sample. The objective of this key comparison is to compare the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. Main text. To reach the main text of this paper, click on Final Report. The final report has been peer-reviewed and approved for publication by the CCQM.

Final report on international comparison CCQM-K83: Halocarbons in dry whole air

The growing awareness of climate change/global warming and continuing concerns regarding stratospheric ozone depletion will require future measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track and control the emissions of these species globally in the atmosphere, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. This report describes the results of a key comparison for several of the more important halocarbons at atmospheric concentration levels. The comparison includes the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC 12), trichlorofluoromethane (CFC 11), and 1,1,2 trichlorotrifluoroethane (CFC 113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC 22) and 1-chloro-1,1-difluoroethane (HCFC 142b); and the hydrofluorocarbon (HFC) 1,1,1,2 tetrafluoroethane (HFC 134a), all in a dried whole air sample. The objective of this key comparison is to compare the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. 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 (CIPM MRA).