Development of a fifteen component hydrocarbon gas standard reference material at 5 nmol/mol in nitrogen

Primary gravimetric gas cylinder standards containing fifteen alkane, alkene and aromatic hydrocarbons (C₂–C₁₀) were prepared. A procedure previously developed to prepare gas cylinder standards for volatile organic compounds at the 5 nmol/mol (ppb) level was used. The set of primary hydrocarbon gas standards prepared by this procedure were intercompared by using gas chromatography with a hydrogen flame ionization detector (GC-FID). The linear regression analysis showed excellent agreement among the standards for each compound. Similar mixtures containing many of these hydrocarbons have been evaluated over time and have shown stability of the concentrations in aluminum gas cylinders for three years. This research resulted in the production and certification of Standard Reference Material (SRM) 1800, which contains fifteen hydrocarbons in nitrogen at a nominal concentration of 5 nmol/mol for each analyte. A batch of twenty-four cylinders containing the mixture was prepared at NIST following previously demonstrated protocols for their preparation. Each cylinder was analyzed against one cylinder from the batch, designated as the “lot control”, for each of the fifteen hydrocarbons. The data showed that the batch was homogeneous, from 0.2 to 0.7% depending on the compound, and stable for each hydrocarbon in the mixture resulting in certification and issuance of SRM 1800.     

Development of perfluorocarbon (PFC) primary standards for monitoring of emissions from aluminum production

An EPA Voluntary Aluminum Industrial Partnership (VAIP) program has been formed to help US primary producers focus on reducing the emissions of two perfluorocarbons (PFCs), tetrafluoromethane (CF4) and hexafluoroethane (C2F6), during the production of aluminum. To ensure comparability of measurements over space and time, traceability to national sources was desirable. Hence, the EPA approached the NIST to develop a suite of primary standards to cover a mole fraction (concentration) range of 0.1 to 1400 micromol mol(-1) for CF4 and 0.01 to 150 micromol mol(-1) of C2F6. A total of eight gravimetric PFC gas standards were prepared with relative expanded uncertainties of < or = 0.52% (approximately 95% confidence level). These primary standards were ultimately used to assign values to a series of secondary gas standards at three mole-fraction levels with relative expanded uncertainties ranging from +/- 0.7% to 5.3% (approximately 95% confidence level). This series of secondary standards was used within the aluminum industry to calibrate instruments used to make emission measurements. Assignment of values to the secondary standards was performed by use of gas chromatography with flame-ionization detection (GC-FID) and Fourier transform infrared spectrometry (FTIR). Real time pot-line and stack samples from a local aluminum plant were also obtained and sub-samples sent to each participating facility for analysis. The data generated from each facility were sent to NIST for analysis. The maximum difference between the NIST and individual facilities' values for the same sub-sample was +/- 26%.     

Analysis of natural gas: the necessity of multiple standards for calibration

The importance of natural gas as an international trading commodity and the cost to consumers has made the accuracy of determinations for the components of natural gas very important. Pricing of natural gas is based on the heating value of the gas determined from either calorimetry measurements or calculations based on individual component concentrations determined by gas chromatography (GC). Due to the expense of accurate calibration standards, many analysts and laboratories will use a single calibration standard to perform natural gas determinations. Therefore, the purpose of this study was to determine whether an analyst could accurately measure the components of natural gas, in particular methane, using a single standard, or whether a suite of standards is necessary to calibrate the analytical instrument. A suite of eight gravimetric primary standards was prepared covering a concentration range for methane of 64-94 mol%, with uncertainties of +/-0.05% relative (95% confidence interval). These natural gas primary standards also contained nitrogen, carbon dioxide, ethane, propane, iso-butane, n-butane, iso-pentane, n-pentane, and n-hexane with varying concentrations from 0.02 to 14%. A single analytical method was used in which only the amount of sample injected onto the column was altered. The results show that when injecting a 0.5 ml sample volume a second-order regression through the standards is necessary for the determination of methane. The results for nitrogen, ethane and propane also show the same trend. Only those individual standards whose methane concentration is within 1% of the test mixture predicted a concentration within 0.05% of the regression value. Those individual primary standards whose methane concentration is different by more than +/-1% of the test mixture predicted values differing by +/-0.5 to +/-2.0% from the regression value. These differences lie well outside the predicted concentration uncertainty interval of +/-0.20%. A smaller sample volume, 0.1 ml, resulted in a set of data that could be fit using linear regression. Each of the eight primary standards individually predicted the methane in the test mixture to be within +/-0.11% of the predicted value from linear regression. The data confirm that it is imperative to fully characterize the analytical system before proceeding with an analysis.     

Development of a gas standard reference material containing eighteen volatile organic compounds

Summary A procedure to prepare primary gas cylinder standards for eighteen volatile organic compounds (VOC's) at the 1–15 nmol/mol (ppb) level was developed. The gas standards that were prepared by this procedure were intercompared by using gas chromatography with flame ionization detection (GC-FID) and electron capture detection (GC-ECD). The data, gravimetric concentration of the standards versus the respective GC peak area response, were plotted for each compound and fitted using linear regression. The regression analysis showed excellent agreement among the standards for each compound. These gas standards were evaluated over a period of 2 years and were determined to be stable and accurate. This research resulted in the development of Standard Reference Material (SRM) 1804, which contains these 18 volatile organic compounds in nitrogen at a nominal concentration of 5 nmol/mol for each compound. A batch of cylinders containing the mixture was procured from a commercial supplier. Each cylinder in the batch was analyzed for each of the 18 components. The data showed that the batch was homogeneous and stable for 15 of the 18 organic compounds, resulting in certification and issuance of SRM 1804.