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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Monitoring of CoS 2 reactions using high-temperature XRD coupled with gas chromatography (GC)

High-temperature X-ray diffraction with concurrent gas chromatography (GC) was used to study cobalt disulfide cathode pellets disassembled from thermal batteries. When CoS 2 cathode materials were analyzed in an air environment, oxidation of the K(Br, Cl) salt phase in the cathode led to the formation of K 2 SO 4 that subsequently reacted with the pyrite-type CoS 2 phase leading to cathode decomposition between ~260 and 450 °C. Here, independent thermal analysis experiments, i.e. simultaneous thermogravimetric analysis/differential scanning calorimetry/mass spectrometry (MS), augmented the diffraction results and support the overall picture of CoS 2 decomposition. Both gas analysis measurements (i.e. GC and MS) from the independent experiments confirmed the formation of SO 2 off-gas species during breakdown of the CoS 2 . In contrast, characterization of the same cathode material under inert conditions showed the presence of CoS 2 throughout the entire temperature range of analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Qualitative Characterization of the Aqueous Fraction from Hydrothermal Liquefaction of Algae Using 2D Gas Chromatography with Time-of-flight Mass Spectrometry

Two-dimensional gas chromatography coupled with time of flight mass spectrometry is a powerful tool for identifying and quantifying components in complex mixtures. It has been used to analyze gasoline, jet fuel, diesel, bio-diesel and organic fraction of bio-crude/bio-oil. In these experiments, the first dimension of separation was non-polar, followed by a polar separation. Aqueous fractions of bio-crude and other aqueous samples have been examined with similar column combinations. However, sample preparation techniques such as derivatization, solvent extraction, and solid-phase extraction were necessary prior to analysis. In this study, aqueous fraction obtained from hydrothermal liquefaction of algae was characterized by two-dimensional gas chromatography coupled with time of flight mass spectrometry without prior sample preparation techniques using a polar separation in the first dimension followed by a non-polar separation. Two-dimensional plots from this analysis were compared with those obtained from the more traditional column combination. Results from qualitative characterization aqueous fractions of algal bio-crude are discussed in detail. The advantages of using a polar separation followed by a non-polar separation for characterization of organics in aqueous samples by two-dimensional gas chromatography coupled with time of flight mass spectrometry are highlighted.

aquatic biomass↗
DOE OSTI2015

Characterization of the aqueous fraction from hydrothermal liquefaction of algae using 2D gas chromatography with time-of-flight mass spectrometry

Two-dimensional gas chromatography coupled with time of flight mass spectrometry is a powerful tool for identifying and quantifying components in complex mixtures. It has been used to analyze gasoline, jet fuel, diesel, bio-diesel and organic fraction of bio-crude/bio-oil. In these experiments, the first dimension of separation was non-polar, followed by a polar separation. Aqueous fractions of bio-crude and other aqueous samples have been examined with similar column combinations. However, sample preparation techniques such as derivatization, solvent extraction, and solid-phase extraction were necessary prior to analysis. In this study, aqueous fraction obtained from hydrothermal liquefaction of algae was characterized by two-dimensional gas chromatography coupled with time of flight mass spectrometry without prior sample preparation techniques using a polar separation in the first dimension followed by a non-polar separation. Two-dimensional plots from this analysis were compared with those obtained from the more traditional column combination. Results from qualitative as well as quantitative characterization of aqueous fractions of algal bio-crude are discussed in detail. The advantages of using a polar separation followed by a non-polar separation for characterization of organics in aqueous samples by two-dimensional gas chromatography coupled with time of flight mass spectrometry are highlighted.

Panisko, Ellen A.↗
DOE OSTI2023

Comprehensive two-dimensional gas chromatography under low-pressure conditions

The analysis of thermally labile and high-boiling point compounds by gas chromatography (GC) can be a challenge. One technique to overcome these challenges is low-pressure GC, which uses the vacuum produced from the mass spectrometer and wide-bore columns to elute compounds at significantly lower temperatures. While GC-MS is a powerful technique, comprehensive two-dimensional gas chromatography (GC × GC), allows for resolution of compounds that would typically coelute using GC. Here, in this study, a pesticide standard mixture (8270 MegaMix Standard) was analyzed using a conventional GC × GC-TOFMS configuration (0.25 mm inner diameter (i.d.) to a 0.18 mm i.d. column) and low-pressure GC × GC-TOFMS configuration (0.53 mm i.d. to a 0.53 mm i.d. column). Elution temperatures, sensitivity, and peak capacity were investigated for both configurations. Compounds eluted an average of 30 °C less on the low-pressure GC × GC-TOFMS configuration compared to the conventional GC × GC-TOFMS configuration. Moreover, the compounds were separated in ~13 min on the low-pressure GC × GC-TOFMS as opposed to 33 min for conventional GC × GC-TOFMS. However, due to the wide-bore columns and faster runtimes the low-pressure GC × GC-TOFMS had a lower, β corrected 2D peak capacity, n c,β,2D , of 1260 while the conventional GC × GC-TOFMS was 3588. Interestingly, both configurations yielded a similar peak capacity production of 93 peaks/min and 107 peaks/min for low-pressure and conventional GC × GC-TOFMS, respectively. A “real world” sample of diesel fuel was tested on the low-pressure and conventional GC × GC-TOFMS configurations and similar results were obtained compared to the pesticide standard mix except the peak capacity production of the low-pressure GC × GC-TOFMS configuration was higher than that of the conventional GC × GC-TOFMS method.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Measuring Solvation Interactions of Deep Eutectic Solvents Formed by Metal Chlorides and an Imidazolium Salt by Inverse Gas Chromatography

Deep eutectic solvents (DESs) represent a class of solvents that offer a number of advantages including minimal toxicity, affordability, low vapor pressure, and simple, environmentally friendly preparation methods. They have found utility in areas, such as gas absorption, metal plating, and extractions. However, the relationship between their solvation properties and chemical composition remains poorly understood. In this study, a broad range of Type I DESs composed of metal chlorides and an imidazolium salt were prepared, employed as gas chromatographic stationary phases, and characterized using the Abraham solvation parameter model by inverse gas chromatography. The Abraham solvation parameter model allows for the study of DES solvation properties and the effects of varying structural components on system constants using a linear-free energy relationship. The DESs were investigated by systematically varying their composition, including the type of metal chloride and the molar ratio between the metal chloride and the imidazolium salt. The results show that hydrogen bond acidity, hydrogen bond basicity, and dipolarity/polarizability interactions are strongly influenced by the type of metal chloride within the DES and the ratio of metal chloride to imidazolium salt in the eutectic mixture. Furthermore, a column pretreatment procedure is presented that enables the effective coating of highly polar DESs onto open tubular capillary gas chromatography columns.

deep eutectic solvent↗
DOE OSTI2023

Development of a Gas Chromatography with High-Resolution Time-of-Flight Mass Spectrometry Methodology for BDNPA/F

Analysis of thermally labile compounds such as bis(2,2-dinitropropyl) acetal/formal (BDNPA/F), an energetic plasticizer, is usually performed via liquid chromatography (LC) as opposed to gas chromatography (GC) due to thermal decomposition in the inlet or the analytical column. While LC is a powerful technique, the analysis of volatile and semivolatile compounds is best suited to GC. Herein, a method was developed for a gas chromatograph coupled to high-resolution mass spectrometer (GC-HRMS), utilizing a programmable temperature vaporizer (PTV) inlet. A subset of the native compounds and several produced by the thermal decomposition of BDNPA/F in the inlet were evaluated by using multiple PTV inlet parameters to determine the optimal ramp rate and final temperature of the inlet (60 °C/min from 60 to 325 °C). The optimized GC-HRMS method nearly reduced all thermal decomposition, allowing for an excellent separation to be obtained. Furthermore, multiple ionization methods, including electron impact (EI), negative chemical ionization (NCI), and positive chemical ionization (PCI), were used to explore the many chemical differences between the BDNPA/F samples. A preliminary investigation of the benefits of using GC-HRMS to evaluate the chemical differences between unaged and aged BDNPA/F samples for unique insight was evaluated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Hydrogen Analysis by Gas Chromatography–Mass Spectrometry

The detection of hydrogen in complex gas mixtures is essential for many applications. Conventional approaches such as gas chromatography (GC) with thermal conductivity detection (TCD) and residual gas analyzers (RGAs) face significant limitations: TCD exhibits poor response when helium is used as a carrier gas, whereas RGAs lack chromatographic separation, preventing reliable quantification of hydrogen because of interference from other species. Traditional GC methods rely on dual-column configurations with packed or molecular-sieve porous layer open tubular (PLOT) columns to separate hydrogen from O2, N2, CO, CO2, CH4, and other hydrocarbons, increasing system complexity and limiting compatibility with mass spectrometry (MS) detection. In this work, we developed and validated a robust GC–MS method capable of directly detecting and quantifying hydrogen using electron ionization (EI) without dopants, reagent gases, or ion–molecule reaction schemes. By integrating a modified EI source and a cryogenically cooled single capillary column configuration, we achieved baseline separation of hydrogen from all major permanent gases and hydrocarbons in a refinery gas mixture using helium as the carrier gas. The method demonstrated excellent linearity, high sensitivity, and exceptional reproducibility. Adjustable sample-loop volumes and split ratios enabled optimization of peak shape and signal-to-noise performance for trace-level and percent-level hydrogen concentrations. Beyond hydrogen quantitation, the method provides simultaneous compositional profiling of other gases in a mixture in a single run, making it valuable for a wide range of tasks.

Lobodin, Vlad [ORNL]↗
DOE OSTI2021

Physicochemical Gas–Solid Sorption Properties of Geologic Materials Using Inverse Gas Chromatography

The goal of this study was to determine the physicochemical properties of a variety of geologic materials using inverse gas chromatography (IGC) by varying probe gas selection, temperature, carrier gas flow rate, and humidity. This is accomplished by measuring the level of interaction between the materials of interest and known probe gases. Identifying a material’s physicochemical characteristics can help provide a better understanding of the transport of gaseous compounds in different geologic materials or between different geological layers under various conditions. Our research in this study focused on measuring the enthalpy (heat) of adsorption, Henry’s constant, and diffusion coefficients of a suite of geologic materials, including two soil types (sandy clay-loam and loam), quartz sand, salt, and bentonite clay, with various particle sizes. The reproducibility of IGC measurements for geologic materials, which are inherently heterogeneous, was also assessed in comparison to the reproducibility for more homogeneous synthetic materials. This involved determining the variability of physicochemical measurements obtained from different IGC approaches, instruments, and researchers. For the investigated IGC-determined parameters, the need for standardization became apparent, including the need for application-relevant reference materials. The inherent physical and chemical heterogeneities of soil and many geologic materials can make the prediction of sorption properties difficult. Characterizing the properties of individual organic and inorganic components can help elucidate the primary factors influencing sorption interactions in more complex mixtures. This research examined the capabilities and potential challenges of characterizing the gas sorption properties of geologic materials using IGC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Crosslinked polymeric ionic liquid stationary phases incorporating a combination of silver(I) and copper(II) ions for olefin separations by gas chromatography

The development of efficient and selective olefin separation technologies is a critical challenge within the chemical industry given the high energy demands of conventional cryogenic distillation methods. To address this, the study explores the effectiveness of polymeric ionic liquid (PIL) stationary phases in gas chromatography (GC) that incorporate both silver(I) ([Ag + ]) and copper(II) ([Cu 2+ ]) ions for enhanced olefin separation via π-complexation interactions. Further, the effects of both non-crosslinked and crosslinked PIL stationary phases containing varying ratios of [Ag⁺] and [Cu²⁺] ions were systematically investigated to evaluate their impact on the separation of olefins from paraffins and structurally similar olefins. Retention measurements using a broad range of olefinic probes revealed that [Ag⁺] ions provided stronger and more consistent π-complexation in PIL-based stationary phases, while [Cu²⁺] ions preferentially enhance olefin retention in crosslinked systems. Furthermore, thermal stability studies showed that [Ag + ]-containing PIL stationary phases maintain stable olefin separation efficiency over prolonged exposure under elevated temperatures, while crosslinked PIL stationary phases containing [Cu 2+ ] ions exhibited stronger retention due to increased surface adsorption. These findings provide insight into the tunability of metal–olefin interactions using PIL-based stationary phases and suggest design strategies for achieving thermally stable and highly selective chromatographic separations of unsaturated hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Metal-Organic Framework Thin Films as Stationary Phases in Microfabricated Gas-Chromatography Columns.

The overarching goal of this project is to integrate Sandia's microfabricated gas-chromatography ( GC) columns with a stationary phase material that is capable of retaining high-volatility chemicals and permanent gases. The successful integration of such a material with GCs would dramatically expand the repertoire of detectable compounds for Sandia's various microanalysis systems. One such promising class of candidate materials is metal-organic frameworks (MOFs). In this report we detail our methods for controlled deposition of HKUST-1 MOF stationary phases within GC columns. We demonstrate: the chromatographic separation of natural gas; a method for determining MOF film thickness from chromatography alone; and the first-reported GC x GC separation of natural gas -- in general -- let alone for two disparate MOF stationary phases. In addition we determine the fundamental thermodynamic constant for mass sorption, the partition coefficient, for HKUST-1 and several light hydrocarbons and select toxic industrial chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Non-targeted discovery-based analysis for gas chromatography with mass spectrometry: A comparison of peak table, tile, and pixel-based Fisher ratio analysis

The ability to discover minute differences between samples or sample classes for gas chromatography coupled to mass spectrometry (GC-MS) can be a challenging endeavor, especially when those differences are not a priori . Fisher ratio (F-ratio) analysis is an apt technique to probe the differences between GC-MS chromatograms. F-ratio analysis is a supervised, non-targeted, discovery-based method that compares two different samples (or sample classes) to reduce the GC-MS dataset into a hit list composed of class distinguishing compounds. Three different F-ratio techniques, peak table, tile, and pixel-based were used to “discover” nine non-native analytes that were spiked into gasoline at four different nominal concentrations of 250, 85, 25, 5 parts-per-million (ppm). For the tile and pixel-based F-ratio calculations, a novel methodology is introduced to improve the sensitivity of the F-ratio calculations while reducing false positives. Furthermore, we use a combinatorial technique using null class comparisons, termed null distribution analysis, to determine a statistical F-ratio cutoff for analysis of the hit lists. The pixel-based algorithm was the most sensitive method and was able to “discover” all nine spiked analytes at a nominal concentration of 250 ppm albeit with one false positive interspersed towards the bottom of the hit list. The pixel-based software was also able to “discover” more of the spiked analytes at the lower concentrations with seven of the spiked analytes “discovered” at 85 ppm, four of the spiked analytes “discovered” at 25 ppm, and one analyte “discovered” at 5 ppm.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Understanding Biomass and Polymer Feedstock Variability Through Analytical Pyrolysis and Two Dimensional Gas Chromatography and Mass Spectrometry

Moving toward a circular carbon economy requires enabling reuse of carbon-based macromolecules like those in biomass and polymers. Meeting this goal requires increased upcycling of waste products into higher value products. For biomass waste such as corn stover, pine needles, or bark, one approach is using pyrolysis to convert these feedstocks into bio-oil that can be used for liquid fuel or transformed into other hydrocarbon based products, like bio-polymers. Waste plastics can be upcycled or recycled into new products, or alternatively converted into bio-oil by pyrolysis. Macromolecules from biomass and polymers are challenging to convert into liquid fuel or chemical feedstocks, due to large and sometimes heterogeneous networks of polymeric bonds. We work with the Idaho National Laboratory’s Biomass Feedstock National User Facility and Department of Energy’s Feedstock Conversion Interface Consortium to develop a molecular understanding of biomass variability that occurs naturally and as a result of storage or preprocessing techniques applied to feedstocks, to understand chemical reactions occurring during pyrolysis and other biomass or polymer conversion techniques. Using two dimensional gas chromatography mass spectrometry coupled to analytical pyrolysis provides insight into the molecular changes that occur during the pyrolysis event, and these insights can extend to bench or pilot scale pyrolysis conversions. Understanding pyrolysis of biomass and polymers at a molecular level contributes to development of new tools to predict and manipulate the optimum conditions and identify the best storage, preprocessing, and conversion techniques to maximize output of specific high-value chemical species in the conversion to fuels, or to characterize feedstocks for blending before pyrolysis. Identification and understanding of the molecular level changes resulting from novel preprocessing techniques that can be used to control and manipulate the chemical output of bench or pilot scale pyrolysis is another focus of investigation, including the use of gamma irradiation, acid, or enzyme pre-treatments. We also focus on the impacts of storage conditions and techniques, which can affect moisture levels, degradation, and impacts from naturally occurring microbes in the environment.

09 BIOMASS FUELS↗
DOE OSTI2024

Deep eutectic solvents as green and sustainable diluents in headspace gas chromatography for the determination of trace level genotoxic impurities in pharmaceuticals

Genotoxic impurities (GTIs) are potential carcinogens that need to be controlled down to ppm or lower concentration levels in pharmaceuticals under strict regulations. The static headspace gas chromatography (HS-GC) coupled with electron capture detection (ECD) is an effective approach to monitor halogenated and nitroaromatic genotoxins. Deep eutectic solvents (DESs) possess tunable physico-chemical properties and low vapor pressure for HS-GC methods. In this study, zwitterionic and non-ionic DESs have been used for the first time to develop and validate a sensitive analytical method for the analysis of 24 genotoxins at sub-ppm concentrations. Compared to non-ionic diluents, zwitterionic DESs produced exceptional analytical performance and the betaine: 7 (1,4- butane diol) DES outperformed the betaine: 5 (1,4-butane diol) DES. Limits of detection (LOD) down to the 5-ppb concentration level were achieved in DESs. Wide linear ranges spanning over 5 orders of magnitude (0.005–100 µg g –1 ) were obtained for most analytes with exceptional sensitivities and high precision. The method accuracy and precision were validated using 3 commercially available drug substances and excellent recoveries were obtained. Finally, this study broadens the applicability of HS-GC in the determination of less volatile GTIs by establishing DESs as viable diluent substitutes for organic solvents in routine pharmaceutical analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗