Composition Determination of Low-Pressure Gas-Phase Mixtures by 1H NMR Spectroscopy.

1H NMR spectroscopy was used to analyze gas-phase mixtures of methane and propane at pressures near 0.1 MPa. The mixtures were prepared gravimetrically and had low uncertainty in their composition. The primary mixture used for this work had a methane mole fraction of xmethane,grav = (0.506875 ± 0.00019) and a propane mole fraction of xpropane,grav = (0.493125 ± 0.00019). NMR samples were prepared in two types of commercially available sample tubes that seal with a PTFE piston. Sample pressures ranged from 0.02 to 0.5 MPa. An analysis of measurement uncertainty for the NMR method resulted in combined standard uncertainties that decreased from 0.0082 x to 0.0010 x, as the pressure increased from 0.02 to 0.5 MPa. The larger uncertainties at lower pressures were primarily caused by uncertainties associated with phasing and baseline correction. A key difficulty in working with gas-phase samples, especially at lower pressures, is that the spectral peaks are inherently broad. Consequently, peak overlap was problematic, and it was not always possible to integrate a high percentage of a peak's intensity. However, with corrections to the integrated areas, based on the assumption of ideal Lorentzian peak shapes, excellent agreement between the NMR analyses and the gravimetric composition was observed across the entire pressure range. These experiments demonstrate the potential of 1H NMR for quantitative composition determinations of low-pressure gas-phase mixtures.

Direct nuclear magnetic resonance observation of odorant binding to mouse odorant receptor MOR244-3.

Mammals are able to perceive and differentiate a great number of structurally diverse odorants through the odorant's interaction with odorant receptors (ORs), proteins found within the cell membrane of olfactory sensory neurons. The natural gas industry has used human olfactory sensitivity to sulfur compounds (thiols, sulfides, etc.) to increase the safety of fuel gas transport, storage, and use through the odorization of this product. In the United States, mixtures of sulfur compounds are used, but the major constituent of odorant packages is 2-methylpropane-2-thiol, also known as tert-butyl mercaptan. It has been fundamentally challenging to understand olfaction and odorization due to the low affinity of odorous ligands to the ORs and the difficulty in expressing a sufficient number of OR proteins. Here, we directly observed the binding of tert-butyl mercaptan and another odiferous compound, cis-cyclooctene, to mouse OR MOR244-3 on living cells by saturation transfer difference (STD) nuclear magnetic resonance (NMR) spectroscopy. This effort lays the groundwork for resolving molecular mechanisms responsible for ligand binding and resulting signaling, which in turn will lead to a clearer understanding of odorant recognition and competition.

Modeling RP-1 fuel advanced distillation data using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry and partial least squares analysis.

Recent efforts in predicting rocket propulsion (RP-1) fuel performance through modeling put greater emphasis on obtaining detailed and accurate fuel properties, as well as elucidating the relationships between fuel compositions and their properties. Herein, we study multidimensional chromatographic data obtained by comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GC × GC-TOFMS) to analyze RP-1 fuels. For GC × GC separations, RTX-Wax (polar stationary phase) and RTX-1 (non-polar stationary phase) columns were implemented for the primary and secondary dimensions, respectively, to separate the chemical compound classes (alkanes, cycloalkanes, aromatics, etc.), providing a significant level of chemical compositional information. The GC × GC-TOFMS data were analyzed using partial least squares regression (PLS) chemometric analysis to model and predict advanced distillation curve (ADC) data for ten RP-1 fuels that were previously analyzed using the ADC method. The PLS modeling provides insight into the chemical species that impact the ADC data. The PLS modeling correlates compositional information found in the GC × GC-TOFMS chromatograms of each RP-1 fuel, and their respective ADC, and allows prediction of the ADC for each RP-1 fuel with good precision and accuracy. The root-mean-square error of calibration (RMSEC) ranged from 0.1 to 0.5 °C, and was typically below ∼0.2 °C, for the PLS calibration of the ADC modeling with GC × GC-TOFMS data, indicating a good fit of the model to the calibration data. Likewise, the predictive power of the overall method via PLS modeling was assessed using leave-one-out cross-validation (LOOCV) yielding root-mean-square error of cross-validation (RMSECV) ranging from 1.4 to 2.6 °C, and was typically below ∼2.0 °C, at each % distilled measurement point during the ADC analysis.

High-density biosynthetic fuels: the intersection of heterogeneous catalysis and metabolic engineering.

Biosynthetic valencene, premnaspirodiene, and natural caryophyllene were hydrogenated and evaluated as high performance fuels. The parent sesquiterpenes were then isomerized to complex mixtures of hydrocarbons with the heterogeneous acid catalyst Nafion SAC-13. High density fuels with net heats of combustion ranging from 133-141 000 Btu gal(-1), or up to 13% higher than commercial jet fuel could be generated by this approach. The products of caryophyllene isomerization were primarily tricyclic hydrocarbons which after hydrogenation increased the fuel density by 6%. The isomerization of valencene and premnaspirodiene also generated a variety of sesquiterpenes, but in both cases the dominant product was δ-selinene. Ab initio calculations were conducted to determine the total electronic energies for the reactants and products. In all cases the results were in excellent agreement with the experimental distribution of isomers. The cetane numbers for the sesquiterpane fuels ranged from 20-32 and were highly dependent on the isomer distribution. Specific distillation cuts may have the potential to act as high density diesel fuels, while use of these hydrocarbons as additives to jet fuel will increase the range and/or time of flight of aircraft. In addition to the ability to generate high performance renewable fuels, the powerful combination of metabolic engineering and heterogeneous catalysis will allow for the preparation of a variety of sesquiterpenes with potential for pharmaceutical, flavor, and fragrance applications.

Weathering Patterns of Ignitable Liquids with the Advanced Distillation Curve Method.

One can take advantage of the striking similarity of ignitable liquid vaporization (or weathering) patterns and the separation observed during distillation to predict the composition of residual compounds in fire debris. This is done with the advanced distillation curve (ADC) metrology, which separates a complex fluid by distillation into fractions that are sampled, and for which thermodynamically consistent temperatures are measured at atmospheric pressure. The collected sample fractions can be analyzed by any method that is appropriate. Analytical methods we have applied include gas chromatography (with flame ionization, mass spectrometric and sulfur chemiluminescence detection), thin layer chromatography, FTIR, Karl Fischer coulombic titrimetry, refractometry, corrosivity analysis, neutron activation analysis and cold neutron prompt gamma activation analysis. We have applied this method on product streams such as finished fuels (gasoline, diesel fuels, aviation fuels, rocket propellants), crude oils (including a crude oil made from swine manure) and waste oils streams (used automotive and transformer oils). In this paper, we present results on a variety of ignitable liquids that are not commodity fuels, chosen from the Ignitable Liquids Reference Collection (ILRC). These measurements are assembled into a preliminary database. From this selection, we discuss the significance and forensic application of the temperature data grid and the composition explicit data channel of the ADC.

Findings and Recommendations From the Joint NIST-AGA Workshop on Odor Masking.

Since the days of the alchemist, the observation that some substances have a smell while other substances do not has been a source of fascination. The sense of smell, or olfaction, is our least understood sense, however it is important for many human functions, including digestion, food selection and hazard avoidance. The detailed explanation of why individual chemicals (called odorants) might have a particular smell is still elusive. The situation with mixtures of odorants is even more complex and interesting. A number of distinct odorant mixture phenomena have been documented. Odorant suppression (sometimes called masking), conjugation (as described first by Zwaadermaker) and cross-adaptation are among a collection of such phenomena. They are related to the differential effects that one odorant species will have when mixed with another. Masking is a term that describes situations in which one odorant can overpower the sensation of another. There may be profound technological implications in a number of industrial sectors, most prominently in the fuel gas sector. Here, masking is suspected when the odorant that is added to natural gas can be detected by analytical instrumentation, but cannot be properly detected by an observer with a normal sense of smell. Note that this phenomenon is distinct from odor fade, which more properly describes a decrease in the concentration of an odorant rather than a decrease, disappearance or qualitative change in the perception of the odor in the absence of a change in absolute concentration. Anecdotal descriptions of masking events in the natural gas industry have persisted for over a decade, with the frequency of such events on the rise. Pursuant to the philosophy that the technological problem cannot be addressed until the basic science is understood, NIST, in collaboration with the American Gas Association (AGA), sponsored a workshop that brought together olfactory scientists and natural gas operations personnel in an effort to achieve a common understanding and identify critical research questions. This document is a summary of that workshop, and most importantly, a compendium of the findings and recommendations that resulted from the meeting.

Trace headspace sampling for quantitative analysis of explosives with cryoadsorption on short alumina porous layer open tubular columns.

Quantitative headspace (HS) measurements have been performed on the practical industrial and military plastic bonded explosives (PBX) tagged-C-4, Semtex-1A, Semtex-H, detonating cord (detcord), and sheet explosive (Detaflex). The measurements were made by a modified purge and trap technique developed in our laboratory on the basis of cryoadsorption on short alumina-coated porous layer open tubular (PLOT) columns. Trace compounds (of both high and low volatility) were identified and quantitated as a function of HS collection temperature. The data are presented in the form of van't Hoff equations. The linear relationship of the recovered mass as a function of inverse collection temperature reveals the predictive capabilities of the methodology employed here. Knowledge of the compounds that can be detected, along with the expected concentrations to be collected, can aid in detection of explosive materials. Additionally, these data can aid in the standardization, calibration, and certification of energetic material detection devices and can aid in the training of canines for explosive detection.

Complex fluid analysis with the advanced distillation curve approach.

An improved method for measuring distillation curves reveals the physicochemical properties of complex fluids such as fuels.

Simple, quantitative headspace analysis by cryoadsorption on a short alumina PLOT column.

The use of purge and trap methods for sampling volatile organic compounds prior to chromatographic analysis is a mature technology. Application to low volatility compounds has been far less facile and sensitive. Especially problematic has been applications that require precise quantitative analysis and analyses as a function of sample temperature, especially for low volatility analytes. In this paper, we have applied short lengths of alumina-coated PLOT columns as purge traps and operate the traps at low temperature during the collection cycles to improve efficiency in a method called cryoadsorption. We have applied the method as a function of temperature to a medium volatility solid, coumarin, as a demonstration, with further application to the pure explosive compound 2,4,6-trinitrotoluene (TNT) and the practical explosive C-4. We estimate that by use of mass spectrometry, the sampling method discussed in this paper can provide a detection limit of 0.0019 microg TNT per gram of substrate (determined with a 60 min sweep with the sample held at 60 degrees C). Moreover, for quantitative results, we can achieve a percent standard deviation (coefficient of variation) of 10% with samples as low as 0.064 microg TNT per gram of substrate.

A Distillation Approach to Phase Equilibrium Measurements of Multicomponent Fluid Mixtures.

By building on the Advanced Distillation Curve (ADC) approach to measuring the volatility of fuels and other fluid mixtures, the ADC with Reflux or ADCR technique was developed to address the difficulty of experimentally determining the vapor-liquid equilibrium of fluids containing many components. For fuels and other multicomponent mixtures, the ADCR collects data about the chemical compositions of both liquid and vapor phases across a range of temperatures, elucidating the two-phase region at constant pressure. Two simple mixtures were used to demonstrate the ADCR method: an n-decane/n-tetradecane binary and the Huber-Bruno surrogate, a ternary mixture designed to represent the volatility of an aviation turbine kerosene. These mixtures were chosen to test the method because they have been extensively studied and modeled in previous work. For both test fluids, the ADCR measurements of vapor-liquid equilibrium were in good agreement with model predictions. We conclude that the ADCR is a useful method for determining the T-P-x-y behavior of fluid mixtures with many components. The experimental approach presented may support the development of fuels, design of separations, and forensic sciences that use vapor analysis, especially arson fire debris analysis, by providing quantitative data with well-characterized uncertainty describing the relationships between the vapor and condensed phases of a fuel subjected to thermal weathering.

Determination of Cannabinoid Vapor Pressures to Aid in Vapor Phase Detection of Intoxication.

The quest for a reliable means to detect cannabis intoxication with a breathalyzer is ongoing. To design such a device, it is important to understand the fundamental thermodynamics of the compounds of interest. The vapor pressures of two important cannabinoids, cannabidiol (CBD) and Δ9-tetrahydrocannabinol (Δ9-THC), are presented, as well as the predicted normal boiling temperature (NBT) and the predicted critical constants (these predictions are dependent on the vapor pressure data). The critical constants are typically necessary to develop an equation of state (EOS). EOS-based models can provide estimations of thermophysical properties for compounds to aid in designing processes and devices. An ultra-sensitive, quantitative, trace dynamic headspace analysis sampling called porous layered open tubular-cryoadsorption (PLOT-cryo) was used to measure vapor pressures of these compounds. PLOT-cryo affords short experiment durations compared to more traditional techniques for vapor pressure determination (minutes versus days). Additionally, PLOT-cryo has the inherent ability to stabilize labile solutes because collection is done at reduced temperature. The measured vapor pressures are approximately 2 orders of magnitude lower than those measured for n-eicosane, which has a similar molecular mass. Thus, the difference in polarity of these molecules must be impacting the vapor pressure dramatically. The vapor pressure measurements are presented in the form of Clausius-Clapeyron (or van't Hoff) equation plots. The predicted vapor pressures that would be expected at near ambient conditions (25 °C) are also presented.

Application of the Advanced Distillation Curve Method to the Comparison of Diesel Fuel Oxygenates: 2,5,7,10-Tetraoxaundecane (TOU), 2,4,7,9-Tetraoxadecane (TOD), and Ethanol/Fatty Acid Methyl Ester (FAME) Mixtures.

Although they are amongst the most efficient engine types, compression-ignition engines have difficulties achieving acceptable particulate emission and NOx formation. Indeed, catalytic after-treatment of diesel exhaust has become common and current efforts to reformulate diesel fuels have concentrated on the incorporation of oxygenates into the fuel. One of the best ways to characterize changes to a fuel upon the addition of oxygenates is to examine the volatility of the fuel mixture. In this paper, we present the volatility, as measured by the advanced distillation curve method, of a prototype diesel fuel with novel diesel fuel oxygenates: 2,5,7,10-tetraoxaundecane (TOU), 2,4,7,9-tetraoxadecane (TOD), and ethanol/fatty acid methyl ester (FAME) mixtures. We present the results for the initial boiling behavior, the distillation curve temperatures, and track the oxygenates throughout the distillations. These diesel fuel blends have several interesting thermodynamic properties that have not been seen in our previous oxygenate studies. Ethanol reduces the temperatures observed early in the distillation (near ethanol's boiling temperature). After these early distillation points (once the ethanol has distilled out), B100 has the greatest impact on the remaining distillation curve and shifts the curve to higher temperatures than what is seen for diesel fuel/ethanol blends. In fact, for the 15% B100 mixture most of the distillation curve reaches temperatures higher than those seen diesel fuel alone. In addition, blends with TOU and TOD also exhibited uncommon characteristics. These additives are unusual because they distill over most the distillation curve (up to 70%). The effects of this can be seen both in histograms of oxygenate concentration in the distillate cuts and in the distillation curves. Our purpose for studying these oxygenate blends is consistent with our vision for replacing fit-for-purpose properties with fundamental properties to enable the development of equations of state that can describe the thermodynamic properties of complex mixtures, with specific attention paid to additives.

Field portable low temperature porous layer open tubular cryoadsorption headspace sampling and analysis part I: Instrumentation.

Building on the successful application in the laboratory of PLOT-cryoadsorption as a means of collecting vapor (or headspace) samples for chromatographic analysis, in this paper a field portable apparatus is introduced. This device fits inside of a briefcase (aluminum tool carrier), and can be easily transported by vehicle or by air. The portable apparatus functions entirely on compressed air, making it suitable for use in locations lacking electrical power, and for use in flammable and explosive environments. The apparatus consists of four aspects: a field capable PLOT-capillary platform, the supporting equipment platform, the service interface between the PLOT-capillary and the supporting equipment, and the necessary peripherals. Vapor sampling can be done with either a hand piece (containing the PLOT capillary) or with a custom fabricated standoff module. Both the hand piece and the standoff module can be heated and cooled to facilitate vapor collection and subsequent vapor sample removal. The service interface between the support platform and the sampling units makes use of a unique counter current approach that minimizes loss of cooling and heating due to heat transfer with the surroundings (recuperative thermostatting). Several types of PLOT-capillary elements and sampling probes are described in this report. Applications to a variety of samples relevant to forensic and environmental analysis are discussed in a companion paper.

Field portable low temperature porous layer open tubular cryoadsorption headspace sampling and analysis part II: Applications.

This paper details the sampling methods used with the field portable porous layer open tubular cryoadsorption (PLOT-cryo) approach, described in Part I of this two-part series, applied to several analytes of interest. We conducted tests with coumarin and 2,4,6-trinitrotoluene (two solutes that were used in initial development of PLOT-cryo technology), naphthalene, aviation turbine kerosene, and diesel fuel, on a variety of matrices and test beds. We demonstrated that these analytes can be easily detected and reliably identified using the portable unit for analyte collection. By leveraging efficiency-boosting temperature control and the high flow rate multiple capillary wafer, very short collection times (as low as 3s) yielded accurate detection. For diesel fuel spiked on glass beads, we determined a method detection limit below 1 ppm. We observed greater variability among separate samples analyzed with the portable unit than previously documented in work using the laboratory-based PLOT-cryo technology. We identify three likely sources that may help explain the additional variation: the use of a compressed air source to generate suction, matrix geometry, and variability in the local vapor concentration around the sampling probe as solute depletion occurs both locally around the probe and in the test bed as a whole. This field-portable adaptation of the PLOT-cryo approach has numerous and diverse potential applications.

Composition of the C6+ Fraction of Natural Gas by Multiple Porous Layer Open Tubular Capillaries Maintained at Low Temperatures.

As the sources of natural gas become more diverse, the trace constituents of the C6+ fraction are of increasing interest. Analysis of fuel gas (including natural gas) for compounds with more than 6 carbon atoms (the C6+ fraction) has historically been complex and expensive. Hence, this is a procedure that is used most often in troubleshooting rather than for day-to-day operations. The C6+ fraction affects gas quality issues and safety considerations such as anomalies associated with odorization. Recent advances in dynamic headspace vapor collection can be applied to this analysis and provide a faster, less complex alternative for compositional determination of the C6+ fraction of natural gas. Porous layer open tubular capillaries maintained at low temperatures (PLOT-cryo) form the basis of a dynamic headspace sampling method that was developed at NIST initially for explosives in 2009. This method has been recently advanced by the combining of multiple PLOT capillary traps into one "bundle," or wafer, resulting in a device that allows the rapid trapping of relatively large amounts of analyte. In this study, natural gas analytes were collected by flowing natural gas from the laboratory (gas out of the wall) or a prepared surrogate gas flowing through a chilled wafer. The analytes were then removed from the PLOT-cryo wafer by thermal desorption and subsequent flushing of the wafer with helium. Gas chromatography (GC) with mass spectrometry (MS) was then used to identify the analytes.

Comprehensive Assessment of Composition and Thermochemical Variability by High Resolution GC/QToF-MS and the Advanced Distillation-Curve Method as a Basis of Comparison for Reference Fuel Development.

Commercial and military aviation is faced with challenges that include high fuel costs, undesirable emissions, and supply chain insecurity that result from the reliance on petroleum-based feedstocks. The development of alternative gas turbine fuels from renewable resources will likely be part of addressing these issues. The United States has established a target for one billion gallons of renewable fuels to enter the supply chain by 2018. These alternative fuels will have to be very similar in properties, chemistry, and composition to existing fuels. To further this goal, the National Jet Fuel Combustion Program (a collaboration of multiple U.S. agencies under the auspices of the Federal Aviation Administration, FAA) is coordinating measurements on three reference gas turbine fuels to be used as a basis of comparison. These fuels are reference fuels with certain properties that are at the limits of experience. These fuels include a low viscosity, low flash point, high hydrogen content "best case" JP-8 (POSF 10264) fuel, a relatively high viscosity, high flash point, low hydrogen content "worst case" JP-5 (POSF 10259) fuel, and a Jet-A (POSF 10325) fuel with relatively average properties. A comprehensive speciation of these fuels is provided in this paper by use of high resolution gas chromatography/quadrupole time-of-flight - mass spectrometry (GC/QToF-MS), which affords unprecedented resolution and exact molecular formula capabilities. The volatility information as derived from the measurement of the advanced distillation curve temperatures, Tk and Th, provides an approximation of the vapor liquid equilibrium and examination of the composition channels provides detailed insight into thermochemical data. A comprehensive understanding of the compositional and thermophysical data of gas turbine fuels is required not only for comparison but also for modeling of such complex mixtures, which will, in turn, aid in the development of new fuels with the goals of diversified feedstocks, decreased pollution, and increased efficiency.

Diesel Surrogate Fuels for Engine Testing and Chemical-Kinetic Modeling: Compositions and Properties.

The primary objectives of this work were to formulate, blend, and characterize a set of four ultralow-sulfur diesel surrogate fuels in quantities sufficient to enable their study in single-cylinder-engine and combustion-vessel experiments. The surrogate fuels feature increasing levels of compositional accuracy (i.e., increasing exactness in matching hydrocarbon structural characteristics) relative to the single target diesel fuel upon which the surrogate fuels are based. This approach was taken to assist in determining the minimum level of surrogate-fuel compositional accuracy that is required to adequately emulate the performance characteristics of the target fuel under different combustion modes. For each of the four surrogate fuels, an approximately 30 L batch was blended, and a number of the physical and chemical properties were measured. This work documents the surrogate-fuel creation process and the results of the property measurements.

UV/Vis Spectroscopic Evaluation of 4-Nitropyridine N-Oxide as a Solvatochromic Indicator for the Hydrogen-Bond Donor Ability of Solvents.

The potential of 4-nitropyridine N-oxide to act as a solvatochromic indicator of the hydrogen-bond donor ability of solvents has been evaluated. A linear free-energy relationship has been established that is predominantly dependent on the Kamlet-Taft alpha parameter of the solvent. In comparison to the previously reported results obtained for pyridine N-oxide, 4-nitropyridine N-oxide possesses a solvatochromic effect that is located in the long wavelength ultraviolet region (lambda = 330-355 nm) of the spectrum, making it a viable probe for hydrogen-bond donation assessment.

Isothermal Kováts retention indices of sulfur compounds on a poly(5% diphenyl-95% dimethylsiloxane) stationary phase.

Isothermal Kováts retention indices of 21 sulfur compounds relevant to the fuel gas and food industries are reported on a poly(5% diphenyl-95% dimethylsiloxane) capillary column stationary phase. Measurements were performed at four temperatures and the temperature dependence of the values modeled with Antoine-type equations. Indices were calculated using a non-linear technique, and the predicted values were found to agree with values obtained using traditional logarithmic predictions. We demonstrate that there is sufficient separation between retention indices to predict the identity of a compound by its retention index.

Enthalpy of fuel gas odorants on surrogate soil surfaces by gas chromatography.

Heats of adsorption and heats of interaction for natural gas odorants on clay and organo-clay, respectively, were determined by means of wall-coated open-tubular (WCOT) column gas chromatography. The odorants studied are organic thiol and sulfide compounds. Clay stationary phases were created from the synthetic clay Laponite-RD. Subsequent coatings with octadecane created an organo-clay stationary phase. Experimental results show that, as a class, sulfide odorants have larger enthalpies on clay and organo-clay surfaces than thiol odorants. Therefore, we conclude that thiols are less likely to be sequestered on soil surfaces. The effect of hydrated clay surfaces on odorant enthalpies is also presented. Further, we demonstrate that Lewis acid-base chemistry on clay surfaces explains the significant difference in enthalpy magnitudes between the sulfide and thiol classes.