Comparison of gas chromatographic and gas chromatographic/mass spectrometric techniques for the analysis of TNT and related nitroaromatic compounds

The use of capillary column gas chromatography and gas chromatography/mass spectrometry for the analysis of a series of standard solutions (0.1 to 10 μg/ml) of 2,4,6-trinitrotoluene (TNT) and eight other nitroaromatic components was evaluated. The techniques included gas chromatography with electron capture detection (GC/ECD), full scan and selected ion monitoring gas chromatography/mass spectrometry with electron impact ionization (EI/FS and EI/SIM), full scan and selected ion monitoring gas chromatography/mass spectrometry with positive ion chemical ionization using methane reagent gas (PICI/FS and PICI/SIM), and full scan and selected ion monitoring gas chromatography/mass spectrometry with negative ion chemical ionization using methane reagent gas (NICI/FS and NICI/SIM). The performance of the techniques was comapared by determining the linear response range, precision, and detection limits of the analyses.     

Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C(n)mim][NTf2] (n=2.4, 6, 8.10) from simple gas H(2), N(2), to polar CO(2), and C(2)H(6), leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution-diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution-diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H(2), N(2)) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C(2)H(6) and CO(2). With exothermic dissolution enthalpy and large order disruptive entropy, C(2)H(6) displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C(2)H(6) gas molecules "peg" on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO(2)-ILs affinity resulted in a more prolonged "residence time" for the gas molecule, typified by reversed CO(2)/N(2) selectivity and slowest CO(2) transport despite CO(2) possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO(2) are further exploited by examining the residing state of CO(2) molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO(2), which provide an explanation to slower CO(2) transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.     

Recent progress in microporous polymers from thermally rearranged polymers and polymers of intrinsic microporosity for membrane gas separation: Pushing performance limits and revisiting trade-off lines

Polymers are promising materials for gas separation membranes. However, the trade-off relationship between gas permeability and selectivity remains an obstacle for achieving polymer membranes that exhibit high gas permeation with desirable separation efficiency. Improving polymer microporosity is of interest in gas separation membranes to enhance gas transport behavior. Polymer modifications by (a) incorporating intrinsically microporous units and/or (b) increasing chain rigidity can enhance microporosity in conventional polymer membrane materials such as polyimides. These strategies are adopted for new classes of microporous polymers, thermally rearranged (TR) polymers, and polymers with intrinsic microporosity (PIMs), to maximize gas transport properties. Their outstanding gas separation performances have redefined the traditional trade-off lines. This review aims to explore the advances in microporous polymers for gas separation applications. The approaches on TR polymers and PIMs to enhance their microporosity are listed, and their developments are evaluated in the context of revisiting performance limits for industrially relevant gas separation applications.     

A comparison of argon and mixed gas plasmas for inductively coupled plasma-mass spectrometry

The effects of adding N₂ to the outer gas flow of an Ar plasma in inductively coupled plasma mass spectrometry (ICP-MS) are illustrated. With 5% N₂ added to the outer gas flow and provided the central (nebulizer) gas flow is increased, modest signal enhancements (up to a factor of 4) are observed. The degree of enhancement depends on the extent to which an element forms a strong metal oxide bond and also, to some extent, on ionization potential. An important feature of N₂ mixed gas plasmas for ICP-MS is that the signals for analyte oxide species (MO⁺) and certain background species (ArO⁺, ArOH⁺, Ar₂⁺, ClO⁺, and ArCl⁺) are significantly reduced (an order of magnitude) by the addition of N₂ to the outer gas flow. In addition to these observations, some results are also presented for O₂ and air (outer gas) mixed gas plasmas and N₂ (central gas) mixed gas plasmas.     

Phase behavior of condensate gas and CO2 / CH4 re-injection performance on its retrograde condensation

Wenchang A Depression in Pearl River Mouth Basin is the largest hydrocarbon generating depression in the west of the area. After more than 30 years of exploitation, a large amount of gas condensate has been produced near the wellbore, which will cause gas condensate damage to the reservoir. It is planned to reinject the self-produced gas from Well WC9-2-X and the gas transported from the WC14-3 gas field to relieve the condensate damage in the near-wellbore area by means of retrograde condensation. In this article, the phase state change process of condensate gas in Well WC9-2-X with temperature and pressure was firstly investigated, and then the retrograde condensation effect of two types of gas on condensate was investigated. The research shows that when the reservoir temperature is 158.80 °C, the dew point pressure of condensate gas is 20.71 MPa, and the maximum amount of condensate is 1.28% (P = 9.01 MPa). Although Wenchang 9–2 is a low condensate reservoir, in the process of depressurization and production over the years, gas condensate has gradually accumulated, resulting in a large amount of gas condensate near the wellbore. With the increase of the gas re-injection amount, the two types of gas have a significant effect on the retrograde condensation of the gas condensate. From the variation trend of the gas and oil density released by the retrograde condensation, it can be seen that the re-injection gas preferentially dissolves the light components in the condensate, and then gradually dissolves the heavy components. The self-produced gas (gas No. 1) of Well WC9-2-X is dominated by CH₄ (78.33 mol%), and the CO₂ / CH₄ contents in the input waste gas (gas No. 2) of the WC14-3 gas field are 42.50 mol% / 41.60 mol%, respectively. The retrograde condensation effect of gas No. 2 is better than gas No. 1, mainly because the content of CO₂ in gas No. 2 is high, and it is easier to achieve the effect of miscible dissolution of condensate when mixed with condensate.It is recommended that gas No.2 should be preferentially used in WC9-2-X well for reinjection of retrograde condensation to relieve condensate damage. This article provides theoretical support for gas re-injection to relieve condensate damage in Wenchang 9–2 gas field, and has important significance for long-term exploitation of condensate gas reservoir.     

Complexes between HC1 and proton acceptors in gas and low temperature argon matrices

FT-IR spectra of mixtures of HC1 and various proton acceptors have been recorded in the gas phase and the enhancement gradient of theP(1) HC1 band with pressure of added gas measured. Bands arising from other collisions to form complexes with longer lifetimes were also measured in the gas and matrix phases. The two kinds of interactions are correlated with proton affinity and dipole moment of added gas.     

Packing density and gas permeability of copolyimides containing bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride constituent

Packing density and gas permeability of two copolyimide series containing an alicyclic monomer, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCDA), and a fluorinated monomer, hexafluoroisopropylidene,2,2-bis(phthalic acid anhydride) (6FDA), were measured. Incorporation of a rigid BCDA segment in 6FDA polyimides either increases gas permeability or improves gas selectivity, depending on the base 6FDA polyimide. In the case of the highly gas permeable 6FDA polyimide, introduction of BCDA further increases gas permeability despite a loss in the amount of free volume. In the moderately gas permeable 6FDA polyimide, on the other hand, the introduction improves gas selectivity. © 1995 John Wiley & Sons, Inc.     

FTIR and GC as complementary tools for analysis of corrosive gases

The gas metrology laboratory of the National Metrology Institute of South Africa has developed methodology for the gravimetric preparation of corrosive gas mixtures such as nitric oxide (NO) in nitrogen, as well as sulphur dioxide (SO₂) in nitrogen or synthetic air. Fourier transform infrared (FTIR) spectroscopy has been used to analyse for trace and ultra trace levels of infrared active gaseous species, such as NO, nitrogen dioxide and SO₂ that are difficult to analyse by other means. These corrosive gas mixtures are also analysed using gas chromatography with pulsed helium ionisation detection to complement the work done using FTIR with infrared active impurities. A comparison between the techniques of FTIR, gas chromatography and non-dispersive infrared spectroscopy for corrosive gas analysis is also presented.     

二甲醚气相色谱相对重量校正因子的测定

用冰冷却水吸收二甲醚配制样品,将ＴＣＤ和ＦＩＤ串联使用,测定出二甲醚在ＴＣＤ和ＦＩＤ上相对于甲醇的重量校正因子分别为０．８６和０．５５,并通过用甲醇催化脱水生成的二甲醚和水的化学计量关系,在线间接测定二甲醚在ＴＣＤ上相对于甲醇的重量校正因子,从而使上述测定结果得到佐证。     

Solvation studies of electrospray ions—method and early results

Experiments are described in which bare (completely desolvated) ions are separated from their source gas and mixed with a bath gas of any desired temperature and precisely controlled composition. The resulting mixture of ions and bath gas is transported by free jet expansion into a vacuum system for mass analysis to reveal the extent to which the ions have formed adducts with other species in the bath gas. Because the ions are separated from their source gas or vapor before they are mixed with the bath gas, the compositions of the bath gas and source gas are completely independent. Thus, one can examine solvation or adduction by any desired species contained in the bath gas without any interference from other species that might be present in the source gas. Reported here are results obtained on the solvation of electrospray ions of a small peptide, leucine-enkephalin, by water and several alkanols. One provocative finding is that a substantial fraction of ions thought to be singly charged monomers turned out to be doubly charged dimers.     

Ambient temperature gas purifier suitable for the trace analysis of carbon monoxide and hydrogen and the preparation of low-level carbon monoxide calibration standards in the field

A novel gas purifier based upon Sofnocat 682, a catalyst containing platinum and palladium on a hydrophobic tin oxide support, is described for the quantitative removal at ambient temperatures of ppm (v/v) and sub-ppm (v/v) levels of carbon monoxide and hydrogen from air and nitrogen gas cylinders. This method provides a simple means of generating either a laboratory or field source of “zero grade” gas for both the trace analysis of carbon monoxide and hydrogen and the preparation of working calibration gas standards of carbon monoxide by using a simple one-step dilution of a higher concentration certified gas standard.     

Hydrothermal Synthesis and Primary Gas Sensing Properties of CuO Nanosheets

Uniformity nanosheets of CuO were prepared by a mild hydrothermal synthesis method. Phase analysis was carried out using x-ray diffraction (XRD) and the result confirmed the CuO nanosheets as a single phase. The field-emission scanning electron microscopy (FE-SEM) was used to observe the morphology of CuO nanosheets while the gas sensing properties of these unique CuO nanosheets were tested at a static state system. The results show that the CuO has uniformity nanosheets, and the gas sensing property show that the CuO nanosheets gas sensor has a stable gas response and the same gas sensitivity trend to tested gases. This method may be suitable for larger-scale production of these CuO nanosheets for practical applications.     

Solid suspension and gas dispersion in gas-solid-liquid agitated systems

The aim of the research work was to investigate the effect of superficial gas velocity and solids concentration on the critical agitator speed, gas hold-up and averaged residence time of gas bubbles in an agitated gas-solid-liquid system. Experimental studies were conducted in a vessel of the inner diameter of 0.634 m. Different high-speed impellers: Rushton and Smith turbines, A 315 and HE 3 impellers, were used for agitation. The measurements were conducted in systems with different physical parameters of the continuous phase. Liquid phases were: distilled water (coalescing system) or aqueous solutions of NaCl (non-coalescing systems). The experiments were carried out at five different values of solids concentration and gas flow rate. Experimental analysis of the conditions of gas bubbles dispersion and particles suspension in the vessel with a flat bottom and four standard baffles showed that both gas and solid phases strongly affected the critical agitation speed necessary to produce a three-phase system. On the basis of experimental studies, the critical agitator speed for all agitators working in the gas-solid-liquid systems was found. An increase of superficial gas velocity caused a significant increase of the gas hold-up in both coalescing and non-coalescing three-phase systems. The type of the impeller strongly affected the parameters considered in this work. Low values of the critical impeller speed together with the relatively short average gas bubbles residence time tR in three phase systems were characteristic for the A 315 impeller. Radial flow Rushton and Smith turbines are high-energy consuming impellers but they enable to maintain longer gas bubbles residence time and to obtain higher values of the gas hold-up in the three-phase systems. Empirical correlations were proposed for the critical agitator speed, mean specific energy dissipated and the gas hold-up prediction. Its parameters were fitted using experimental data.     

Gas permeability in polymer- and surfactant-stabilized bubble films

The gas permeabilities of thin liquid films stabilized by poly(N-isopropylacrylamide) (PNIPAM) and PNIPAM-SDS (sodium dodecyl sulfate) mixtures are studied using the "diminishing bubble" method. The method consists of forming a microbubble on the surface of the polymer solution and measuring the shrinking rates of the bubble and the bubble film as the gas diffuses from the interior to the exterior of the bubble. PNIPAM-stabilized films exhibit variable thicknesses and homogeneities. Interestingly, despite these variable features, the gas permeability of the film is determined principally by the structure of the adsorbed polymer layer that provides an efficient gas barrier with a value of gas permeability coefficient that is comparable to that of an SDS Newton black film. In the presence of SDS, both the film homogeneity and the gas permeability coefficient increase. These changes are related to interactions of PNIPAM with SDS in the solution and at the interface, where coadsorption of the two species forms mixed layers that are stable but that are more porous to gas transfer. The mixed PNIPAM-SDS layers, studied previously for a single water-air interface by neutron reflectivity, are further characterized here in a vertical free-draining film using X-ray reflectivity.     

灰熔聚流化床气化炉分布分离结构的模拟研究

通过CFD双欧拉模型模拟了灰熔聚流化床气化炉内气体、固体颗粒于不同气体分布器、灰分离器结构下的流动行为，阐明了不同中心射流气速下的气体、固体流动循环状况；环管内气流分布与扩管张角的关系以及对颗粒运动的影响。研究结果为认识和改善气化炉煤灰的结渣、团聚、分离等过程提供了一定的理论基础。     

Tuning methane content in gas hydrates via thermodynamic modeling and molecular dynamics simulation

Storage and transportation of natural gas as gas hydrate (“gas-to-solids technology”) is a promising alternative to the established liquefied natural gas (LNG) or compressed natural gas (CNG) technologies. Gas hydrates offer a relatively high gas storage capacity and mild temperature and pressure conditions for formation. Simulations based on the van der Waals–Platteeuw model and molecular dynamics (MD) are employed in this study to relate the methane gas content/occupancy in different hydrate systems with the hydrate stability conditions including temperature, pressure, and secondary clathrate stabilizing guests. Methane is chosen as a model system for natural gas. It was found that the addition of about 1% propane suffices to increase the structure II (sII) methane hydrate stability without excessively compromising methane storage capacity in hydrate. When tetrahydrofuran (THF) is used as the stabilizing agent in sII hydrate at concentration between 1% and 3%, a reasonably high methane content in hydrate can be maintained (∼85–100, v/v) without dealing with pressures more than 5 MPa and close to room temperature.     

Identification of gas emanated from human skin: methane, ethylene, and ethane.

We investigated whether methane, ethylene and ethane gas can be detected in gas emanating from human skin, which is called skin gas. Skin gas was collected with a homemade stainless-steel trap system, which was cooled with liquid nitrogen, and analyzed with a gas chromatograph fitted with a flame ionization detector (FID). Skin-gas samples were obtained by covering a hand for 30 min with a polyfluorovinyl bag in which pure helium gas was introduced. The bag, the trap system and GC were set up online to avoid any contamination by air. Methane, ethylene and ethane in skin gas were successfully collected at an average amount emanated for 30 min (from ten subjects) of 150 +/- 63, 20 +/- 11 and 17 +/- 8 [mean +/- SD] pg/cm2, respectively.     

超临界水中煤与聚苯乙烯的共液化研究

在间歇式高压反应装置中,研究了兖州烟煤与塑料聚苯乙烯(PS)在超临界水中的共液化,考察了水/物料比(质量比10～30)、反应温度(360℃～430℃)和塑料添加量(10%～40%)对煤液化转化率及产物收率的影响.结果表明,随着水/物料比的增加,煤液化转化率先升高,之后变化不大;油气产率则呈上升的趋势.反应温度高于420...     

Nanobubbles at the interface between water and a hydrophobic solid

A very thin layer (5-80 nm) of gas phase, consisting of discrete bubbles with only about 40 000 molecules, is quite stable at the interface between a hydrophobic solid and water. We prepare this gas phase from either ambient air or from CO(2)(g) through a solvent exchange method reported previously. In this work, we examine the interface using attenuated total internal reflection infrared spectroscopy. The presence of rotational fine structure in the spectrum of CO(2) and D(2)O proves that molecules are present in the gas phase at the interface. The air bubbles are stable for more than 4 days, whereas the CO(2) bubbles are only stable for 1-2 h. We determine the average gas pressure inside the CO(2) bubbles from the IR spectrum in two ways: from the width of the rotational fine structure (P(gas) < 2 atm) and from the intensity in the IR spectrum (P(gas) = 1.1 +/- 0.4 atm). The small difference in gas pressure between the bubbles and the ambient (1 atm) is consistent with the long lifetime. The dimensions and curvature of a set of individual bubbles was determined by atomic force microscopy. The pressures of individual bubbles calculated from the measured curvature using the Laplace equation fall into the range P(gas) = 1.0-1.7 atm, which is concordant with the average pressure measured from the IR spectrum. We believe that the difference in stability of the CO(2) bubbles and the air bubbles is due to a combination of the much lower pressure of CO(2) in the atmosphere and the greater solubility of CO(2) in water, compared to N(2) and O(2). As expected, smaller bubbles have a shorter average lifetime than larger bubbles, and the average pressure and the curvature of individual bubbles decreases with time. Surface plasmon resonance measurements provide supporting evidence that the film is in the gas state: the thin film has a lower refractive index than water, and there are few common contaminants that satisfy this condition. Interfacial gas bubbles are not ubiquitous on hydrophobic solids: bubble-free and bubble-decorated hydrophobic interfaces can be routinely prepared.     

Investigation into the determination of trimethylarsine in natural gas and its partitioning into gas and condensate phases using (cryotrapping)/gas chromatography coupled to inductively coupled plasma mass spectrometry and liquid/solid sorption techniques

Speciation of trialkylated arsenic compunds in natural gas, pressurized and stable condensate samples from the same gas well was performed using (Cryotrapping) Gas Chromatography-Inductively Coupled Plasma Mass Spectrometry. The major species in all phases investigated was found to be trimethylarsine with a highest concentration of 17.8 ng/L (As) in the gas phase and 33.2 μg/L (As) in the stable condensate phase. The highest amount of trimethylarsine (121 μg/L (As)) was found in the pressurized condensate, along with trace amounts of non-identified higher alkylated arsines. Volatile arsenic species in natural gas and its related products cause concern with regards to environment, safety, occupational health and gas processing. Therefore, interest lies in a fast and simple field method for the determination of volatile arsenicals. Here, we use simple liquid and solid sorption techniques, namely absorption in silver nitrate solution and adsorption on silver nitrate impregnated silica gel tubes followed by total arsenic determination as a promising tool for field monitoring of volatile arsenicals in natural gas and gas condensates. Preliminary results obtained for the sorption-based methods show that around 70% of the arsenic is determined with these methods in comparison to volatile arsenic determination using GC-ICP-MS. Furthermore, an inter-laboratory- and inter-method comparison was performed using silver nitrate impregnated silica tubes on 14 different gas samples with concentrations varying from below 1 to 1000 μg As/m³ natural gas. The results obtained from the two laboratories differ in a range of 10 to 60%, but agree within the order of magnitude, which is satisfactory for our purposes.