Liquid–Gas Adsorption Chromatography

The history of the discovery, physical and chemical properties, and analytical potentialities of chromatographic methods using the stationary gas phase, such as liquid–gas and liquid–gas adsorption chromatography, are considered. Taking into account the retention of the stationary gas phase in the pores of a hydrophobic support, one can optimize the conditions for the separation and extraction of volatile substances from aqueous solutions on hydrophobic adsorbents in solid-phase extraction and reversed-phase liquid chromatography. Scientific progress is the progress of a method. M.S. Tswett     

Direct measurement of the capillary pressure characteristics of water–air–gas diffusion layer systems for PEM fuel cells

A method and apparatus for measuring the relationship between air–water capillary pressure and water saturation in PEMFC gas diffusion layers is described. Capillary pressure data for water injection and withdrawal from typical GDL materials are obtained, which demonstrate permanent hysteresis between water intrusion and water withdrawal. Capillary pressure, defined as the difference between the water and gas pressures at equilibrium, is positive during water injection and negative during water withdrawal. The results contribute to the understanding of liquid water behavior in GDL materials which is necessary for the development of effective PEMFC water management strategies.     

Surface tension of lead–lithium melts

The temperature and concentration dependences of the surface tension of lithium alloys based on lead are experimentally determined for the first time in a field of compositions with up to 20 at % lithium in lead in the temperature range from the liquidus up to 700 K. The isotherm of surface tension of the studied alloys in the range of compositions with ~10 at % Li in lead contains a minimum, as does the adsorption isotherm of lithium in the sub-eutectic area of PbLi compounds.     

High-temperature Water–Gas Shift catalysts for hydrogen enrichment of a gas produced by biomass steam gasification

To improve the hydrogen content of a biomass steam gasification syngas, Water–Gas Shift Fe/CeO₂ catalysts supported on ceramic foams were developed. The impregnation of ceria as washcoat led to an increase in the support surface area (BET) and to the formation of well-dispersed iron particles (XRD and TPR) by iron oxide impregnation. Catalytic tests were performed at atmospheric pressure with minor pressure drops, under a gas mixture similar to that produced at the gasifier outlet. A satisfactory CO conversion and a large increase in H₂ content were reached by adjusting the operating parameters of the WGS and the catalysts’ composition. After-test characterizations indicated in situ catalysts activation with no over-reduction and a positive action of ceria on iron dispersion and sintering prevention.     

Interaction between cetyltrimethylammonium bromide and β-cyclodextrin: surface tension and interfacial dilational viscoelasticity studies

The interaction between cetyltrimethylammonium bromide (CTAB) and β-cyclodextrin (β-CD) was studied via surface tension and dilational viscoelasticity methods. The effect of sodium bromide and sodium chloride on the interaction between CTAB and β-CD were studied as well. The surface tension isotherms provided a series of parameters, including apparent critical micelle concentration (cmc*), surface tension at the cmc* (γ_cmc), stoichiometry of the complex (R), and the efficiency of adsorption (pC ₂₀ ). The addition of NaBr and NaCl decreases the cmc* of CTAB/β-CD solution. CTAB molecules enter the cavities of β-CD molecules thus formed both 1:1 and 1:2 inclusion complexes. From the change of γ_cmc, it can be seen that the CTAB/β-CD complexes (1:1) act as short-chain alcohol, which decrease γ_cmc, but the depression of cmc* is too small to be detected. R first decreases then increases as a function of NaBr and NaCl. Compared to NaCl, NaBr increases R more efficiently. The presence of NaBr and NaCl increases pC ₂₀ of CTAB/β-CD solution. The results obtained from the dilational viscoelasticity measurements at low dilational frequencies (0.005–0.1 Hz) reveal that the dilational modulus passes through a maxium value with increasing concentration of β-CD at a given concentration of CTAB. The addition of both NaBr and NaCl decreases the dilational modulus of a given concentration CTAB/β-CD solution. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Catalysis of Carbon–Gas Reactions

The characteristic features on the catalysis of carbon–gas reactions has been studied by combining various techniques such as transient kinetics, temperature-programmed desorption and others. Some of recent achievements are presented to comprehend the state of the art. Many industrial processes associated with catalytic carbon–gas reactions are then discussed in relation to the fundamental chemistry of catalysis.     

In situ measurement of gas adsorption processes using Flux Response Technology

Flux Response Technology (FRT) is being developed as a powerful in situ perturbation technique to facilitate detailed characterisation of heterogeneous catalysts. FRT works by measuring minuscule changes in flowrate between two gas streams for potentially any gaseous process involving a change in volume (dV/dt). FRT functions analogous to an electrical Wheatstone bridge assembly whereby gas molecules represent electrons and flow capillaries represent resistors. A perturbation of pressure, temperature, but particularly of concentration causes an imbalance in the system, which is measured directly by a very sensitive differential pressure transducer (DPT). It is demonstrated how FRT can provide a simple, inexpensive, highly accurate means of quantifying the acidic sites of zeolites using ammonia ad/desorption as well as determining the dynamically available surface areas of catalysts using nitrogen adsorption at liquid nitrogen temperature. Temperature programmed experiments (temperature perturbations) can also be employed with FRT to rapidly compare catalyst activity directly (for catalyst development but also for quality control) without the need for much calibration.     

Mercapturic acids derived from toluene in rat urine samples: identification and measurement by gas chromatography–tandem mass spectrometry

Toluene is one of the most widely used CMR chemicals in industry. Worker exposure to this compound is regulated in France, but new, more sensitive methods are required to effectively monitor this exposure. A gas chromatography-tandem mass spectrometry (GC-MS/MS) method was developed and fully validated for the simultaneous determination of urinary toluene mercapturic acids derived from side chain and ring oxidation, i.e., benzylmercapturic acid and the three isomers o-, m- and p-toluylmercapturic acids, respectively. The method involves a simple and efficient two-step preparation procedure consisting of liquid-liquid extraction of the urinary acids followed by a microwave-assisted esterification of the isolated compounds using 2-propanol. The method meets all the required validation criteria: high selectivity, intra-day and inter-day precision ranges between 1.0?% and 12.4?%, with close to 100?% recovery. Linearity has been shown over the reduced concentration range 0.03-0.5?mg/L whereas a multiplicative model (ln-ln transformation) had to be used to describe the full range of concentrations 0.03-20?mg/L. The limits of detection for the four analytes, ranging from 2.8 to 5.5?μg/L, made the method suitable for their identification and quantification in urine from rats inhaling toluene in the 2 to 200?ppm concentration range. All urine samples from exposed rats contained measurable amounts of all metabolites. This is the first time that o- and m-toluylmercapturic acids have been shown to occur. Our results confirm the hypothesis that toluene mercapturic acids derived from ring oxidation exist in three forms.     

LED–LED portable oxygen gas sensor

A portable instrument for oxygen determination, based on the quenching of phosphorescent octaethylporphyrin by gaseous O₂, has been developed using the fluorimetric paired emitter–detector diode technique (FPEDD). The instrument configuration consists of two light-emitting diodes (LEDs) facing each other, with an interchangeable support containing a phosphorescent membrane in between, in which one of the LEDs is used as the light source (emitter LED) and the other, working in reverse bias mode, as the light detector. The feasibility of using a LED as a luminescence detector is studied. Its small size enables integration of the instrument into a portable measurement system. A systematic study of the system capabilities as a portable instrument was performed to optimize range, sensitivity, short term and long term stability, dynamic behaviour, effect of temperature and humidity, and temporal drift.     

Path dependence of surface–tension scaling in binary mixtures

A mean-field free-energy functional for an n-component mixture with an integral non-local interaction is introduced and then written explicitly for a binary mixture. We use this functional to calculate the liquid–vapor surface tension with parameters chosen to model CO₂/n–C₄H₁₀ and CO₂/n–C₁₀H₂₂, and we examine the scaling of the surface tension as a function of the difference in density between the liquid and vapor phases as various critical points are approached. Each critical point is approached on either a constant-temperature or constant-pressure path; we investigate the path dependence of the scaling behavior. For the constant-temperature paths in the CO₂/n–C₄H₁₀ mixture, we compare our calculated results with experimental data. We find no significant dependence of the scaling on the path to the critical point. We note that the asymptotic scaling holds for a larger range of densities the higher the temperature of the critical point.     

The density and surface tension of In–Sn and Cu–In–Sn alloys

Abstract  

The density and surface tension of binary In–Sn and ternary Cu–In–Sn alloys have been measured by a sessile-drop method. Decrease of the density and of the surface tension was observed with rising temperature. With increased Sn content in the alloys, the density increased while the surface tension reduced slightly. Addition of Cu could significantly increase the density and surface tension in the Cu–In–Sn system. The surface tension of the Cu–In–Sn alloys was also calculated by means of Butler’s equation, and compared with experimental values, showing good agreement.     

Gas–liquid equilibrium data for mixture gas of carbon dioxide + nitrogen in 1,2-ethanediamine + triethylene glycol aqueous solution

Isothermal gas–liquid equilibrium (GLE) data were measured for the system of 1,2-ethanediamine (EDA) + triethylene glycol (TEG) + H₂O + carbon dioxide (CO₂) + N₂ at T = 293.15, 298.15, 303.15 and 308.15 K and p = 121.74, 126.94 and 129.87 kPa with CO₂ partial pressure ranging from 0 to 13.0 kPa. Measurements were carried out using a saturation method in a glass absorption apparatus, which was controlled at the constant temperature by a thermostatic circulation bath with a Beckmann thermometer. The measurement uncertainties for temperature, total pressure, CO₂ concentration in the gas phase and CO₂ concentration in the liquid phase were less than ±0.02 K, ±0.15 kPa, ±2.5% and ±0.6, respectively. The results indicate that the addition of TEG into the aqueous EDA solution could significantly improve the stability of EDA in CO₂ absorption process, thus enhancing the performance of aqueous amine-based CO₂ scrubbing.     

Estimation of measurement uncertainty of pesticides,polychlorinated biphenyls and polyaromatic hydrocarbons in sediments by using gas chromatography–mass spectrometry

The evaluation of the uncertainty associated to analytical methods is essential in order to demonstrate quality of a result. However, there is often lack of information about uncertainty of methods to estimate persistent organic pollutants concentration in complex matrix. Current work has thoroughly evaluated uncertainty associated to quantification of several organochloride pesticides, PCBs and PAHs in sediments. A discussion of the main contributions to the overall uncertainty is reported, allowing authors to establish the accuracy of results and plan future improvements. Combined uncertainties ranged between 5–9% (pesticides), 4–7% (PCBs) and 5–10% (PAHs), being uncertainty derived of calibration the main contribution. Also, the analytical procedure was validated analysing a standard reference material (IAEA-408).