Two-Dimensional Gas Chromatography. Concepts,Instrumentation, and Applications – Part 1: Fundamentals,Conventional Two-Dimensional Gas Chromatography,Selected Applications

The writer of this review published in 1978 a three-part article on two-dimensional gas chromatography in the first three issues of this journal [1]. The review was written at a time when capillary column GC was still in its infancy. Commercial columns were (essentially) unavailable and sample introduction into capillary columns was done exclusively in the split mode. Two-dimensional separations were explored in only a few laboratories. The limitations of capillary column technology made this exercise rather difficult. The introduction of fused silica capillary columns in the early eighties drastically changed the landscape in which gas chromatography was practiced. It took the chromatographic community just a few years to convert from packed columns to capillary columns. Instrumentation and accessories specifically designed for capillary column use came onto the market. This writer had great hopes that the revolution in capillary column GC would be mirrored in the development of instrumentation for Two-Dimensional Gas Chromatography. This never materialized. On the contrary, tentative steps taken by a few manufacturers and suppliers of chromatographic equipment fizzled out. It was perhaps the introduction of relatively inexpensive and user friendly GC/MS instrumentation, in combination with nearly indestructible fused silica capillary columns that took away the incentive to develop commercially viable Two-Dimensional Gas Chromatography. Much of the thinking went like this: why insist on good chromatography if mass spectrometry can do the job without the need for complete separation. Some progress in the further development of conventional Two-Dimensional Gas Chromatography has certainly been made over the last 20 years but there has not been a great deal of excitement. Applications have also been relatively sparse and they are limited to just a few areas. Science does not remain static and chromatography is no exception. Progress in gas chromatography is driven by new technology and ideas. Substantial improvements in two-dimensional GC were not forthcoming until Phillips and his research group introduced and implemented an entirely new form of Two-Dimensional Gas Chromatography, called comprehensive two-dimensional GC, or GC×GC. This breakthrough occurred only in 1991 [2]. It does take some time before scientists change attitudes and habits. There is always a time lag between the introduction of new technology and its general acceptance. The public's attitude toward comprehensive Two-Dimensional Gas Chromatography is probably no exception. The number of scientists who are actively pursuing this new branch of gas chromatography is still very small. It is often a single individual who carries the torch. J.B. Phillips' name is synonymous with comprehensive Two-Dimensional Gas Chromatography. He is not only its inventor and proponent but his fertile mind has initiated research in other related areas. Sadly, he passed away shortly before this review was written. This contribution is dedicated to his memory.     

Performance of metal and polymeric O-ring seals during beyond-design-basis thermal conditions

This paper summarizes the small scale thermal exposure test results of the performance of metallic and polymeric O-ring seals typically used in radioactive material transportation packages. Five different O-ring materials were evaluated: Inconel/silver, ethylene-propylene diene monomer (EPDM), polytetrafluoroethylene (PTFE), silicone, butyl, and Viton. The overall objective of this study is to provide test data and insights to the performance of these O-ring seals when exposed to beyond-design-basis temperature conditions due to a severe fire. Tests were conducted using a small-scale stainless steel pressure vessel pressurized with helium to 2 bar or 5 bar at room temperature. The vessel was then heated in an electric furnace to temperatures up to 900 °C for a pre-determined period (typically 8 h–9 h). The pressure drop technique was used to determine if leakage occurred during thermal exposure. Out of a total of 46 tests performed, leakage (loss of vessel pressure) was detected in 13 tests.     

Solar Electricity and Solar Fuels: Status and Perspectives in the Context of the Energy Transition

The energy transition from fossil fuels to renewables is already ongoing, but it will be a long and difficult process because the energy system is a gigantic and complex machine. Key renewable energy production data show the remarkable growth of solar electricity technologies and indicate that crystalline silicon photovoltaics (PV) and wind turbines are the workhorses of the first wave of renewable energy deployment on the TW scale around the globe. The other PV alternatives (e.g., copper/indium/gallium/selenide (CIGS) or CdTe), along with other less mature options, are critically analyzed. As far as fuels are concerned, the situation is significantly more complex because making chemicals with sunshine is far more complicated than generating electric current. The prime solar artificial fuel is molecular hydrogen, which is characterized by an excellent combination of chemical and physical properties. The routes to make it from solar energy (photoelectrochemical cells (PEC), dye‐sensitized photoelectrochemical cells (DSPEC), PV electrolyzers) and then synthetic liquid fuels are presented, with discussion on economic aspects. The interconversion between electricity and hydrogen, two energy carriers directly produced by sunlight, will be a key tool to distribute renewable energies with the highest flexibility. The discussion takes into account two concepts that are often overlooked: the energy return on investment (EROI) and the limited availability of natural resources—particularly minerals—which are needed to manufacture energy converters and storage devices on a multi‐TW scale.     

Perovskites-like composites for CO2 photoreduction into hydrocarbon fuels

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Raman microscopic studies of the liquid-liquid interface between an organic layer and an aqueous solution containing metal ions

Raman microscopic studies of liquid-liquid interfaces between an organic layer and aqueous solutions of metal ions containing extractants are described for the first time. Using a specially constructed cell, the observation of third-phase formation which hinders the mass transfer of metals from the aqueous to the organic layers has been monitored and the spectra discussed in terms of the processes involved and the molecular interactions. The system selected for study was tri-n-butylphosphate-odourless kerosene with zirconium(IV) in aqueous nitric acid solution, a model of an industrial process for nuclear fuels reprocessing. Particulate matter at the interface between the organic and aqueous layers was identified spectroscopically as a carbonate from wash solutions used in neutralisation of the aqueous acid component.     

Modeling of carbonic acid pretreatment process using ASPEN-plusŖ

ASPEN-Plus^Ŗ process modeling software is used to model carbonic acid pretreatment of biomass. ASPEN-Plus was used because of the thorough treatment of thermodynamic interactions and its status as a widely accepted process simulator. Because most of the physical property data for many of the key components used in the simulation of pretreatment processes are not available in the standard ASPEN-Plus property databases, values from an in-house database (INHSPCD) developed by the National Renewable Energy Laboratory were used. The standard non-random-two-liquid (NRTL) or renon route was used as the main property method because of the need to distill ethanol and to handle dissolved gases. The pretreatment reactor was modeled as a “black box” stoichiometric reactor owing to the unavailability of reaction kinetics. The ASPEN-Plus model was used to calculate the process equipment costs, power requirements, and heating and cooling loads. Equipment costs were derived from published modeling studies. Wall thickness calculations were used to predict construction costs for the high-pressure pretreatment reactor. Published laboratory data were used to determine a suitable severity range for the operation of the carbonic acid reactor. The results indicate that combined capital and operating costs of the carbonic acid system are slightly higher than on H₂SO₄-based system and highly sensitive to reactor pressure and solids concentration.     

Liquid Chromatography/Electrochemistry/Mass Spectrometry as Screening Technique for Alcohols and Phenols in Fuels

Liquid chromatography (LC)/electro-chemistry/mass spectrometry (MS) with atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) has been used for the determination of several alcohols and alkylphenols in gasoline and diesel fuels. After rapid sample preparation and a derivatization step with ferrocenecarboxylic acid chloride, the LC separation resulted in complex chromatograms. Selected mass traces helped to identify several groups of alcohols and phenols. Only a sum parameter could be obtained for alcohols and phenols of the same molecular mass because of the large number of structural isomers that were not chromatographically resolved in the mass traces. The results for qualitative screening of seven gasoline and four diesel fuel samples are presented. Apart from alcohols and phenols, several other compounds were also found in the samples. Many of these unknown compounds could be arranged in four series of homologues with a mass difference of 14 mass units. The potential of the method to analyze alcohol and phenol patterns without chromatographic separation was studied using both nanospray and electrospray ion sources in combination with tandem-MS.     

Dealuminated ZSM-5 Zeolite Catalyst for Ethylene Oligomerization to Liquid Fuels

Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Bronsted acid sites in the formation of higher hydrocarbons. The oligomerization of olefins, dependent on the acidity of ZSM-5 zeolite, is an important step in the conversion of natural gas to liquid fuels. The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst. ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios. The FT-IR analysis revealed that the integrated framework aluminum band, non-framework aluminum band, and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated. The performance of the dealuminated zeolite was tested for ethylene oligomerization. The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion, but the gasoline selectivity was reduced compared to the performance     

Capillary GC analysis of diesel fuels using simultaneous parallel triple detection

Diesel fuels from different parts of the UK have been analyzed for polycyclic aromatic hydrocarbons (PAH), nitrogen-containing PAH, and sulfur-containing PAH using capillary column GC with simultaneous parallel triple detection. The concentrations of polyaromatic compounds (PAC) were high and showed considerable variability amongst the fuels. The PAH are mainly naphthalene, fluorene, and phenanthrene and their alkylated homologs; the PANH are mainly carbazole and its methyl derivatives; the PASH are mainly dibenzothiophene and its methyl derivatives.     

Coupling of the Decarboxylation of 2‐Cyano‐2‐phenylpropanoic Acid to Large‐Amplitude Motions: A Convenient Fuel for an Acid–Base‐Operated Molecular Switch

The decarboxylation of 2‐cyano‐2‐phenylpropanoic acid is fast and quantitative when carried out in the presence of 1 molar equivalent of a [2]catenane composed of two identical macrocycles incorporating a 1,10‐phenanthroline unit in their backbone. When decarboxylation is over, all of the catenane molecules have experienced large‐amplitude motions from neutral to protonated catenane, and back again to the neutral form, so that they are ready to perform another cycle. This study provides the first example of the cyclic operation of a molecular switch at the sole expenses of the energy supplied by the substrate undergoing chemical transformation, without recourse to additional stimuli.