Quantitative determination of gas mixture composition by gas chromatography—New approach

Summary A new method has been developed for the quantitative determination of gas mixture composition where air penetration during gas sample collection would lead to erroneous results. It requires the use of a stationary phase that separates gas sample components and the air and involves 4–5 analyses of samples of equal volumes containing different amounts of air. By graphical extrapolation of the air peak area (S _air ) as a function of the peak areas of the individual components (S _comp ) the areas for these components in the absence of air can be obtained forS _air =0. Using calibration curves for the pure gas components the true quantitative composition of the gas mixture is estimated.     

Firms discuss cross-border gas pipeline

China and Kazakhstan are reviewing the possibility of building a pipeline to deliver natural gas from western Kazakhstan to Xinjiang Uygur Autonomous Region, on China‘s western border, to satisfy the country‘s increasing gas demands.     

Gas–gas experimental interfacial tension measurement

A thermodynamically stable interface can only exist between two immiscible fluids, nonetheless in this work an “immiscible interface” between two gases (CO₂–methane) has been observed and is documented within this paper. This work is the first ever attempt to measure the interfacial tension (IFT) in a gas–gas system, the interfacial tension of supercritical carbon dioxide (SCO₂–methane) was measured at temperatures of 368.15 and 433.15 K and pressures between 6.9 and 41.37 MPa, using a modified pendant drop method. This study was undertaken to investigate the effects of CO₂ injection into a gas reservoir or enhanced gas recovery.     

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.     

Solid-state potentiometric gas sensors—a supplement

Potentiometric in situ gas probes with solid electrolytes were described for the first time 50 years ago. It is the intention of the present communication to give some additions on oxygen sensors in reducing gases which have been neglected in a recent review (J Solid State Electrochem, 13:3, 2009). Today, the most frequently used solid electrolyte gas sensors are the lambda probes. In their electrodes is a very quick change between gas phases with excess of oxygen and excess of components of reducing gases. Changes in the interpretation of the mechanism of the interaction between gas and solid electrolyte in the gas sensors are discussed. At low temperatures, mixed potentials appear which have to be expected at oxygen electrodes also with air and technical oxygen, if these gases are not cleaned particularly. Among the CO₂ sensors, the system with the reference electrode SiO₂, Na₂Si₂O₅ on ß-alumina must be mentioned. This system has special advantages and in the commercially available device it reaches excellent long-term stability. A report about long-term measurements of SO₂ traces in air is worth mentioning. For measurements of SO₂ in industrial gases, Westinghouse has offered a complicated system in the 1980s.     

‘Intelligent’ alarm detector of gas leaks

Three types of tin oxide gas sensors have been developed and a gas-detecting apparatus using the developed sensors has been manufactured. This apparatus has the ability to identify the type of leaking gas out of isobutane, ethanol, hydrogen and carbon monoxide. It can also be used for accumulating data as the terminal unit of a microcomputer. When city gas or carbon monoxide gas is leaking, a pulse is output from the apparatus to an electromagnetic valve which cuts off the path of the gas. The use of the apparatus and microcomputer composes a countermeasure system against gas leak accidents.     

Experimental and mechanism studies on simultaneous desulfurization and denitrification from flue gas using a flue gas circulating fluidized bed

The oxidizing highly reactive absorbent was prepared from fly ash,industry lime,and an oxidizing additive M.Experiments of simultaneous desulfurization and denitrification were carried out in a flue gas circulating fluidized bed(CFB).The effects of influencing factors and calcium availability were also investigated on the removal efficiencies of desulfurization and denitrification.Removal efficiencies of 95.5%for SO2 and 64.8%for NO were obtained respectively under the optimal experimental conditions. The component of the spent absorbent was analyzed with chemical analysis methods.The results in- dicated that more nitrogen species appeared in the spent absorbent except sulfur species.A scanning electron microscope(SEM)and an accessory X-ray energy spectrometer were used to observe micro-properties of the samples,including fly ash,oxidizing highly reactive absorbent and spent absorbent.The simultaneous removal mechanism of SO2 and NO based on this absorbent was pro- posed according to the experimental results.     

Kinetic characteristics of gas–liquid ozone reactions

An experimental chemical method for determining the kinetic characteristics (volumetric mass transfer coefficient and rate constant of a second-order reaction) of gas–liquid ozone reactions in a bubble column reactor is described. The calculation formulas are substantiated, and the ranges of values of the experimental factors that determine the method’s limits of applicability are found. The conditions under which the boundary-value problem of a gas–liquid ozone reaction of the second order can be reduced to a problem of a pseudo-first order reaction allowing an analytical solution are revealed.     

Determination of β-blockers and β-agonists using gas chromatography and gas chromatography-mass spectrometry--a comparative study of the derivatization step

There is a growing demand for the rapid screening of multiple β-blockers and β-agonists in a single analytical run in clinical toxicology, antidoping control, forensic and environmental science. Although GC-MS is very often used to determine pharmaceuticals from these groups of drugs, the literature data on the derivatization and MS analysis of mixtures of these compounds is limited. This paper compares and evaluates derivatization procedures for the determination of six β-blockers (acebutolol, atenolol, metoprolol, nadolol, propranolol, pindolol) and two β-agonists (salbutamol, terbutaline) using GC techniques. Nineteen different derivatizing reagents (nine of them used for the first time with almost all the drugs) were employed in order to obtain a single derivative for each target compound with the greatest effectiveness of this reaction. Trimethylsilylation, tert-butyldimethylsilylation, acylation (e.g. trifluoroacetylation), combined trimethylsilylation and acylation, and the formation of cyclized silyl derivatives were carried out and the mass spectra (EI, 70 eV) recorded. The influence of the reaction time and temperature on these procedures was investigated. Additionally, the effects of the type of solvent and the amount of added trimethylchlorosilane (TMCS) on the silylation of the target compounds using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) were tested. Among of the five mentioned above derivatization procedures applied - trimethylsilylation was found to be the most effective for derivatizing the analytes. The best results were obtained with a 1:1 (v/v) mixture of 99% BSTFA+1% TMCS and ethyl acetate at 60 °C for 30 min. The MS data for different types of β-blocker and β-agonist derivatives is presented. The information in this paper is valuable for scientists working on the determination of β-blockers and β-agonists in biological and environmental matrices.     

UV photolysis of α-cyclohexanedione in the gas phase

Ultraviolet absorption spectrum of α-cyclohexanedione (α-CHD) vapor in the wavelength range of 220-320 nm has been recorded in a 1 m long path gas cell at room temperature. With the aid of theoretical calculation, the band has been assigned to the S(2) ← S(0) transition of largely ππ* type. The absorption cross section at the band maximum (～258 nm) is nearly 3 orders of magnitude larger compared to that for the S(2) ← S(0) transition of a linear α-diketo prototype, 2,3-pentanedione. The photolysis was performed by exciting the sample vapor near this band maximum, using the 253.7 nm line of a mercury vapor lamp, and the products were analyzed by mass spectrometry as well as by infrared spectroscopy. The identified products are cyclopentanone, carbon monoxide, ketene, ethylene, and 4-pentenal. Geometry optimization at the CIS/6-311++G** level predicts that the carbonyl group is pyramidally distorted in the excited S(1) and S(2) states, but the α-CHD ring does not show dissociative character. Potential energy curves with respect to a ring rupture coordinate (C-C bond between two carbonyl groups) for S(0), S(1), S(2), T(1), T(2), and T(3) states have been generated by partially optimizing the ground state geometry at DFT/B3LYP/6-311++G** level and calculating the vertical transition energies to the excited states by TDDFT method. Our analysis reveals that the reactions can take place at higher vibrational levels of S(0) as well as T(1) states.     

Intramolecular penning ionization in benzonitrile—rare gas clusters

A supersonic beam of benzonitrile (Bn) seeded into He, Ar or Kr was ionized by VUV photons from the electron storage ring BESSY at Berlin. Photoionization efficiency curves were measured for Bn, Bn₂, Bn-Ar and Bn-Kr. Resonance peaks in the PIE curves show that excitation energy of the rare gas atom is transferred to the Bn molecule within the heterogeneous cluster, leading to ionization of the molecule and fragmentation of the cluster.     

Mechanisms and solubility equations of gas dissolving in water

The two mechanisms of gas dissolving in water, interstice filling and aquation, are proposed. General equations of gas solubility have been deduced from the mechanisms and experimental observations. Dependence of Henry's coefficient on temperature, pressure, aquation equilibrium constant and gas molecular wlume is discussed. The theoretical equations were verified by experimental data, which shows that the theoretical results of the solubility of methane are in good agreement with the experimental data in the range of 20 -160℃ and under a pressure of less than 60 MPa.     

Direct and indirect photoinduced gas–liquid phase transitions

The condensation of supersaturated vapors of various substances in air under UV irradiation in a cloud chamber has been studied. The irradiation and subsequent photodissociation greatly facilitate the condensation of vapors in comparison with unirradiated mixtures, wherein both a vapor that directly absorbs radiation (direct photoinduced phase transition) and, for example, water vapor in the presence of photodissociating impurities (indirect photoinduced transition) can be condensed.     

The design of membrane vapor–gas separation systems

Membrane vapor–gas separation systems are beginning to be applied to a number of gas separation problems in the petrochemical and refinery areas. In this paper, some of the factors that affect the design of these systems are described using, as an application example, the separation of propylene from nitrogen in polyolefin resin degassing vents.     

Phoenix mars mission—The thermal evolved gas analyzer

The Phoenix spacecraft that was launched to Mars in August 2007 landed safely on the Martian northern arctic region on May 25, 2008. It carried six experiments to study the history of water on the planet and search for organic molecules in the icy subsurface Martian soil. The spacecraft is a lander with an arm and scoop designed to dig a trench though the top soil to reach an expected ice layer near the surface. One of the instruments on board is the thermal evolved gas analyzer (TEGA), which consists of two components, a set of eight very small ovens that will heat samples of the ice soil mixtures from the trench to release imbedded gases and mineral decomposition products, and a mass spectrometer that serves as the analysis tool for the evolved gases, and also for measurements of the composition and isotopic ratios of the gases that comprise the atmosphere of Mars. The mass spectrometer is a miniature magnetic sector instrument controlled by microprocessor-driven power supplies. One feature is the gas enrichment cell that will increase the partial pressures of the noble gases in an atmosphere sample by removing all the active gases, carbon dioxide, and nitrogen, to improve the accuracy of their isotopic ratio measurements.     

Analysis of 28 insecticides in curry leaves (Murraya koenigii L.) by gas chromatography and gas chromatography–mass spectrometry

A simple and efficient method was developed for analysis of 28 insecticides (organochlorines, organophosphates and synthetic pyrethroids) in curry leaves (Murraya koenigii L.). The extraction of the analytes was carried out with acidified acetonitrile and purification with magnesium sulphate, primary secondary amine along with graphitised carbon black to remove excess chlorophyll content in curry leaves. Acetonitrile extracts were changed into hexane + acetone (9 + 1) and hexane + toluene (9 + 1) in the final step. In another method ethyl acetate was used for extraction and purification was carried out as above. The analytes in the samples were determined by gas chromatography (GC) and confirmed by gas chromatography–mass spectrometry (GC–MS). Use of ethyl acetate increased the recovery of the analytes, but co-extractive interference led to higher GC maintenance. Acidified acetonitrile was found to be a better extraction solvent compared with ethyl acetate. The use of hexane:toluene (9:1) as exchange solvent increased the recovery of organochlorine insecticides compared with hexane:acetone (9:1). The limit of quantification (LOQ) of the method was 0.01 mg kg^?1 for organochlorine insecticides and 0.05 mg kg^?1 for organophosphates and synthetic pyrethroids. The recoveries of organochlorines were within 70.36–82.45%; organophosphates, 82.54–90.93% and synthetic pyrethroids, 88.45–90.71% at the LOQ level. The method developed was found suitable for analysis of real samples of curry leaves. The pesticides detected in curry leaves collected from the retail market were mainly organophosphates and synthetic pyrethroids.