Gas-permeation continuous flow coulometric analysis: determination of sulphur dioxide

 A gas permeation system using two gaseous streams flowing on both sides of a membrane is developed. This gas permeation device and a coulometric detector are adapted for the continuous measurement of relatively high concentrations of sulphur dioxide. The interferences of other gases (NO₂, NO and CO₂) can be eliminated by using a scrubber behind the gas permeation device in the acceptor stream. The effects of the donor flow rates and gas pressure as well as the membrane thickness on the signal are discussed. The relative standard deviation is 1.3% (n=7) for 2.002×10^-3 mol/mol certified sulphur dioxide. Received: 19 July 1996/Revised: 22 October 1996/Accepted: 29 October 1996     

Application of the radioactive ionisation detector to the determination of permanent gases by gas chromatography and some uses in studies of chemical kinetics

It has been found possible to determine volumes of hydrogen, methane, and carbon dioxide within the range 0.1–10 ml at S.T.P. and carbon monoxide and nitrogen within the range 0.1–0.4ml at S.T.P. with an accuracy of around 5 % in a gas chromatograph using the radioactive ionisation detector, provided that the detector temperature and the rate of carrier gas flow through the column are maintained between stated limits. Results of experiments on the sensitivity of the instrument to oxygen, sulphur dioxide, ethane, propane and n-pentane are also reported. Particular attention has been directed towards selecting the most suitable parameter of the response peaks for use in quantitative analysis.

Some particular applications of the argon chromatograph in studies of chemical kinetics involving permanent gases are described, and a method for the removal of corrosive gases from mixtures to be analysed is discussed.     

Evaluation and comparison of selective gas chromatographic detectors for the analysis of pesticide residues

Summary A series of studies is described on the evaluation and comparison of some selective gas chromatographic detectors used in pesticide residue analysis. A detailed study of the optimization and response characteristics of the CsBr and RbCl three-electrode alkali flame ionization detector for N and P compounds, the Coulson electrolytic conductivity detector in the nitrogen, sulphur and pyrolytic modes of operation and the sulphur phosphorus emission detector, a type of flame photometric detector, was carried out to obtain maximum sensitivity and reliability for the analysis of pesticide residues in various biological substrates. It was observed that the alkali flame and electrolytic conductivity detector responses to nitrogen compounds were of the same order, while the electrolytic conductivity detector was more sensitive than the flame photometric detector to sulphur compounds. Also, attempts were made to correlate the responses from these different detector systems using the insecticide chlorpyrifos which contains P, S, Cl and N atoms. The use of chlorpyrifos as an evaluation standard in verifying the acceptable performance of these types of detectors is recommended.Chemistry and Biology Research Institute Contribution No 901     

Improving the Selectivity of Semiconductor Gas Sensors Using the Pulse Adsorption Mode

A procedure is proposed for improving the selectivity of semiconductor gas sensors by the pulsed supply of the test gas mixture, with the use of transient spectroscopy for the separation and assessment of component contributions to the response of an electrical conductivity detector. The experimental verification of the procedure showed that the selective determination of several compounds and their mixtures can be performed using the same SnO₂ detector. The simulation of the detector response as the sum of simplest relaxations revealed three types of surface sites on SnO₂ films, with energy levels of 0.97, 1.38, and 1.50 eV. This means that the number of gas components that can be selectively determined with a single detector is limited to three.     

Quantitative gas chromatographic analysis of hydrocarbon systems using the lovelock diode detector and capillary columns

The application of gas chromatography using capillary columns and the lovelock diode detector to the quantitative analysis of a variety of hydrocarbons in the C₆—C₁₂ molecular weight range is described. The hydrocarbons studied include aliphatics, aromatics, alicyclics, and olefinics. With these molecules and in this molecular weight range, excellent quantitative results are easy to achieve. The response of the lovelock diode under the conditions employed is such that an excellent agreement between weight per cent in the sample and area per cent on the chromatogram exists. The operating parameters of the capillary-diode system have been studied. It has been found that sample size and scavenger flow rate are the only critical parameters controlling quantitative results.     

the microwave-excited emissive detector in gas-phase chromatography-I Some studies with sulphur compounds

An examination is made of the characteristics of a microwave-excited emissive detector and its potential use in the gas chromatography of sulphur compounds. The column was operated slightly above atmospheric pressure (ca. 105 kN m (2)) and the microwave detector at a convenient reduced pressure (e.g., 13-40 mbar). It is concluded that the most sensitive and specific wavelengths for analytical purposes are not necessarily the same for all the sulphur compounds examined, viz. carbon disulphide, thiophen, thioglycollic acid, dimethylsulphoxide and sulphur dioxide. The spectra obtained for each compound with argon or helium as carrier gas were characterized and only the atomic lines due to sulphur at 190.0 and 191.5 nm, the CS system with a bandhead around 257.6 nm and the C(2) bandhead at 516 nm were shown to be common to the organic compounds (except CS for thioglycollic acid). Carbon disulphide was the most easily fragmented and gave a limit of detection of 0.2 ng of sulphur at 257.6 nm even with the low luminosity monochromator used. Thioglycollic acid was the least easily fragmented compound.     

The atomic emission detector in gas chromatographic trace analysis

Summary The atomic emission detector for element-selective detection in gas chromatography shows high selectivities for many elements vs. carbon, coupled with a large dynamic range and relatively low limits of detection. In this work we report on our experience with the detector with respect to the response in dependence on the chemical form of the element monitored, the limit of detection, the selectivity vs. carbon and efforts to improve the limit of detection by varying the flow rate of the make-up gas. Applications discussed include the quantification of a dibenzodioxin/dibenzofuran standard solution, dual-isotope monitoring and the determination of elemental ratios in organic compounds. The work centers on the elements carbon, sulphur, chlorine, bromine and oxygen.Dedicated to Prof. Dr. V. Krivan on the occasion of his 60th birthdayIn part presented at the 20th International Symposium on Environmental Analytical Chemistry, Strasbourg, France, April 1990.     

Configuration and optimization of semiconductor gas sensors as gas chromatographic detectors

A tin oxide, gas-sensitive semiconductor sensor was configured as a gas chromatographic detector and its performance was optimized. Two sensor housings were compared but little difference was found in performance. The flow rate and temperature of the column and the internal heater voltage of the sensor affected both the sensitivity and peak shape. The temperature of the sensor surface was the most critical parameter. Optimal conditions for the gas chromatographic detection of a mixture of alkanes (C₁–C₅) and hydrogen were identified by using the simplex technique. The detection limit for hydrogen was improved by a factor of five to 20 ppb (v/v), illustrating the value of optimization and the excellent sensitivity of the detector. It is concluded that semiconductor gas sensors offer significant advantages as gas chromatographic detectors for the determination of reducing gases.     

Halogenated compound response in an oxygen doped ion mobility detector for capillary gas chromatography

An ion mobility detector that has been specifically developed for interfacing with capillary gas chromatography is investigated in the negative ion mode. Like the electron capture detector, to which this instrument is closely related, the ion mobility detector shows an enhanced response to low molecular weight halogenated compounds when a small quantity of oxygen is doped into the make-up gas flow. Under O₂ doping conditions, the device can operate in a reactant ion monitoring mode responding universally to compounds capable of capturing thermal electrons and in a tunable selective product ion mode providing increased selectivity over that achieved by the ECD. At an oxygen concentration of 0.5%, minimum detectable amounts as low as 600 femtograms have been realized for carbon tetrachloride. Selectivity of chloro- versus bromo- compounds is demonstrated using a mixture of p-dichlorobenzene and p-dibromobenzene.     

The effect of column characteristics on the minimum analyte concentration and the minimum detectable amount in capillary gas chromatography

The need for faster and more efficient separations of complex mixtures of organic compounds by gas chromatography has led to the development of small inner diameter open tubular columns. Owing to their decreased plate height, extremely narrow peaks are obtained. When differently sized columns with equal plate numbers are compared, injection of a fixed amount of a solute will give the highest detector signals for the smallest bore columns. When P is defined as the ratio of the column inlet and outlet pressures, it can be seen from theory that under normalized chromatographic conditions the minimum detectable amount (Q_º) for a mass flow sensitive detector increases proportionally to the square of the column diameter for P = 1. In the situation of greater interest in the practice of open tubular gas chromatography where P is large, a linear relationship is derived between Q_º and the column diameter. It is a widespread misunderstanding, however, that narrow bore capillary columns should be used for this reason in trace analysis. If a fixed relative contribution of the injection band width to the overall peak variance is allowed, a decreased plate height drastically restricts the maximum sample volume to be injected. It is shown that the minimum analyte concentration in the injected sample (C_º) is inversely proportional to the column inner diameter when a mass flow sensitive detector is used. For actual concentrations less than C_º, sample preconcentration is required. The effect of peak resolution and selectivity of the stationary phase in relation to C_º and Q_º will be discussed as well. The validity of the given theory is experimentally investigated. Minimum analyte concentrations and minimum detectable amounts are compared using columns with different inner diameter.     

Determination of sulphur anions by flow injection with a molecular emission cavity detector

A molecular emission cavity detector is attached to a flow injection system for the determination of sulphide, sulphite and sulphate in the ranges 2–130, 3–150 and 5–250 ng S, respectively, in 3-μ1 samples. The sample throughput is abort 100 h^?1. Resolution of mixtures of these anions is also possible, based on the sequential appearance of their S₂ emission peaks. The use of a hydrogen peroxide carrier stream allows the determination of total sulphur.     

Critical appraisal of the flame photometric detector in petroleum analysis

Summary This paper summarises experience gained at the British Petroleum Limited Research Centre, Sunbury-on-Thames, with sulphur selective gas chromatography (GC) detectors. A single flame photometric detector (SFPD) has been in use for three years for research and routine applications. Three areas of interest are described demonstrating in turn different characteristics of the detector. Firstly, a determination of trace levels of individual organo-sulphur compounds in the 15–65°C cut of crude oils illustrates the complexity of using an SFPD in a rigorously quantitative manner. Secondly, the use of an SFPD as a qualitative tool for the comparison of the sulphur distribution of crude oils up to the temperature limit of GC is cited. Finally, a third section describes the properties of a dual flame photometric detector (DFPD) which are compared and contrasted with those of the SFPD.     

Monitoring of odorant components in British natural Gas

Summary The individual sulphur compounds that make up the odorant in natural gas are analysed with purpose-made equipment, using chromatographic separation and a flame photometric detector. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Investigation of sulphur compounds in coal tar using monodimensional and comprehensive two-dimensional gas chromatography

Coal is a non renewable fossil fuel, used mainly as a source of electrical energy and in the production of coke. It is subjected to thermal treatment, pyrolysis, which produces coke as a main product, in addition to a condensed liquid by-product, called tar. Tar is a complex mixture of organic compounds which contains different chemical classes, presenting aromatic and sulphur heterocyclic compounds. In general, identification of these compounds requires steps of isolation and fractionation, mainly due to co-elution of these compounds with polyaromatic hydrocarbons (PAH). The objective of this work is to characterize the sulphur compounds present in the coal tar obtained via pyrolysis, using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry detector (GC×GC/TOFMS). Coal samples from the State of Paraná, Brazil were subjected to laboratorial scale pyrolysis. Several experimental conditions were tested, such as sample weight (5, 10 and 15g), heating ramp (10, 25 and 100°C/min) and final temperature (500, 700 and 900°C). Samples were analyzed by one dimensional gas chromatography (1D-GC) coupled to a quadrupole mass spectrometry detector (GC/qMS) and two-dimensional gas chromatography with time-of-flight mass spectrometry detector (GC×GC/TOFMS). The higher amount of sulphur compounds was obtained at a final temperature of 700°C and a heating ramp of 100°C/min. The main classes observed in the color plot were thiophenes, benzothiophenes and alkylated dibenzothiophenes. GC×GC/TOFMS allowed the identification of the greater number of compounds and the separation of several sulphur compounds from one another. Moreover, separation of sulphur compounds from polyaromatic hydrocarbons and phenols was achieved, which was not possible by 1D-GC. Comparing GC×GC/TOFMS and 1D-GC (SIM mode) also showed that 1D-GC, one of the most employed quantification tools for sulphur compounds, can be misleading for detection, identification and quantification, as the number of isomers of sulphur compounds found was greater than theoretically possible.     

Application of a New pH‐Sensitive Electrode as a Detector in Flow Injection Potentiometry

A new pH sensitive detector for flow‐through potentiometry was developed on the basis of a graphite/quinhydrone composite electrode. The detector was constructed of two polymethylmethacrylate plates between which a 0.1 mm thick sensitive layer is situated. After drilling a hole through the plates, a ring of the sensitive layer is exposed to the solution stream. A conventional calomel reference electrode was placed downstream following the flow‐through sensor. The response behavior in different electrolyte solutions was investigated. The detector shows a Nernstian behavior for injections of hydrochloric acid into a KCl background solution as well as for the steady state response in concentration step experiments using hydrochloric acid and buffer solutions. The response time is sufficiently short for FIA applications (T₉₅ between 3 and 5.4 s). The influences of flow rate and injection volume on the detector signal are discussed.     

Thiosteroids in sewage sludge and its post-treatment products

Different sulphur compound derivatives from steroids were detected and quantified in the analysis of the lipidic fraction of sewage sludge and its post-treatment products, including thermally dried sludge and compost. Some steroid thiols: 5α-cholestane-3β-thiol, 24-methyl-5α-cholestane-3β-thiol and 24-ethyl-5α-cholestane-3β-thiol were detected in the gas chromatography with mass spectrometry detector (GC-MS) analysis. These three compounds, related to the thiostanol family, have only been encountered in previous studies in sea sediments. Gas chromatography with sulphur-selective flame photometric detector (GC-FPD) was used with the objective of detecting other related compounds in sludge. It allowed the detection of other compounds, whose mass spectra could correspond with the one of the steroid enethiols. The research focused on detecting the formation point of these sulphur compounds in the sludge treatment process, as well as their biodegradation resistance in the post-treatment processes. The amount of these products in the sludge was quantified using gas chromatography with flame ionization detector (GC-FID). The result of this study confirms that the identified compounds are not easily biodegradable.     

Effects of contamination on ion mobility detection after gas chromatography

The ion mobility detector is a device that can be used for the selective, ultratrace detection of organic compounds after capillary gas chromatography. It is the only gas chromatographic detector which does not require heteroatomic compounds for selective response, yet concern is often expressed over its quantitative capabilities. Being a secondary ionization device, competitive charge transfer reactions from unseparated compounds or detector gas contamination may decrease the accuracy of measurement. This paper investigates the effects of both electronegative and electro-positive contaminants on the detector's response. In general, it was found that contamination of the detector did affect response but no more severely than in conventional detectors such as the electron-capture detector or the flame ionization detector.     

Determination of trace amounts of hydrogen sulfide in a gas flow using a piezoelectric detector

The following parameters are substantiated and optimized in the detection of H₂S in a gas flow: the nature and flow rate of the carrier gas; the qualitative and quantitative composition of a sensing coating; the technique of its application onto the electrodes of a piezoelectric detector; and the geometrical parameters (volume and configuration) of a flow detecting cell. A testing unit for detecting H₂S in the range from 3 to 18 mg/m³ is developed on the basis of a modified piezoelectric resonator with high frequency characteristics (13–16 MHz).     

On the application of a ZrO2‐based solid electrolyte in isotope ratio mass spectrometry

The application of a high‐temperature electrochemical reactor based on stabilized zirconium dioxide (0.9 ZrO₂0.1 Y₂O₃) for organic gas sampling in continuous‐flow isotope‐ratio mass spectrometry (CF‐IRMS) has been found to be efficient. This solid electrolyte reactor (SER) can also be used as a chromatographic detector for the quantitative measurements of organic gases. A three‐electrode SER system was studied. Complete stoichiometric oxidation of organic gases has been achieved at 900–950°C due to the large catalytic surface area of the porous platinum coating. At this temperature, the oxygen ions formed from the oxygen of ambient air on the outer surface of the reactor migrate through the solid electrolyte under the action of the applied electric field and allow combustion of gases being analyzed to be effected. It should be noted that oxygen gas was not introduced into the gas‐carrier flow. Similar results for the measurements of carbon isotope ratios were obtained at the oxidation of hydrocarbon gases in both the standard and the solid electrolyte reactors. Copyright © 2009 John Wiley & Sons, Ltd.     

Optimisation of the selectivity of a pulsed flame photometric detector for unknown compound screening

Identification of traces of chemical warfare agents (CWA) is generally performed with spectral methods such as mass spectrometry (MS) or NMR, but the use of element-specific detectors is most often required to extract interesting signals from gas chromatographic (GC) data heavily masked by natural interferents. The pulsed flame phosphorus detector (P-FPD) is able to detect phosphorus, sulphur and arsenic, and thus should be very well-suited to CWA detection. However, first results using standard operating conditions recommended by the manufacturer of P-FPD led to false positive detection of phosphorus-containing compounds on the sulphur line. Therefore, an optimisation process of the selectivity of P-FPD for phosphorus versus sulphur or arsenic was undertaken, and allowed to identify gate delay and gate width as crucial parameters for the performance of P-FPD. While selectivity could be significantly improved, unexpectedly, this resulted in a concurrent important loss of sensitivity (ca. 45%) for arsenic, which suggests that this detector should be carefully optimised with respect, and prior to its purported use.