Automation of the gas analysis of14C-labelled compounds utilizing a piston-type counter tube

In this paper an automatic apparatus designed for the radioactivity measurement of¹⁴C-labelled organic compounds in the gaseous phase is described. The labelled organic compounds are combusted in a mixture of argon and oxygen. After combustion the oxygen content of the gas is eliminated by passing it through a copper packing. The water and heteroelements present are also removed and the radioactive carbon dioxide gas is swept by argon carrier gas into a piston-type counter tube. In the counter tube the piston forming a dividing wall moves forward in accordance with the rate of combustion and sweeping, and thus sucks the gases leaving the combustion tube into the effective tube volume. The anode wire is carried by a reel located in the piston and a spring device ensures its stretched state. At the end of the sweeping period methane is fed into the counter tube and the activity of the argon—methane—carbon dioxide mixture is measured in the limited proportional region. Manual and automatic operation is possible. The piston-type counter tube provides possibility for strandardization by means of extrapolation and for measurement of absolute activities.     

Massenspektrometrische untersuchungen zur elementaranalyse organischer verbindungen—III: Verbrennungsvorgänge im leeren rohr

A measuring system is described which permits study of all stages of combustion processes as functions of carrier gas, temperature, residence time and tube filling. The organic sample is fed at constant speed into a stream of carrier gas. The mixture reaches the combustion chamber within a few milliseconds via a transfer capillary. With the help of a viscous inlet system, a sample of the resulting reaction products is taken and fed into a mass spectrometer. Reaction time and temperature can be adjusted within wide ranges or varied continuously. A plot of the extent of reaction of the various combustion products against temperature at a chosen reaction time yields an oxidation-thermogram which gives a clear picture of the combustion process. It is evident from thermograms of selected compounds that the samples decompose in the presence of oxygen at appreciably lower temperatures than in inert gas. The primary step of the decomposition is “oxidative pyrolysis” which often leads to other products than “inert pyrolysis”. The intermediate products found are partly structurally specific and, especially with nitrogen-containing samples, are numerous and long-lived (for example, carbon monoxide, nitric oxide, cyanogen, hydrocyanic acid, cyanic acid and methyl cyanate). The notorious “difficult combustibility” is largely due to the fact that carbon monoxide, cyanic and hydrocyanic acids undergo complete combustion only at very high temperature. The combustion properties of the “empty tube” can be improved noticeably by a filling of quartz wool and markedly by partly filling with platinum wool.     

Sample decomposition in an electrically heated cold-trap inlet system for high speed gas chromatography

Thermal decomposition of some hydrocarbon and chlorinated hydrocarbon compounds in metal capillary tubes used in an inlet system for high speed gas chromatography has been investigated. The metal tube is cooled to about ?75°C by a flow of cold nitrogen gas in order to focus a vapor sample cryogenically. A capacitive discharge power supply is then used to heat the metal tube resistively in order to revaporize the sample and introduce it to the separation column as a plug 5-10 ms wide. The effects of tube temperature, tube material, sample vapor residence time, and type of carrier gas on thermal cracking are described. Use of a copper-nickel alloy tube resulted in less cracking than either pure platinum or pure nickel. Cracking is more significant with hydrogen as carrier gas than with helium. Cracking also increases with increasing sample residence time in the hot tube. Quantitative sample injection with minimum decomposition can be obtained for a variety of aliphatic and aromatic hydrocarbons and chlorinated hydrocarbon compounds.     

The use of argon as carrier gas in the microdetermination of oxygen in organic compounds

Argon is recommended as carrier gas in order to improve the efficiency of the method for the microdetermination of oxygen in organic compounds. To demonstrate that the use of argon is advantageous, parallel determinations were performed on a series of organic and inorganic compounds to establish the maximum amounts of substance quantitatively pyrolysable under normal analytical conditions. With argon, the maximum amount of the organic compound giving correct results was usually remarkably increased at all stages of the working life of the tube. This greater efficiency of the system in the conversion to carbon monoxide leads to higher reliability, allows a substantial decrease in the analysis time, and prolongs the life of the filling. The inconvenience of positive blank values with argon can be avoided if reaction tubes of very pure quartz are used.     

Isotope gas analysis of tritium-labelled organic compounds based on pyrolytical decomposition

Summary A procedure has been developed for the activity measurement of tritium-labelled organic compounds in the gas phase. The organic compounds are pyrolysed in hydrogen carrier gas at 1150° and the decomposition products are swept through a carbon packing in accordance with the principle of the oxygen determination developed byUnterzaucher andBürger. The radioactive gas mixture obtained from the sample is swept by the hydrogen carrier gas flowing continuously through the reactor into a proportional counter tube, after the addition of propanebutane counter gas. By closure of the counter tube at a suitable moment, the radioactive gas is quantitatively trapped in the counter tube. The activity is measured in the limited proportional region. No memory effect occurs. The preparation of the sample requires 12 minutes; the relative standard deviation of analysis is <0.5%.

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Zusammenfassung Ein Verfahren zur Aktivitätsbestimmung bei tritium-markierten organischen Verbindungen in der Gasphase wurde ausgearbeitet. Die organischen Substanzen werden in Wasserstoff als Trägergas bei 1150° pyrolysiert. Die Zersetzungsprodukte werden wie bei der Sauerstoffbestimmung nachUnterzaucher bzw.Bürger über eine Kohleschicht geleitet. Das radioaktive Gas-gemisch aus der Probe gelangt mit dem kontinuierlich strömenden Trägergas in ein Proportionalzählrohr, nachdem Propan-Butan-Zählgas zugesetzt wurde. Man schließt das Zählrohr im richtigen Augenblick, um das radioaktive Gas quantitativ zu erfassen. Die Aktivität wird im Proportionalbereich gemessen. Ein Memory-Effekt tritt nicht auf. Die Vorbereitung der Probe beansprucht 12 Minuten. Die relative Standardabweichung ist kleiner als 0,5%.

     

Dual Adsorber-Capillary Column System for Gas Chromatographic Analysis of Air Samples

Abstract

An interface which allows thermal desorption and subsequent capillary gas chromatographic analysis of air samples is described. A small solid-sorbent trap is positioned between the sampling tube and capillary column. A sample thermally released from the sampling tube is transferred by a carrier gas at high flow rate to the trap and retained. From there it is again thermally released and transferred to the capillary column by carrier gas at a low flow rate, as required by capillary GC. The transfer and injection steps are effected by means of externally placed solenoid valves. The performance of the system depends on the desorption temperature and time allowed for transfer of the sample between the two adsorbers and the column. These parameters are programmable and can be changed to suit the requirements of a particular analysis. The system allows the analysis of sub-parts-per-billion concentrations of organic compounds in a comparatively simple and reproducible manner. Operation of the system does not require cryogenic cooling of either the trap or the GC oven. Chromatograms of a variety of air samples are presented and discussed.     

气相色谱-微波等离子体炬原子发射光谱检测器及其响应特性的研究

报道了一种气相色谱用微波等离子体炬原子发射光谱检测器(GC-MPT-AED),以氩气为载气和等离子体工作气体,氧气为清洗气和屏蔽气,研究了MPT-AED对有机化合物中碳元素的响应特性,探讨了氧气作为GC-MPT-AED屏蔽气对碳元素检测性能的影响.     

天然铁矿石为氧载体的生物质化学链气化制合成气实验研究

在一个小型鼓泡流化床反应器上以Ar气为流化介质,对以天然铁矿石为氧载体的生物质化学链气化制合成气过程进行了研究。考察了反应温度对合成气组分、气体产率、碳转化率以及气化效率的影响,反应时间对合成气组分的影响;探讨了氧载体存在对生物质气化过程的影响。结果表明,天然铁矿石可以作为生物质化学链气化制合成气反应过程的氧载体,代替富氧空气或高温水蒸气作为生物质气化的气化剂;随着温度的升高,产物气体中CO、H₂的浓度逐渐增加,CO₂、CH₄浓度缓慢降低;随着反应时间的延长,合成气中H₂、CO、CH₄的相对浓度缓慢增加,而CO₂相对浓度逐渐降低;氧载体的存在能显著提高气体产率和碳的转化率及气化效率。扫描电镜-能谱(SEM-EDS)分析表明,当超过850 ℃时,铁矿石氧载体颗粒表面烧结现象明显,但反应前后,颗粒表面的成分及含量基本保持不变。     

A modified inlet system for high speed gas chromatography using inert metal tubing with a carbon dioxide cooled cryotrap

Ten different metal tubings were investigated for thermal decomposition of analytes when used as the trap tube in a cryotrap/thermodesorption inlet system. No noticeable sample decomposition of hydrocarbons, chlorinated hydrocarbons and a brominated hydrocarbon was observed for six of the tubings with hydrogen as the carrier gas. This observation may be partly attributed to the developed deactivation techniques that produce inert metal tubings that are being widely adopted by many column manufacturers, the different trap materials used in comparison to previous studies and the decreased sample residence time in the hot trap tube. A cryotrap using carbon dioxide was constructed and tested as a alternative to the previously used liquid nitrogen based systems. This cryotrap was able to trap compounds with a boiling point of 80°C.     

Determination of micro amounts of oxygen in silicon by inert-gas fusion

A chromatographic inert-gas fusion method using an Ni-Sn fusion bath and helium as carrier gas has been developed for determining micro amounts of oxygen in silicon. With the Ni-Sn bath, the oxygen determination can be done at lower temperatures (1650-1700 degrees ) in a heated graphite crucible than in an empty crucible (with no molten metal bath) in which the sample is directly in contact with the carbon. Four samples can be analysed in succession in a single crucible with a relatively short time for oxygen extraction (5 min). Careful control of experimental conditions, and the use of a water-cooled quartz tube and a small unshielded graphite crucible have resulted in a lower blank (0.1 mug of oxygen), and better reproducibility, enabling oxygen in silicon to be determined down to 1 ppm. A calibration curve for determining oxygen in single crystals of silicon by measuring the infrared absorption at 9 mum has been constructed and gives results agreeing with those obtained by alpha-particle activation analysis.     

An innovative molybdenum column liner for oxygen and hydrogen stable isotope analysis by pyrolysis

The most widely used method for pyrolysing samples for hydrogen or oxygen isotopic analysis involves heating them to greater than 1300 degrees C in a helium stream passed through a glassy carbon tube in an alumina casing. There are a number of difficulties with this. Glassy carbon tubes are expensive and interaction between the carbon tube and the outer casing produces unwanted carbon monoxide by reduction of the alumina at high temperatures. The latter effect is overwhelming if temperatures of 1400 degrees C or greater are used for pyrolysis. We experimented with lining alumina casings with pure molybdenum sheet. It is relatively cheap, conforms well to the interior of the reactor tube (to avoid carrier and sample bypassing of the carbon pack), resists high temperatures and neither oxidises excessively nor absorbs the gases. The main disadvantages are that silver sample cups must be used and that the molybdenum degrades over time by formation of the carbide. We can maintain sharp peaks, high precision and good accuracy over more than 700 solid samples for both hydrogen and oxygen. The reactors last longer for water injections. The molybdenum in the columns does not contribute greatly to memory effects. The precision of analysis is dependent on other factors as well as the pyrolysis column, but for oxygen we typically achieve approximately <0.2 per thousand (sucrose), <0.25 per thousand (water) and <0.25 per thousand (leaf), sometimes using only a linear correction of drift, after dividing the run into 1 to 3 segments.     

Analysis of gases containing inorganic and organic compounds using a combination of a thick-film capillary column and a packed adsorption column

A gas chromatographic system consisting of one multiport valve, two (hot-wire and flame-ionization) detectors and two analytical columns (one thick-film capillary and one packed adsorption column) is used for the analysis of gas samples containing a number of inorganic compounds (hydrogen, argon, oxygen, nitrogen, carbon monoxide, and carbon dioxide) and organic compounds. Examples include samples containing hydrocarbons up to n-nonane and benzene and toluene. The system also permits the analysis of more complicated samples containing, for example, alcohols, in addition to hydrocarbons.     

The palladium/silver membrane focusing injector — A new inlet system for thermal desorption capillary gas chromatography

Summary A new sample focusing technique for capillary gas chromatography is described. The system is designed as a focusing inlet for thermally desorbed gas samples. A solid-sorbent trapped sample is thermally released from the sample tube, transferred to a palladium/silver membrane chamber by a hydrogen carrier gas stream and retained there by the gas separation membrane, which is highly permeable to the carrier gas. After focusing in the membrane chamber the sample is injected onto the separation column. This technique allows focusing and injection of highly volatile compounds in capillary gas chromatography without using any coolant. The injection performance for n-alkanes is shown to be comparable to the cryofocusing technique.     

Automatic microanalyzers: II. Automatic analyzer for rapid microdetermination of oxygen

A commercially available analyzer for the microanalytic determination of oxygen in organic and some inorganic compounds is described. The technique rests upon the application of the Schütze-Unterzaucher principle; it involves flash pyrolysis of the sample in nitrogen atmosphere and reduction of pyrolitic gases with carbon black at 1120 °C in order to produce carbon monoxide which is oxidized into carbon dioxide; the latter is finally titrated by protonometric coulometry.The use of a vertical reactor makes possible a complete automation of the technique and besides it preserves the initial properties of the aging carbon black filling which is a very important feature for correct oxygen determination. The flash pyrolysis of samples in the vertical tube makes also possible a very important shortening of analysis time: for routine operation, a 7 min duration is generally chosen by the operator but it can be reduced to only 5 min at will.This technique covers a very broad analytical field and the apparatus can be provided with an automatic sample dispenser now commercially available, so that series determinations are carried out without operator save for the previous weighing out of all samples.     

Determination of very volatile organic compounds in environmental water by injection of a large amount of headspace gas into a gas chromatograph

An injection method for a large amount of headspace gas which enables determination of trace amounts of very volatile organic compounds (VVOCs), dichlorodifluoromethane, chloromethane, vinyl chloride, bromomethane, chloroethane and trichlorofluoromethane in all kinds of environmental water was developed. A gas phase equilibrated with the water phase in a vial was purged with helium for a short time. The VVOCs were then introduced into a trapping tube packed with Tenax TA, which had been cooled using carbon dioxide. After trapping, the VVOCs were thermally desorbed and put into a GC–MS system for subsequent analysis. This method is applicable to various types of samples.     

微波蒸馏-固相微萃取-气相色谱-质谱-嗅觉检测器联用分析鳙鱼鱼肉中的挥发性成分

用微波蒸馏(MD)-固相微萃取装置(SPME)提取鳙鱼鱼肉中的挥发性成分,利用气相色谱-质谱联用仪(GC-MS)对气味化合物成分进行了定性分析,同时利用嗅觉检测器鉴别了部分挥发性物质的气味特征。实验中优化了MD的操作条件(加热功率、加热时间及载气流速等)、SPME参数(萃取头种类、萃取温度、萃取时间、无机盐离子浓度及搅拌速率等)。通过NIST 02质谱数据库检索共定性确定出鳙鱼鱼肉挥发性成分中的53种化合物,其中主要为 C6~C9 的羰基化合物和挥发性醇类。经过嗅觉检测器分析,这些成分分别具有青草味、鱼腥味、泥土味等气味特征,其协同作用构成了鳙鱼鱼肉特殊的鱼腥味、泥腥味。该方法可用于水产品中挥发性成分的分析,并可为不良风味化合物的定量研究提供参考。     

Oxygen determination in organic fluorine compounds by means of a glassy-carbon pyrolysis tube

A conventional apparatus for determination of oxygen in organic compounds has been improved for application to organic fluorine compounds. A feature of the apparatus is the use of a pyrolysis tube made of glassy carbon instead of quartz, which eliminates effects due to hydrogen fluoride produced in pyrolysis of the sample. Ten analyses of dexamethasone with the apparatus gave a mean value of 20.44% for oxygen (theory, 20.38%), with a standard deviation of 0.16%. Oxygen in 9 organic fluorine compounds was accurately determined by using the apparatus, with an average error of +0.1%. One analysis by a gravimetric or a coulometric method took about 40 or 25 min, respectively.     

Zirconium dioxide-based solid electrolyte as a means of oxidation of organic compounds during isotopic assay of carbon

It is demonstrated that a high-temperature electrochemical reactor on the basis of zirconium dioxide (0.9ZrO₂ · 0.1Y₂O₃) with platinum electrodes may be promising as a device for preparing samples of organic gases for isotopic assay of carbon. Owing to a high catalytic activity of the surface of a porous platinum coating, it is possible to realize full oxidation of organic gases to stoichiometric oxides at 900–950°C and an oxygen flux equivalent to an electric current of 100 μA and higher. The reproducibility of the results of isotopic assay is better than that yielded by a standard oxidation reactor. Use of the solid-electrolyte reactor in a new device as a sensor makes it possible to simultaneously measure the concentration of organic gases passing through the reactor on the basis of the charge transported by oxygen ions through the wall of a ceramic tube. Simultaneously one can monitor purity of the carrier gas. Original Russian Text ? V.S. Sevast’yanov, E.M. Galimov, N.E. Babulevich, A.A. Arzhannikov, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 4, pp. 472–478.     

Application of Microflame Atomizer to Gas Chromatography-Atomic Absorption Spectrometry

One of the successful methods for the determination of organometallic compounds is the combination of Gas Chromatography-Atomic Absorption Spectrometry (GC-AAS). The atomizer of AAS was connected with the column of GC by a transfer tube. Three types of the atomizer were reported as flame burner,electrothermal quartz tube and graphite furnace. A large amount of gas or electric energy was required to produce a high temperature for the atomization of analytes, A microflame atomizer of GC-AAS was developed in this paper to circumvent above problems. The volume of the atomizer is one-fifth of the normal flame burner, and a hydrogen gas was used as the carrier gas (35ml/min) and the fuel gas for the atomization of analytes.     

辅助气燃烧接口对有机化合物碳同位素测定的影响

对多种烷烃及芳香化合物采用不同类型的反应管进行了碳同位素分析, 旨在阐明燃烧接口对有机化合物色谱行为的影响. 结果表明, 在反应管中填充较少的催化剂有助于提高化合物的分离度, 这可能是由于反应管中载气具有较高的线速度, 从而减少了化合物的扩散加宽. 然而, 不同反应管对分离度的改善作用相对有限. 对于不同的反应管, 化合物的灵敏度变化主要与开口分流处分流比的变化有关, 而这种变化可能是由反应管内载气流速的变化所致.