Feasibility of high-resolution continuum source molecular absorption spectrometry in flame and furnace for sulphur determination in petroleum products

For the first time, high-resolution molecular absorption spectrometry with a high-intensity xenon lamp as radiation source has been applied for the determination of sulphur in crude oil and petroleum products. The samples were analysed as xylene solutions using vaporisation in acetylene-air flame or in an electrothermally heated graphite furnace. The sensitive rotational lines of the CS molecule, belonging to the ?ν = 0 vibrational sequence within the electronic transition X¹∑⁺ → A¹П, were applied. For graphite furnace molecular absorption spectrometry, the Pd + Mg organic modifier was selected. Strong interactions with Pd atoms enable easier decomposition of sulphur-containing compounds, likely through the temporal formation of Pd_xS_y molecules. At the 258.056 nm line, with the wavelength range covering central pixel ± 5 pixels and with application of interactive background correction, the detection limit was 14 ng in graphite furnace molecular absorption spectrometry and 18 mg kg⁻¹ in flame molecular absorption spectrometry. Meanwhile, application of 2-points background correction found a characteristic mass of 12 ng in graphite furnace molecular absorption spectrometry and a characteristic concentration of 104 mg kg⁻¹ in flame molecular absorption spectrometry.The range of application of the proposed methods turned out to be significantly limited by the properties of the sulphur compounds of interest. In the case of volatile sulphur compounds, which can be present in light petroleum products, severe difficulties were encountered. On the contrary, heavy oils and residues from distillation as well as crude oil could be analysed using both flame and graphite furnace vaporisation. The good accuracy of the proposed methods for these samples was confirmed by their mutual consistency and the results from analysis of reference samples (certified reference materials and home reference materials with sulphur content determined by X-ray fluorescence spectrometry).     

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.     

Convenient synthetic route of versatile 21-monothiatetraphenylporphyrins of the A4 and AB3 type

A novel convenient synthetic route for poly-functional 21-monothiatetraphenylporphyrins of the type A₄ und AB₃ having base labile substituents in meso position was developed. Using this method a series of symmetric and asymmetric 21-thiaporphyrins containing different functional groups at the meso position is reported. The new products were characterized by NMR, UV-Vis and mass spectroscopy.     

A Modified Technique for the Preparation of SO2 from Sulphates and Sulphides for Sulphur Isotope Analyses

Abstract

A modified technique for the conversion of sulphates and sulphides to SO₂ with the mixture of V₂O₅—SiO₂ for sulphur isotopic analyses is described. This technique is more suitable for routine analysis of large number of samples. Modification of the reaction vessel and using manifold inlet system allows to analyse up to 24 samples every day. The modified technique assures the complete yield of SO₂, consistent oxygen isotope composition of the SO₂ gas and reproducibility of δ³⁴S measurements being within 0.10‰. It is observed, however, oxygen in SO₂ produced from sulphides differs in δ¹⁸O with respect to that produced from sulphates.     

Gas chromatography-mass spectrometry determination of 3-mercaptohexan-1-ol and 3-mercaptohexyl acetate in wine: a comparison of headspace solid phase microextraction and solid phase extraction methods

A gas chromatography-mass spectrometry method was established using headspace solid phase microextraction (HS-SPME) as the sampling procedure to analyse 3-mercaptohexan-1-ol (3-MH) and 3-mercaptohexyl acetate (3-MHA), two molecules with a tropical fruit aroma, in wine at trace level. This method offers important advantages, as it neither requires time-consuming sample preparation nor uses dangerous organic compounds, thus making control of wine aroma easier and suitable for routine analysis. As a comparison, a solid phase extraction (SPE) method, already described elsewhere for aroma analysis, was applied to quantify these analytes, extending this exhaustive enrichment to two important thiols. Detection limits for both the approaches were close to the sensory threshold value, resulting lower for the HS-SPME procedure and suitable for requirements in the oenological field. The application of the two proposed methods to 52 wines of different varieties gave similar results.     

碘和硫增感剂在卤化银颗粒表面的分布

碘在卤化银微晶中的含量和分布对感光度的影响引起乳剂配方设计者的广泛注意和重视.颗粒中的碘引起其内部结构和表面结构的改变,导致微晶颗粒表面化学及物理性质的改变,从而引起增感敏化斑的位置、分布以及随后潜影斑、灰雾斑的形成等一系列的变化并最终影响乳剂的感光性能.如果我们想有效地控制卤化银乳剂的感光度、灰雾、反差等一系列感光性能,必须调整卤化银乳剂颗粒的表面结构.     

(SO4.-)诱导含硫三电子键自由基的生成机理研究

运用２４８ｎｍ激光光解瞬态吸收光谱,研究了ＳＯ４＾·－单电子氧化Ｄ－甲硫氨酸＊Ｍｅｔ）、Ｌ－甲硫氨酸甲酯（ＭＭＥ）和甲硫氨酰甲硫氨酸（Ｍｅｔ－Ｍｅｔ）的反应过程。观察到反应过程中生成３种含硫三电子键自由基中间体,［Ｓ∴Ｓ］＾＋、［Ｓ∴Ｎ］＾＋［Ｓ∴Ｏ］,并分析了反应机理。     

Measurement of reduced sulphur compounds contained in aqueous matrices by direct injection into a gas chromatograph with a flame photometric detector

An analytical method was developed to measure the concentration of hydrogen sulphide, methyl mercaptan, dimethyl sulphide and dimethyl disulphide contained in aqueous matrices (distilled water, tap water, kraft mill condensates and membrane bioreactor mixed liquor) by direct injection of aqueous samples into a gas chromatograph with a flame photometric detector. The analytical method requires a small sample volume (2 ml), sample preparation and analysis can be completed within 20 min and no complex sampling apparatus is needed. Consistent results and good recoveries were observed in all matrices investigated over the range of concentrations examined. The relationship between the normalized peak area obtained from GC–flame photometric detection and the concentration of the reduced sulphur compounds (RSCs) examined did not follow the theoretical power law exponent of two. The power law exponent appeared to decrease with the organic fraction associated with each RSC. The observed power law exponents for hydrogen sulphide, methyl mercaptan, dimethyl sulphide and dimethyl disulphide were 1.92, 1.90, 1.66 and 1.72, respectively.     

红外法测量钢铁中碳硫示值误差不确定度的评定

依据国家标准方法对不同类型大量台件的红外碳硫分析仪进行检定与测试,采用国家一级或二级标准物质对仪器进行校准,在此过程中获得大量的数据．根据拟订的示值误差数学模型,分别给出输入量的A类或B类不确定度评定结果,按照国际通行方法进行不确定度的合成与扩展,最终得到红外法测量示值误差不确定度的判断。不确定度的大小是评定一种测量方法能力优劣的指标。