Experimental validation of an effective carbon number-based approach for the gas chromatography–mass spectrometry quantification of ‘compounds lacking authentic standards or surrogates’

For the quantitative analysis of ‘compounds lacking authentic standards or surrogates’ (CLASS) in environmental media, we previously introduced an effective carbon number (ECN) approach to develop an empirical equation for the prediction of their response factor (RF). In this research, a series of laboratory experiments were carried out to benchmark the reliability of an ECN approach for sorbent tube/thermal desorption/gas chromatography (GC)/mass spectrometry (MS) applications. First, the ECN values were determined using external calibration data from 25 reference volatile organic compounds (VOCs) using two MS dectectors (quadrupole (Q) and time-of-flight (TOF)). Then, a certified standard mixture of 54 VOCs was analyzed by each system as a simulated unknown sample. The analytical bias, assessed in terms of percentage difference (PD) between the certified and ECN-predicted mass values, averaged 19.2 ± 16.1% (TOF-MS) and 28.2 ± 27.6% (Q-MS). The bias using a more simplified carbon number (CN)-based prediction increased considerably, yielding 53.4 ± 53.3% (TOF-MS) and 61.7 ± 81.3% (Q-MS). However, the bias obtained using the ECN-based prediction decreased significantly to yield average PD values of 9.84 ± 7.28% (TOF-MS) and 16.8 ± 8.35% (Q-MS), if the comparison was limited to 26 (out of 54) VOCs with CN ≥ 4 (i.e., 25 aromatics and hexachlorobutadiene).     

气相色谱法测定大鼠肝微粒体中丁醇的生物转化产物丁醛的含量

丁醇在分离提取的大鼠肝微粒体中,与微粒体中的细胞色素Ｐ４５０ⅡＥ１酶及加入的还原性辅酶Ⅱ（ＮＡＤＰＨ）在特定的温度下作用一定时间后,转化为丁醛。丁醇转化为丁醛的速率可作为评价细胞色素Ｐ４５０ⅡＥ１酶活性的指标。采用顶空气相色谱法可测定丁醇在微粒体中转化产生丁醛的含量。方法的检测限为０．７μｍｏｌ／Ｌ,变异系数８．１％～９．３％,回收率８５．３％。其干扰少、灵敏、快速、准确。方法的建立为间接测定细胞色素Ｐ４５０ⅡＥ１酶活性提供了可靠的测试手段。     

TiO2/AC光催化剂上气体污染物降解的反应动力学模型

 利用二氧化钛与活性炭(AC)共水热处理的方法制备了TiO2/AC复合催化剂,采用空气净化评价装置对其催化降解低浓度气体污染物丁醛的性能进行了模拟评价实验. 基于Langmuir-Hindshelwood方程和一些假设,推导了循环反应系统气体污染物降解的瞬态模型. 结果表明,该动力学模型所得数据与丁醛的模拟评价实验结果基本相符,预示着该模型能够很好地预测污染物的降解行为.     

TiO2/AC复合光催化剂对苯和丁醛的气相光催化降解机理

 利用溶胶-凝胶并水热处理法制备了TiO2光催化剂和TiO2/AC复合光催化剂,在静态光催化反应器中研究了苯和丁醛的气相吸附和光催化降解,利气相色谱分析确定了生成的中间体. 结果表明, TiO2/AC复合光催化剂比TiO2光催化剂具有较强的吸附能力和较高的光催化活性; 在TiO2和TiO2/AC上,苯(或丁醛)光催化降解产生相同的中间体,表明在两种催化剂上发生的光催化反应遵循相同的机理,进而讨论了其可能的光催化氧化途径.     

Determination of Critical Parameters of Carbon Dioxide ＋ Butyraldehyde System with Different Compositions

Supercritical carbon dioxide（SC-CO2 ） is considered in green chemistry as a substitute for conventional solvents in chemical reactions due to its environmentally benign character. Recently we have reported the homogeneous hydroformylation of propylene in supercritical carbon dioxide（ SC-CO2 ） , which is an example of this kind of application of carbon dioxide. The determination for the critical parameters of carbon dioxide ＋ butyraldehyde mixtures is necessary for this reaction design which is the focus of the present paper. The critical parameters of the binary systems were determined via the static visual method at a constant volume with the molar fraction of butyraldehyde ranging from 1.0% to 2. 2% and the pressure ranging from 5 to 10 MPa. The experimental results show that the critical pressure and temperature increased with increasing the molar fraction of butyraldehyde. The bubble（dew） temperatures and the bubble （dew） pressures for the binary systems were also determined experimentally. The p-T Figures at different compositions of the binary systems were described. In addition, the critical compressibility factors Zc of the binary systems at different concentrations of n-butyraldehyde were calculated. It was found that the critical compressibility factor values of the binary systems decreased with increasing the molar fraction of n-butyraldehyde in the experimental range.     

Transformations of butyraldehyde in the presence of catalysts based on large-pore molecular sieves VPI-5 and AlPO4-8

It is found that zeolite-like crystalline aluminophosphates VPI-5, Si-VPI-5, and Mn-VPI-5 as well as those dirived from them, AlPO{in4}-8, SAPO{in4}-8, and MnAPO{in4}-8, are capable of catalyzing aldol condensation and crotonization of butyraldehyde (BA). Pd/AlPO{in4}-8 is catalytically active in hydrocondensation of BA with H{in2} at atmospheric pressure. The activities in BA conversion to 2-ethylhexane-3-ol-1-al increase in the following order: Mn-VPI-5 < Si-VPI-5 < VPI-5. The same order of activities is also found for AlPO{in4}-8, SAPO{in4}-8, and MnAPO{in4}-8. These catalysts are characterized by a lower initial activity in crotonization of BA than M{su+}NaX (CsNaX), but they are much more stable. Pd/AlPO{in4}-8 catalyzes BA conversion to 2-ethylhexanal even in the absence of H{in2} feed to the reaction zone. The influence of catalyst pretreatments and experimental conditions on the catalyst structures and catalytic activities is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khmicheskaya, No. 12, pp. 2123–2129, December, 1994.