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Elucidation of oxidation and degradation products of oxygen containing fuel components by combined use of a stable isotopic tracer and mass spectrometry
Analytica Chimica Acta ( IF 6.2 ) Pub Date : 2017-11-01 , DOI: 10.1016/j.aca.2017.09.009
Marcella Frauscher , Charlotte Besser , Günter Allmaier , Nicole Dörr

In order to reveal the degradation products of oxygen-containing fuel components, in particular fatty acid methyl esters, a novel approach was developed to characterize the oxidation behaviour. Combination of artificial alteration under pressurized oxygen atmosphere, a stable isotopic tracer, and gas chromatography electron impact mass spectrometry (GC-EI-MS) was used to obtain detailed information on the formation of oxidation products of (9Z), (12Z)-octadecadienoic acid methyl ester (C18:2 ME). Thereby, biodiesel simulating model compound C18:2 ME was oxidized in a rotating pressurized vessel standardized for lubricant oxidation tests (RPVOT), i.e., artificially altered, under 16O2 as well as 18O2 atmosphere. Identification of the formed degradation products, mainly carboxylic acids of various chain lengths, alcohols, ketones, and esters, was performed by means of GC-EI-MS. Comparison of mass spectra of compounds under both atmospheres revealed not only the degree of oxidation and the origin of oxygen atoms, but also the sites of oxidative attack and bond cleavage. Hence, the developed and outlined strategy based on a gas-phase stable isotopic tracer and mass spectrometry provides insight into the degradation of oxygen-containing fuels and fuel components by means of the accurate differentiation of oxygen origin in a degradation product.

中文翻译:

结合使用稳定同位素示踪剂和质谱法阐明含氧燃料组分的氧化和降解产物

为了揭示含氧燃料组分的降解产物,特别是脂肪酸甲酯,开发了一种新方法来表征氧化行为。加压氧气氛下人工改变、稳定同位素示踪剂和气相色谱电子轰击质谱 (GC-EI-MS) 的组合用于获得有关 (9Z)、(12Z)-十八碳二烯氧化产物形成的详细信息酸甲酯 (C18:2 ME)。因此,生物柴油模拟模型化合物 C18:2 ME 在为润滑剂氧化测试 (RPVOT) 标准化的旋转加压容器中被氧化,即在 16O2 和 18O2 气氛下人工改变。鉴定形成的降解产物,主要是各种链长的羧酸、醇、酮和酯,通过 GC-EI-MS 进行。两种气氛下化合物的质谱比较不仅揭示了氧化程度和氧原子的来源,还揭示了氧化攻击和键断裂的位置。因此,基于气相稳定同位素示踪剂和质谱的开发和概述的策略通过准确区分降解产物中的氧来源,提供了对含氧燃料和燃料组分降解的深入了解。
更新日期:2017-11-01
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