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Vapor/Solid chemisorption model for passive sampling of aldehydes.

机译:气相/固体化学吸附模型,用于醛的被动采样。

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摘要

The vapor-phase chemisorption isotherms of valeraldehyde (n-valeraldehyde; 1-pentanal) and acrolein (2-propenal) above the critical face velocity (7.5 cm/s) were investigated at 25 degrees C and 36 percent relative humidity (RH) for a passive air sampling pellet of 10 percent O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine hydrochloride (PFBHA) on Tenax TA solid sorbent (80/100 mesh). A dynamic air dilution system with syringe pumps generated the vapor concentrations and humidity for the exposure chamber. The O-oxime derivatives were desorbed with hexane for gas chromatographic analysis on a nonpolar capillary column and electron capture detection. The pellet capacity was about 30 micromoles. Adsorption of valeraldehyde was best fitted by a Langmuir or Brunauer-Emmett-Teller (BET) I model. That for acrolein was described best by a Dubinin-Radushkevich model. A microporosity model explained why all the classical isotherms described the chemisorption behavior. An activated extrinsic precursor was suggested to facilitate the addition reaction by production of a protonated intermediate formed by the transfer of a proton to the aldehyde from an activated reaction site consisting of at least 2 PFBHA molecules.
机译:在25°C和36%的相对湿度(RH)下,研究了高于临界面速度(7.5 cm / s)的戊醛(n-戊醛; 1-戊醛)和丙烯醛(2-丙醛)的气相化学吸附等温线。在Tenax TA固体吸附剂(80/100目)上的10%O-(2,3,4,5,6-五氟苄基)-羟胺盐酸盐(PFBHA)的被动空气采样颗粒。带有注射泵的动态空气稀释系统为暴露室产生了蒸气浓度和湿度。 O-肟衍生物用己烷解吸,用于非极性毛细管柱上的气相色谱分析和电子捕获检测。粒料容量为约30微摩尔。 Langmuir或Brunauer-Emmett-Teller(BET)I模型最适合戊醛的吸附。 Dubinin-Radushkevich模型最好地描述了丙烯醛的含量。微孔模型解释了为什么所有经典的等温线都描述了化学吸附行为。建议活化的外在前体通过产生质子化的中间体来促进加成反应,所述质子化的中间体是由质子从至少两个PFBHA分子组成的活化的反应位点转移至醛而形成的。

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