Dow Chemical Canada, P.O. BAG 16, Highway 15, Fort Saskatchewan, Alberta T8L 2P4, Canada.
J Chromatogr A. 2010 Jan 15;1217(3):348-52. doi: 10.1016/j.chroma.2009.11.042. Epub 2009 Nov 18.
A practical gas chromatographic procedure has been developed and implemented for the measurement of arsine and phosphine in hydrocarbons such as propylene at the part-per-billion level. The successful measurement of arsine and phosphine at the level mentioned was attained by incorporating a large volume injection technique to increase the mass of solutes delivered for sensitivity improvement, capillary flow technology to keep the matrix from entering the detector by either back-flushing through the inlet vent, or by heart-cutting if required, and dielectric barrier discharge detector operating in argon mode for sensitivity enhancement, as well as offering improved selectivity towards the solutes cited. Using the technique described a complete analysis can be conducted in less than 4 min. A relative standard precision of less than 1.7% was achieved with repeated injections at the concentration level of 25 and 125 ppb (v/v) each of arsine and phosphine in nitrogen with a practical detection limit at the 5 ppb (v/v) level. Correlation coefficients of greater than 0.9999 were obtained for arsine and phosphine over a range from 10 to 2500 ppb (v/v). The analytical methodology was proven to be reliable in continuous operation during the first 6 months of deployment.
已经开发并实施了一种实用的气相色谱程序，用于测量丙烯等碳氢化合物中的砷烷和膦，其浓度达到十亿分之几的水平。通过采用大体积进样技术来增加溶质的质量，以提高灵敏度；采用毛细管流动技术，通过入口通风口反向冲洗，或者在需要时进行中心切割，防止基质进入检测器；采用介电阻挡放电检测器在氩气模式下运行，以提高灵敏度，并对所提到的溶质具有更好的选择性，从而成功地实现了砷烷和膦在上述水平的测量。使用所述技术，在不到 4 分钟的时间内即可完成完整的分析。在氮中以 25 和 125 ppb（v/v）的浓度重复进样，砷烷和膦的相对标准精密度小于 1.7%，实际检测限为 5 ppb（v/v）。在 10 至 2500 ppb（v/v）的范围内，砷烷和膦的相关系数均大于 0.9999。在部署的头 6 个月中，该分析方法已被证明在连续运行中是可靠的。
