Research Group in Polymer Science, Engineering and Sustainability, Esenttia, Mamonal Industrial Zone, Km. 8, Cartagena, Colombia; Research Center in Polymers, Catalysts and analytical chemistry, CePoCat&A, Cartagena, Colombia; Universitat Politecnica de Valencia (UPV), Institute of Materials Technology (ITM), Plaza Ferrándiz y Carbonell s/n 03801 Alcoy, Alicante, Spain.
Universitat Politecnica de Valencia (UPV), Institute of Materials Technology (ITM), Plaza Ferrándiz y Carbonell s/n 03801 Alcoy, Alicante, Spain.
J Chromatogr A. 2021 Jan 25;1637:461833. doi: 10.1016/j.chroma.2020.461833. Epub 2020 Dec 22.
The reliable determination of arsine (AsH) and phosphine (PH) in hydrogen (H), nitrogen (N) and liquefied petroleum gas (LPG) is of great importance because of its drastic effects on the efficiency of catalysts, as well as the strict regulations associated with health, safety and environmental issues. It is challenging for an analyst to determine the parts per billion of AsH and PH in H, N, and LPG at low and high pressures without collection procedures using adsorption, desorption, and dissolution techniques. To overcome this analytical need an analytical methodology was developed, employing a variable pressure sampler (VPS) coupled to a gas chromatograph (GC) with mass spectrometry (MS) for the identification and quantification of traces of AsH and PH. The instrumentation, tubing and accessories of the VPS were made of passivated steel to avoid losses from absorption of AsH and PH in the steel which would generate significant analytical problems. The VPS had a homogeneous heating block that prevented analyte losses from condensation. With the VPS, 24 AsH and PH standards were prepared between 0.005 and 0.1 mg kg in balance of H, N and LPG. The separation and quantification of the analytes was achieved with an improved GC with 4 valves and 5 columns in series that guaranteed the elimination of impurities. The proposed method was optimized in VPS and GC-MS and then validated showing highly accaptable linearity (r > 0.9999), detection limits (<0.0009 mg kg), limits of quantification (<0.003 mg kg), intra-day and inter-day precision and accuracy (<1.14% and ≤3.0% respectively), recovery for the standard addition (86-109%), P values> 0.05 for the test Student's t paired who evaluated the effect of the matrix on pressure and concentration. The speed of analysis was high (<5.2 min). The method was applied to real samples, showing values between 0.005 and 0.1 mg kg and an effect on the efficiency of the Ziegler Natta catalyst between 5 and 56%.
由于砷烷 (AsH) 和膦 (PH) 对催化剂效率具有严重影响，并且与健康、安全和环境问题有关的法规非常严格，因此可靠地测定氢气 (H)、氮气 (N) 和液化石油气 (LPG) 中的砷烷和膦具有重要意义。对于分析师来说，在没有使用吸附、解吸和溶解技术进行收集程序的情况下，在高低压下测定 H、N 和 LPG 中的 AsH 和 PH 的 ppm 级是具有挑战性的。为了克服这一分析需求，开发了一种分析方法，采用可变压力采样器 (VPS) 与配备质谱 (MS) 的气相色谱仪 (GC) 结合，用于鉴定和定量痕量的 AsH 和 PH。VPS 的仪器、管道和配件均采用钝化钢制成，以避免 AsH 和 PH 在钢中吸收造成的损失，这将产生重大的分析问题。VPS 具有均匀的加热块，可防止因冷凝而导致分析物损失。使用 VPS，在 H、N 和 LPG 的平衡中制备了 24 个 AsH 和 PH 标准品，浓度在 0.005 至 0.1 mg kg 之间。通过使用具有 4 个阀门和 5 个串联柱的改进型 GC 实现了分析物的分离和定量，该 GC 保证了杂质的消除。该方法在 VPS 和 GC-MS 中进行了优化，然后进行了验证，显示出高度可接受的线性度 (r > 0.9999)、检测限 (<0.0009 mg kg)、定量限 (<0.003 mg kg)、日内和日间精密度和准确度 (<1.14%和 ≤3.0%），标准加入回收率（86-109%），对于评估基质对压力和浓度影响的检验学生 t 配对检验的 P 值> 0.05。分析速度很快（<5.2 min）。该方法应用于实际样品，结果在 0.005 至 0.1 mg kg 之间，对 Ziegler Natta 催化剂的效率有 5 至 56%的影响。
