Russell David V, Sadergaski Luke R, Einkauf Jeffrey D, Delmau Laetitia H, Burns Jonathan D
Department of Chemistry, University of Alabama at Birmingham, Birmingham, Alabama 35294, United States.
Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States.
ACS Omega. 2024 Oct 31;9(45):45600-45609. doi: 10.1021/acsomega.4c08219. eCollection 2024 Nov 12.
This study presents an effective method for the quantification of nitric acid (0.1-9 M) and the temperature (20-60 °C) through optimal experimental design, chemometrics, and Raman spectroscopy. Raman spectroscopy can be deployed using fiber-optic cables in hot cell environments to support processing operations in the nuclear field and industry. Chemical operations frequently use nitric acid and operate at nonambient temperatures either by design or by circumstance. Examples of Raman spectroscopy for the quantification of nitric acid with applications in the industrial field are profuse. However, the effect of temperature on quantification is often ignored and should be considered in real-world scenarios. Statistical design of experiments was used to build training sets for partial least-squares regression and support vector regression (SVR) models. The SVR model with a nonlinear kernel outperformed the top partial least-squares models with respect to temperature and resulted in percent root-mean-square error of prediction of 1.8% and 2.3% for nitric acid and temperature, respectively. The D-optimal design strategy decreased the sampling time by 75% compared to a more traditional seven-level full factorial option. The new method advances chemometric applications within and beyond the nuclear field and industry.
本研究通过优化实验设计、化学计量学和拉曼光谱法，提出了一种定量分析硝酸（0.1 - 9 M）和温度（20 - 60 °C）的有效方法。拉曼光谱可通过光纤电缆在热室环境中部署，以支持核领域和工业中的处理操作。化学操作经常使用硝酸，并且无论是出于设计还是实际情况，都在非环境温度下进行。在工业领域中，用于定量分析硝酸的拉曼光谱应用实例众多。然而，温度对定量分析的影响常常被忽视，在实际场景中应予以考虑。实验的统计设计用于构建偏最小二乘回归和支持向量回归（SVR）模型的训练集。具有非线性核的SVR模型在温度方面优于顶级偏最小二乘模型，硝酸和温度的预测均方根误差百分比分别为1.8%和2.3%。与更传统的七级全因子选项相比，D - 最优设计策略将采样时间减少了75%。这种新方法推动了化学计量学在核领域和工业内外的应用。
