{"title":"Determining the Total Content of Similar Substances Using Integrated Indices or Multivariate Calibrations at a High Intragroup Selectivity of Signals","authors":"V. I. Vershinin, A. E. Abramova","doi":"10.1134/s0020168523140145","DOIUrl":null,"url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The total content <i>c</i><sub>Σ</sub> of similar organic compounds is conventionally determined without their separation by measuring their generalized spectral signals at one or several analytical wavelengths. The possibility of the correct <i>c</i><sub>Σ</sub> estimation with the strongly pronounced intragroup selectivity of signals has not been previously tested. To verify this group analysis option, model hexane solutions of the known composition containing mono-, bi-, and tricyclic arenes at <i>c</i><sub>Σ</sub> ~ 10<sup>–4</sup> mol/dm<sup>3</sup> simultaneously have been analyzed. At a fixed wavelength, the molar absorptivities of arenes with different numbers of rings differ by two to three orders of magnitude. Two options of group analysis have been compared: (i) measuring the generalized signal of arenes at 260 nm with the subsequent calculation of the result using the univariate calibration in terms of naphthalene or anthracene and (ii) measuring the generalized signals at <i>m</i> wavelengths in the spectral range of 250–290 nm with the subsequent calculation of the result using the inverted multivariate calibration. The first method (the calculation of the total index) has led to large systematic errors, sometimes over 100% in the absolute value, which do not decrease upon variation in the wavelength and nature of a standard substance. The second method has ensured more correct results, and already at <i>m</i> = 11, the errors of group analysis have been no more than 10%. Thus, at the strongly pronounced intragroup selectivity of the signals, the group analysis can and should be carried out using inverted multivariate calibrations. It has been established that the errors of <i>c</i><sub>Σ</sub> estimation sharply grow if a sample contains components of a desired group that were not taken into account when constructing the inverted calibration.</p>","PeriodicalId":585,"journal":{"name":"Inorganic Materials","volume":null,"pages":null},"PeriodicalIF":0.9000,"publicationDate":"2024-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1134/s0020168523140145","RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The total content cΣ of similar organic compounds is conventionally determined without their separation by measuring their generalized spectral signals at one or several analytical wavelengths. The possibility of the correct cΣ estimation with the strongly pronounced intragroup selectivity of signals has not been previously tested. To verify this group analysis option, model hexane solutions of the known composition containing mono-, bi-, and tricyclic arenes at cΣ ~ 10–4 mol/dm3 simultaneously have been analyzed. At a fixed wavelength, the molar absorptivities of arenes with different numbers of rings differ by two to three orders of magnitude. Two options of group analysis have been compared: (i) measuring the generalized signal of arenes at 260 nm with the subsequent calculation of the result using the univariate calibration in terms of naphthalene or anthracene and (ii) measuring the generalized signals at m wavelengths in the spectral range of 250–290 nm with the subsequent calculation of the result using the inverted multivariate calibration. The first method (the calculation of the total index) has led to large systematic errors, sometimes over 100% in the absolute value, which do not decrease upon variation in the wavelength and nature of a standard substance. The second method has ensured more correct results, and already at m = 11, the errors of group analysis have been no more than 10%. Thus, at the strongly pronounced intragroup selectivity of the signals, the group analysis can and should be carried out using inverted multivariate calibrations. It has been established that the errors of cΣ estimation sharply grow if a sample contains components of a desired group that were not taken into account when constructing the inverted calibration.
期刊介绍：
Inorganic Materials is a journal that publishes reviews and original articles devoted to chemistry, physics, and applications of various inorganic materials including high-purity substances and materials. The journal discusses phase equilibria, including P–T–X diagrams, and the fundamentals of inorganic materials science, which determines preparatory conditions for compounds of various compositions with specified deviations from stoichiometry. Inorganic Materials is a multidisciplinary journal covering all classes of inorganic materials. The journal welcomes manuscripts from all countries in the English or Russian language.
京公网安备 11010802042870号
京ICP备2023020795号-1
分享
求助内容：
应助结果提醒方式：
扫码关注我们
