Comparative characterization of different kinds of chromatographic quantification using the double standard addition method

Abstract

Different algorithms for processing the quantitative gas chromato­gra­­phic ana­lysis data using the double standard addition method are compared for their accuracy. Three principal approaches are possible for such processing: I – simple comparison of values determined by sing­le and double standard additions, II – approximation of «peak area of ana­lyte» (S) – «mass of standard addition» (madd) depen­den­ce by the least squa­res method [linear reg­res­sion, m(S)], and III – independent quantification of analyte with both standard additi­ons follo­wed by the linear extrapolation of two sub-results on the so-cal­led «zero standard addi­tion», mx(madd ® 0). It is concluded that the quantitation results obtained using the various modes of the method are comparable in accuracy, but somewhat underestimated relative to the specified amounts of analytes. The principal reason of such systematic errors is the eva­po­ration of the solvent during the successive injecting of the same samples into the gas chroma­to­graph. Due to this reason the peak are­as, measured after the standard addition, appear to be slight­­ly increased and this leads to the systematic underestimation of the results. The second (less impor­tant) factor is the small increa­se of the samp­le volumes due to the addition of the compo­nents to be determined. It is confirmed that the systematic errors of different modes of standard addition are not exceeding the values of their random uncertainties. The op­ti­mal results (considering their signs of deviations) are provided using the double standard addition method with extrapolation of sub-results on «zero standard addition». In order to exclude the possible influence of «human factor» (increasing the re­sults precision during the series of analyses of similar samples due to the rising experience of analytical chemists) all parallel measurements have been per­for­med by bachelor students of the Chemistry Ins­titute of the St. Petersburg State University in the course of their laboratory practical works in chromatography. Such organization of experiments increases their credibility as it excluded the dependence of the results on the qualification of chemists.