Abstract
Some general problems of qualitative chemical analysis are considered. In particular, the context of its development is outlined, the concept of hypothesis testing as a basis for the detection and identification of chemical substances is presented, a classification of the types of analysis is given, and the uncertainty (reliability, accuracy) of qualitative determinations is discussed. Various errors arising from the use of binary test methods are reviewed, and methods for estimating these errors are surveyed. The estimates are based on the false (or true) rates of positive and negative results. The concentration dependence of these rates is discussed. It is shown that the testing results become more reliable if the prior probability of the presence of the analyte in the sample is known. Another method for improving the validity of analysis is to use two test methods or to confirm the testing data by other analytical means. In these cases, the positive and negative predictive values are estimated using Bayesian statistic. The approaches to the estimation of the uncertainty of test methods widely used in medicine and toxicology are extended to qualitative chemical analysis as a whole.
Similar content being viewed by others
REFERENCES
Zenkevich, I.G., Maksimov, B.N., and Rodin, A.A., Zh. Anal. Khim., 1995, vol. 50, no. 2, p. 118.
De Ruig, W.G., Trends Food Sci. Tech.1996, vol. 7, no.7, p. 234.
Zenkevich, I.G., Zh. Anal. Khim., 1996, vol. 51, no. 11, p. 1140 [J. Anal. Chem.(Engl. Transl.), 1996, vol. 51, no. 11, p. p1041].
Ellison, S.L.R., Gregory, S., and Hardcastle, W.A., Analyst, 1998, vol. 123, no. 5, p. 155.
Milman, B.L., Kovrizhnych, M.A., and Konopelko, L.A., Accred. Qual. Assur., 1999, vol. 4, no. 5, p. 185.
Mil'man, B.L. and Konopel'ko, L.A., Zavod. Lab., 1999, vol. 65, no. 12, p. 58.
Valcarsel, M., Cardenas, S., and Gallego, M., Trends Anal. Chem., 1999, vol. 18, no. 11, p. 685.
Mil'man, B.L. and Konopel'ko, L.A., Tez. dokl. Vseros. konf. “Khimicheskii analiz veshchestv i materialov” (Proc. All-Russia Conf. “Chemical Analysis of Sub-stances and Materials”), Moscow, 2000, pp. 269.
Milman, B.L. and Konopelko, L.A., Fresenius J. Anal. Chem., 2000, vol. 367, no. 7, p. 621.
Milman, B.L. and Kovrizhnych, M.A., Fresenius J.Anal. Chem., 2000, vol. 367, no. 7, p. 629.
Hartstra, J., Franke, J.P., and De Zeeuw, R.A., J. Chro-matogr., A, 2000, vol. 739, no. 1, p. 125.
Valcarsel, M., Cardenas, S., and Gallego, M., Crit. Rev. Anal. Chem., 2000, vol. 30, no. 4, p. 345.
Ellison, S.L.R., Accred. Qual. Assur., 2000, vol. 5, no. 8, p. 346.
Song, R., Schlecht, P.C., and Ashley, K., J. Hazard. Mater., 2001, vol. 83, nos. 1–2, p. 29.
Zenkevich, I.G., Zh. Anal. Khim., 2001, vol. 56, no. 9, p.915 J. Anal. Chem.(Engl. Transl.), 2001, vol. 56, no.9, p. 806].
Milman, B.L., Anal. Chem.2002, vol. 74, no. 7, p. 1484.
Brodskii, E.S., Zh. Anal. Khim., 2002, vol. 57, no. 6, p.585 [J. Anal. Chem. (Engl. Transl.), 2002, vol. 57, no.6, p. 480].
Vershinin, V.I., Derendyaev, B.G., and Lebedev, K.S., Komp'yuternaya identifikatsiya organicheskikh soedine-nii (Computer-Assisted Identification of Organic Compounds), Moscow: Akademkniga, 2002.
Valcarsel, M. Cardenas, S., Barselo, D., et al., Metrology of Qualitative Chemical Analysis, Luxembourg: Office for Official Publications of the European Communities, 2002, p. 166.
Rios, A., Barselo, D., Buydens, L., et al., Accred. Qual. Assur., 2003, vol. 8, no. 2, p. 68.
Mil'man, B.L., in Tez. dokl. V Vseros. konf. po analizu ob”ektov okruzhayushchei sredy “Ekoanalitika-2003” (Proc. V All-Russia Cong. on the Environmental Analysis “Ekoanalitika-2003”), St. Petersburg, 2003, p31.
Zolotov, Yu.A., Ivanov, V.M., and Amelin, V.G., Khimicheskie testmetody analiza (Chemical Test Methods of Analysis), Moscow: Editorial URSS, 2002.
Rukovodstvo po vyrazheniyu neopredelennosti izme-reniya (Guide for the Expression of Measurement Uncertainty), St. Petersburg: VNIIM, 1999.
Quantifying Uncertainty in Analytical Measurement, London: EURACHEM, 1995. Translated under the title Kolichestvennoe opisanie neopredelennosti v anali-ticheskikh izmereniyakh, St. Petersburg: Krismas+, 1997.
Quantifying Uncertainty in Analytical Measurements, 2nd ed., London: EURACHEM–CITAC, 2000. Translated under the title Kolichestvennoe opisanie neoprede-lennosti v analiticheskikh izmereniyakh, St. Petersburg: VNIIM, 2002.
Handbook of Applicable Mathematics. VI: Statistics, Ledermann, W. and Lloyd, E., Eds., New York: Wiley, 1984. Translated under the title Spravochnik po priklad-noi matematike, Moscow: Finansy i Statistika, 1990.
Sharaf, M.A., Illman, D.L., and Kowalski, B.R., Chemo-metrics, New York: Wiley, 1986. Translated under the title Khemometrika, Leningrad: Khimiya, 1989.
Sivia, D.S., Data Analysis: A Bayesian Tutorial, Oxford: Clarendon, 2001.
Elashberg, M.E., Zh. Anal. Khim., 1992, vol. 47, no. 6, p.966.
Peris, M., Crit. Rev. Anal. Chem.1996, vol. 26, no. 4, p.219.
Neiman, Yu.Ch, Vvodnyi kurs teorii veroyatnostei i matematicheskoi statistiki(Introductory Course of Probability Theory and Mathematical Statistics), Moscow: Nauka, 1968.
Larichev, O.I., Theoriya i metody prinyatiya reshenii (Theory and Methods of Decision Making), Moscow: Logos, 2000.
Applied Electrospray Mass SpectrometryPramanik, B.N., Ganguly, A.E., and Gross, M.L., Eds., New York: Marcel Dekker, 2002.
Stump, M.J., Fleming, R.C., Gong, W.H., Jaber, A.J., Jones, J.J., Surber, C.W., and Wilkins, C.L., Appl. Spec-trosc. Rev.2002, vol. 37, no. 3, p. 275.
http://www.cas.org/cgi-bin/regreport.pl.
Kinter, I. and Sherman, N.E., Protein Sequencing and Identification Using Tandem Mass Spectrometry, New York: Wiley Interscience, 2000, p. 207.
Report of the 6th Meeting of Consultative Committee for Amount of Substance (NCQM), Sevres: Bureau Interna-tional des Poids et Mesures, 2000.
Hooijschuur, E.W.J., Hulst, A.G. De Long, A.L., De Reuver, L.P., Van Krimper, S.H., Van Baar, B.L.M., Wils, E.R.J., Kientz, C.E., and Brinkman, U.A.T, Trends Anal. Chem., 2002, vol. 21, no. 2, p. 116.
ASTM Standard Guide for Evaluating the Performance Characteristics of Qualitative Chemical Spot Test Kits for Lead in Paint (ASTM A 1828–96), West Consho-hocken: ASTM, 1996.
Downey, G., Analyst1994, vol. 119, no. 11, p. 2367.
Defernez, M. and Kemsley, A.E., Trends Anal. Chem., 1997, vol. 16, no. 4, p. 216.
Stephany, R.W., Lecture Presented at the EU CRL Work-shop “Establishment of Reference Methods,” Berlin, 1997.
Beyermann, K., Organic Trace Analysis, Chichester: Ellis Horwood, 1984. Translated under the title Oprede-lenie sledovykh kolichestv organicheskikh veshchestv, Moscow: Mir, 1987.
Spiehler, V.R., Odonnell, N.I, and Gokhale, D.V., Clin. Chem., 1988, vol. 34, no.8, p. 1535.
Shaevich, A.B. and Muchnik, V.L., Zh. Anal. Khim., 1989, vol. 44, no. 3, p. 481.
Eriksson, J., Chait, A.O., and Fenyo, D., Anal. Chem., 2000, vol. 72, no. 5, p. 999.
ISO 3534–1:1993, Statistics–Vocabulary and Symbols–Part 1. Probability and General Statistical Terms, ISO, 1993.
Glossary of Terms Commonly Used in Health Care, Washington: Academy Health; http://www.ahsrhp.org/publications/glossary, July 30, 2002.
Desimoni, E., Mannino, S., and Brunetti, A., Accred. Qual. Assur., 2001, vol. 6, no. 11, p. 452.
Andre, F., De Wasch, K.K.G., De Brabander, H.F., Impens, S.R., Stolker, L.A.M., Van Ginkel, L., Stephany, R.W., Schilt, R., Courtheyn, D., Bonnaire, Y., Furst, P., Gowik, P., Kennedy, G., Kuhn, T., Moretain, J.P., and Sauer, M., Trends Anal. Chem., 2001, vol.20, no. 8, p. 435.
Pulido, A., Ruisanchez, I., Boque, R., and Rius, F.X., Anal. Chim. Acta, 2002, vol. 453, no. 2, p. 267.
Easton, V.J. and InNill, J.H. Statistics Glossary. Version 1.1, Glasgow: Univ. of Glasgow; http://www.stats.gla.ac.uk/steps/glossary, July 30, 2002.
Ferrara, S.D., Tedeschi, L., Frison, G., Brusisni, G., Castagna, F., Bernardelli, B., and Soregaroli, D., J. Anal. Toxicol., 1994, vol. 18, no. 5, p. 278.
Shor, Ya.B., Statisticheskie metody analiza i kontrolya kachestva i nadezhnosti(Statistical Methods of Analysis and Quality and Reliability Control), Moscow: Sovetskoe Radio, 1962, p. 171.
McNaught, A.D. and Wilkinson, A., IUPAC Compendium of Chemical Terminology. The Gold Book, 2nd ed., Blackwell Science, 1997; http://www.iupac.org/publica-tions/ books/author/mcnaught.html, Nov. 16, 2003.
Komar', N.P., Osnovy kachestvennogo khimicheskogo analiza(Basics of Qualitative Chemical Analysis), vol.1: Ionnye ravnovesiya (Ionic Equilibria), Kharkov, 1955.
Andreeva, O.V., Vasil'ev, V.V., and Tereshchenko, N.P., Chuvstvitel'nost' kachestvennykh reaktsii (Sensitivity of Qualitative Reactions), Leningrad, 1962.
Bugaevskii, A.A. and Kravchenko, M.S., Zh. Anal. Khim., 1983, vol. 38, no. 1, p. 17.
Pantaler, R.P., Egorova, L.A., Avramenko, L.I., and Blank, A.B., Zh. Anal. Khim.1996, vol. 51, no. 5, p. 521 [J. Anal. Chem. (Engl. Transl.), 1996, vol. 51, no. 5, p.478].
Lead in Air by Chemical Spot Test Method 7700. NIOSH Manual of Analytical Methods, 1996, Issue 1.
Kolb. M., Bahr, A., Hippich, S., and Schulz, W., Acta Hydrochim. Hydrobiol., 1993, vol. 21, no. 6, p. 308.
Vogelgesang, J. and Hadrich, J., Accred. Qual. Assur., 1998, vol. 3, no. 6, p. 242.
Ashley, K., Fischbach, T.J., and Song, R., Am. Ind. Hyg. Ass. J., 1996, vol. 57, no. 2, p. 161.
Bugaevskii, A.A., Kruglov, V.O., and Kravchenko, M.S., Zavod. Lab., 1976, vol. 42, no. 1, p. 68.
Pantaler, R.P., Timchenko, A.K., Avramenko, L.I., and Blank, A.B., Zh. Anal. Khim., 1997, vol. 52, no. 4, p. 384 [J. Anal. Chem. (Engl. Transl.), 1997, vol. 52, no. 4, p.341].
Pantaler, R.P., Timchenko, A.K., Avramenko, L.I., and Blank, A.B., Zh. Anal. Khim., 1998, vol. 53, no. 5, p. 529 [J. Anal. Chem. (Engl. Transl.), 1998, vol. 53, no. 5, p.466].
Ashley, K., Hunter, M., Tait, L.H., Dozier, J., Sea-man, J.L., and Berry, P.F., Field Anal. Chem. Technol., 1998, vol. 2, no. 1, p. 39.
Vlasov, V.V., Meditsina v usloviyakh bednosti: tekh-nologiya i etika raspredeleniya(Medicine under Poverty Conditions: Technology and Ethics of Distribution), Saratov: Agaton, 1999, Sect. 4.4.1; http://agaton.sgu.ru/win/specia/lmedpoor/book/index.html, June 30, 2003.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Mil'man, B.L., Konopel'ko, L.A. Uncertainty of Qualitative Chemical Analysis: General Methodology and Binary Test Methods. Journal of Analytical Chemistry 59, 1128–1141 (2004). https://doi.org/10.1023/B:JANC.0000049712.88066.e7
Issue Date:
DOI: https://doi.org/10.1023/B:JANC.0000049712.88066.e7