The True Value of a Sample Composition Is There

Abstract

The core objective of a chemical composition measurement is to determine its true value. However, when measuring the composition of a macroscopic sample with a large number of atoms or molecules, realizing the true value of the measurand at both the macroscopic and microscopic levels remains an unsolved theoretical problem. We find that the true value of a sample composition exists in any subsample of a homogeneous molecular population of the sample. Here, we propose the Central Law of Measurement of the Amount of Substance: “The homogeneity of a sample molecular population represents the measurement accuracy of the sample composition in an analytical procedure”. The Central Law is based on a homogeneous molecular population axiom in which the molecular composition of a sample is identical for any homogeneous subsample. Furthermore, we point out that, at the microscopic scale, Avogadro’s law does not hold true.

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Yi, H. and Yi, W. (2015) The True Value of a Sample Composition Is There. American Journal of Analytical Chemistry, 6, 285-296. doi: 10.4236/ajac.2015.64027.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] De Bièvre, P. and Günzler, H. (2003) Measurement Uncertainty in Chemical Analysis. Springer-Verlag, Berlin.
http://dx.doi.org/10.1007/978-3-662-05173-3
[2] BIPM, IEC, IFCC, ILAC, ISO, IUPAC, IUPAP and OIML (2008) Guide to the Expression of Uncertainty in Measurement (GUM). JCGM 100:2008.
http://www.bipm.org/utils/common/documents/jcgm/JCGM_100_2008_E.pdf
[3] De Bievre, P., Kaarls, R., Peiser, H.S., Rasberry, S.D. and Reed, W.P. (1996) Measurement Principles for Traceability in Chemical Analysis. Accreditation and Quality Assurance, 1, 3-13.
http://dx.doi.org/10.1007/s007690050026
[4] Cali, J.P. (1974) A Systematic Approach to Accuracy in Clinical Chemistry. Medical instrumentation, 8, 17-21.
[5] Dorsey, N.E. and Eisenhart, C. (1953) On Absolute Measurement. The Scientific Monthly, 77, 103-109.
[6] BIPM, IEC, IFCC, ILAC, ISO, IUPAC, IUPAP and OIML (2012) International Vocabulary of Metrology-Basic and General Concepts and Associated Terms (VIM). 3rd Edition, JCGM 200:2012.
http://www.bipm.org/utils/common/documents/jcgm/JCGM_200_2012.pdf
[7] Cali, J.P. and Reed, W.P. (1976) The Role of the National Bureau of Standards Standard Reference Materials in Accurate Trace Analysis. National Bureau of Standards Special Publication, 422, 41-63.
[8] De Bievre, P. and Taylor, P.D.P. (1997) Traceability to the SI of Amount of Substance Measurements: From Ignoring to Realizing, a Chemist’s View. Metrologia, 34, 67-75.
[9] Youden, W.J. (1961) How to Evaluate Accuracy. Materials Research & Standards, 1, 268-271.
[10] Kadis, R. (2002) Analytical Procedure in Terms of Measurement (Quality) Assurance. Accreditation and Quality Assurance, 7, 294-298.
http://dx.doi.org/10.1007/s00769-002-0484-9
[11] Price, G. (2011) Failures of the Global Measurement System Part 1: The Case of Chemistry. Accreditation and Quality Assurance, 15, 421-427.
http://dx.doi.org/10.1007/s00769-010-0655-z
[12] Yi, H., Li, T.J., Wang, X., Zhang, F.S., Huo, W.G. and Yi, W. (2012) Amount of Substance Measurement Homogeneity Principle: The Discrepancy between XRCD and Watt Balance Results. Metrologia, 49, 62-69.
http://dx.doi.org/10.1088/0026-1394/49/1/010
[13] http://www.iupac.org/fileadmin/user_upload/news/IUPAC_Periodic_Table-1Jun12.pdf
[14] Mills, I., Cvitas, T., Homann, K., Kallay, N. and Kuchitsu, K. (1993) IUPAC Green Book: IUPAC Quantities, Units and Symbols in Physical Chemistry. 2nd Edition, Blackwell Scientific Publications, Oxford.
[15] Danzer, K. (2007) Analytical Chemistry Theoretical and Metrological Fundamentals. Springer, Berlin, 15.
[16] Cuadros-Rodriguez, L., Gamiz-Gracia, L., Almansa-Lopez, E. and Laso-Saènchez, J. (2001) Calibration in Chemical Measurement Processes: I. A Metrological Approach. Trends in Analytical Chemistry, 20, 195-206.
http://dx.doi.org/10.1016/S0165-9936(00)00093-5
[17] BIPM (2006) The International System of Units (SI). 8th Edition, BIPM, Paris.
http://www.bipm.org/utils/common/pdf/si_brochure_8.pdf
[18] Milton, M.J.T. (2011) A New Definition for the Mole Based on the Avogadro Constant: A Journey from Physics to Chemistry. Philosophical Transactions of the Royal Society A, 369, 3993-4003.
http://dx.doi.org/10.1098/rsta.2011.0176
[19] http://physics.nist.gov/cgi-bin/cuu/Value?na|searchfor=avogadro+constant
[20] Becker, P. (2001) History and Progress in the Accurate Determination of the Avogadro Constant. Reports on Progress in Physics, 64, 1945-2008.
http://dx.doi.org/10.1088/0034-4885/64/12/206
[21] MacLeod, R.A.F., Dirks, W.G., Matsuo, Y., Kaufmann, M., Milch, H. and Drexler, H.G. (1999) Widespread Intraspecies Cross-Contamination of Human Tumor Cell Lines Arising at Source. International Journal of Cancer, 83, 555-563.
http://dx.doi.org/10.1002/(SICI)1097-0215(19991112)83:4<555::AID-IJC19>3.0.CO;2-2
[22] Drexler, H.G., Dirks, W.G., Matsuo, Y. and MacLeod, R.A. (2003) False Leukemia-Lymphoma Cell Lines: An Update on Over 500 Cell Lines. Leukemia, 17, 416-426.
http://dx.doi.org/10.1038/sj.leu.2402799
[23] Wheatley, N. (2011) On the Dimensionality of the Avogadro Constant and the Definition of the Mole. Metrologia, 48, 71-82.
http://dx.doi.org/10.1088/0026-1394/48/3/001
[24] Milton, M.J.T. and Quinn, T.J. (2001) Primary Methods for the Measurement of Amount of Substance. Metrologia, 38, 289-296.
http://dx.doi.org/10.1088/0026-1394/38/4/1
[25] Prichard, E. and Barwick, V. (2007) Quality Assurance in Analytical Chemistry. John Wiley & Sons Ltd., England, 70-73.
http://dx.doi.org/10.1002/9780470517772
[26] Matuszewski, B.K., Constanzer, M.L. and Chavez-Eng, C.M. (2003) Strategies for the Assessment of Matrix Effect in Quantitative Bioanalytical Methods Based on HPLC-MS/MS. Analytical Chemistry, 75, 3019-3030.
http://dx.doi.org/10.1021/ac020361s
[27] Andreas, B., Azuma, Y., Bartl, G., Becker, P., Bettin, H., Borys, M., et al. (2011) Counting the Atoms in a 28Si Crystal for a New Kilogram Definition. Metrologia, 48, S1-S13.
http://dx.doi.org/10.1088/0026-1394/48/2/S01
[28] Milton, M.J.T. (2013) The Mole, Amount of Substance and Primary Methods. Metrologia, 50, 158-163.
http://dx.doi.org/10.1088/0026-1394/50/2/158
[29] Perrin, J.B. (1910) Brownian Movement and Molecular Reality. Taylor and Francis, London.
[30] Greiner, W., Neise, L. and Stocker, H. (1995) Thermodynamics and Statistical Mechanics. Springer, New York, 6.
http://dx.doi.org/10.1007/978-1-4612-0827-3
[31] Pathria, R.K. and Beale, P.D. (2011) Statistical Mechanics. 3rd Edition, Elsevier, Singapore, 583-586.
http://dx.doi.org/10.1016/B978-0-12-382188-1.00015-3
[32] Landau, L.D. and Lifshitz, E.M. (1986) Statistical Physics Part 1. 3rd Edition, Elsevier, Singapore, 333-345.
[33] Schwabl, F. (2006) Statistical Mechanics. 2nd Edition, Springer, Berlin, 494-496.

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