Resumen
La absorción molecular en la región espectral entre 160 y 780 nm es causada por la excitación electrónica de especies absorbentes. En longitudes de onda por debajo de 400 nm, la energía de radiación incidente es suficiente para romper los enlaces químicos, mientras que en la región infrarroja (más de 780 nm), se observan principalmente vibraciones moleculares. Dado que las especies químicas que absorben en la región UV-vis del espectro electromagnético tienen amplias bandas de absorción, las determinaciones simultáneas de múltiples especies son más complicadas, dada la dificultad de encontrar longitudes de onda apropiadas que permitan la medición directa de la concentración individual de cada componente en la mezcla. Teniendo en cuenta la situación más simple, donde la muestra consta de solo dos especies absorbentes en solución, los procedimientos más directos y eficientes que pueden usarse para resolver este problema son el método algebraico, el método de espectroscopía de longitud de doble onda y el método de adición estándar en el punto H (HPSAM). De estos, este último parece ser más eficiente, ya que le permite eliminar o reducir los errores sistemáticos. Los procedimientos y cálculos experimentales asociados con estos métodos se presentarán en este trabajo, tomando como ejemplo la determinación simultánea de las concentraciones de dos iones distintos en una solución acuosa ácida.
Referencias
- Vogel AI. Análise Química Quantitativa, Ed.: Jeffery GH, Bassett J, Mendham J, Denney RC., Editora Guanabara Koogan, 5ª ed., Rio de Janeiro, 1992.
- Christian, GD. Analytical Chemistry, John Wiley & Sons, Inc., 5th ed., New York, 1994.
- Skoog DA, Holler FJ, Nieman TA. Princípios de Análise Instrumental, ARTEMED Editora, Porto Alegre, 2002.
- Harris DC. Análise Química Quantitativa, 7a Edição, LTC Editora, Rio de Janeiro, 2008.
- Malhotra P. Analytical Chemistry- Basic Techniques and Methods, Springer Nature Switzerland AG, Switzerland, 2023. https://doi.org/10.1007/978-3-031-26757-4
- Custodio R, Kubota LT, Andrade JC de. Lei dos processos de absorção da radiação, Rev. Chemkeys, 2000, 3: 5 pp. https://doi.org/10.20396/chemkeys.v0i3.9615
- Chance, B. Rapid and Sensitive Spectrophotometry. III. A Double Beam Apparatus, Rev. Sci. Instrum. 1951, 22: 634–638. https://doi.org/10.1063/1.1746021
- Shibata S, Furukawa M, Goto K. Dual Wavelength Spectrophotometry, Part I: General Method. Anal. Chim. Acta, 1969, 46: 271-279.
- Shibata S, Furukawa M, Goto K. Dual Wavelength Spectrophotometry, Part II: The Determination of Mixtures. Anal. Chim. Acta, 1971, 53: 369-377.
- Morton RA, Stubbs AL. Photoelectric spectrophotometry applied to the analysis of mixtures, and vitamin A oils. Analyst, 1946, 71: 348; (1947); Biochem. J., 1947, 41:525: APUD: Maddams, WF. Numerical methods of data analysis. IN: Knowles, A., Burgess, C. (eds), Practical Absorption Spectrometry: Techniques in Visible and Ultraviolet Spectrometry. Springer, Dordrecht, Chap 10, 1984. https://doi.org/10.1007/978-94-009-5550-9_10
- Bader M. A Systematic Approach to Standard Addition Methods in Instrumental Analysis, J. Chem Educ., 1980, 57: 703-706.
- Andrade JC de. Aplicação Quantitativa da Espectroscopia de Absorção Molecular I: Determinação de um Único Componente, Rev. Chemkeys, 2024, v.6(e024003), 9pp .
https://doi.org/10.20396/chemkeys.v6i00.19959
- Kelly WR, Pratt, KW, Guthrie, WF, Martin KR. - Origin and early history of Die Methode des Eichzusatzes or The Method of Standard Addition with primary emphasis on its origin, early design, dissemination, and usage of terms. Anal. Bioanal. Chem., (2011) 400:1805–1812.
doi: https://doi.org/10.1007/s00216-011-4908-4
- Hohn, H. Chemische Analysen mit dem Polarographen, Springer-Verlag, Berlin, 1937, p.51, APUD: Referência 13.
- Lingane JJ, Kerlinger H. Polarographic Determination of Nickel and Cobalt: Simultaneous Determination in Presence of Iron, Copper, Chromium, and Manganese, and Determination of Small Amounts of Nickel in Cobalt Compounds, Ind. Eng. Chem., 1941, 13: 77–80
- Bosch-Reig F, Campins-Falcó P. H-point standard additions method. Part 1. Fundamentals and application to analytical spectroscopy, Analyst, 1988, 113:1011–1016.
- Falcó PC, Bosch-Reig F, Bent AM. Spectrophotometric analysis of mixtures of two components with extensively or completely overlapping spectra by the H-point standard additions method. Fresenius J. Anal. Chem., 1990, 338: 16–21.
- Bosch-Reig F, Campins-Falcó P, Sevillano-Cabeza A, Herraez-Hernandez R, Molins-Legua C. Development of the H-Point Standard-Additions Method for Ultraviolet-visible Spectroscopic Kinetic Analysis of Two-Component Systems. Anal. Chem., 1991, 63: 2424-2429
https://doi.org/10.1021/ac00021a008
- Campins-Falcó P, Bosch-Reig F, Verdú-Andrés J. Evaluation and elimination of the "blank bias error" using the H-point standard addition method. Application to spectrophotometric determinations using absorbent blank. Anal. Chim. Acta, 1992, 270: 253-265.
- Bosch-Reig F, Verdú-Andrés J, Campins-Falcó P, Molins-Legua C. Study of the Behaviour of the Absorbent Blanks in Analytical Procedures by Using the H-Point Standard Additions Method (HPSAM). Talanta, 1994, 41: 39-52.
- Safavi A, Abdollahi H. Application of the H-point standard addition method to the speciation of Fe(II) and Fe(III) with chromogenic mixed reagents. Talanta, 2001, 54: 727–734.
- Abdollahi H, Zeinali S. Spectrophotometric study of complexation equilibria with H-point standard addition and H-point curve isolation methods. Talanta, 2004, 62: 151–163.
- Shams E, H. Abdollahi H, Yekehtaz M, Hajian R. H-Point Standard Addition Method in the Analysis by Differential Pulse Anodic Stripping Voltammetry: Simultaneous Determination of Lead and Tin. Talanta, 2004, 63: 359-364.
- Steliopoulos P. Extension of the standard addition method by blank addition, MethodsX, 2015, 2: 353–359. http://dx.doi.org/10.1016/j.mex.2015.09.001
- Verdú-Andrés J, Bosch-Reig F, Campins-Falcó P. H-Point Standard Additions Method for Analyte Determination in Ternary Mixtures, Analyst, 1995, 120: 299-304
- Pandey S, Powell JR, McHale MER, Acree Jr, WE. Quantitative Determination of Cr(III) and Co(II) Using a Spectroscopic H-Point Standard Addition Method, J. Chem. Educ., 1997, 74: 848-850.
- Baccan N, Andrade JC de, Godinho OES, Barone JS. Química Analítica Quantitativa Elementar, 3ª ed. revisada, 5ª reimpressão, São Paulo, Editora Edgard Blucher, 2008.
- Cotton FA, Wilkinson G. Advanced Inorganic Chemistry: A Comprehensive Text. Interscience Publishers, New York, 1972, p.644.
- Swift TJ. The Kinetics of Structural Transformation of Hydrated Cobalt(II) and Zinc(II) Ions in Aqueous Solution, Inorg. Chem., 1964, 3: 526-529.
- Andrade JC de, Custodio R. Quantidade de matéria e concentração. Revista Chemkeys, 2000, 3: 1-3. https://doi.org/10.20396/chemkeys.v0i3.9648
- Bassi, ABMS. Quantidade de substância, Revista Chemkeys, 2005, 9: 1-3.
https://doi.org/10.20396/chemkeys.v0i9.9659
- Saxberg BEH, Kowalski BR. Generalized Standard Addition Method, Anal. Chem., 1979, 51: 1031-1038.
-Raymond M, Jochum C, Kowalski B.R. Optimal Multicomponent Analysis Using the Generalized Standard Addition Method. J. Chem. Educ. 1983, 60: 1072-1073.
- Tortajada-Genaro LA, Campins-Falcó P, Blasco-Gómez F, Bosch-Reig F. The Generalized H-Point Standard-Additions Method to Determine Analytes Present in two Different Chemical Forms in Unknown Matrix Samples. Part I. General Considerations. Analyst, 2000, 125: 771–776
- Tortajada-Genaro LA, Campins-Falcó P, Blasco-Gómez F, Bosch-Reig F. The Generalized H-Point Standard-Additions Method to Determine Analytes Present in two Different Chemical Forms in Unknown Matrix Samples. Part II. Cr(VI) Determination in Water Samples by Absorption Spectrophotometry. Analyst, 2000, 125: 777–782.
- Adams, MJ. Chemometrics in Analytical Spectroscopy, RCS Analytical Spectroscopy Monographs, Royal Society of Chemistry, Thomas Graham House, Science Park, Cambridge, England, 1995.
- Eskandari H. H-Point Standard Addition Method: First Derivative Spectrophotometry for Simultaneous Determination of Palladium and Cobalt. Spectrochim. Acta, Part A, 2006, 63: 391–397.

Esta obra está bajo una licencia internacional Creative Commons Atribución-NoComercial-CompartirIgual 4.0.
Derechos de autor 2025 João Carlos de Andrade
