Abstract
In the present study, the suitability of the complexation reaction between Co2+ and SCN– in water-organic solvent mixtures for the development of a laboratory experiment for undergraduate students was examined. From the measurement of absorbances of a series of solutions containing equal quantities of the metal (Co2+) but different quantities of the ligand (SCN–), the average ligand number and the equilibrium constant for the complex formation reaction are estimated using a Bent–French method. The students derive an expression for the relation between the experimentally determined values of the equilibrium constants and the stability constants of two adjacent complexes and estimate these stability constants. The experimental conditions and the used instrumentation drastically affect the measured average ligand number and equilibrium constant, and the calculated stability constants. However, the results are illustrative, suitable for educational purposes and reproducible by the various groups of students. The instructions for the students and the example data processing are provided.
References
Belyaev, B. A.; Zobnina, A. N.; Minina N. E; Tkachenko O. Y. Laboratornyj praktikum po himičeskoj termodinamike. Moscow: Moskovskaâ gosudarstvennaâ akademiâ tonkoj himičeskoj tehnologii imeni M. V. Lomonosova, 2002 (In Russian).
Bent, H. E.; French, C. L. The structure of ferric thiocyanate and its dissociation in aqueous solution. Journal of the American Chemical Society. 1941, 63 (2), 568–572. https://doi.org/10.1021/ja01847a059
Brown, W. B.; Steinbach, J. F. Spectrophotometic Determination of Cobalt after Extraction of Thiocyanate Complex with Acetylacetone. Analytical Chemistry. 1959, 31 (11), 1805–1806. https://doi.org/10.1021/ac60155a032
DeGrand, M. J.; Abrams, M. L.; Jenkins, J. L.; Welch, L. E. Gibbs energy changes during cobalt complexation: a thermodynamics experiment for the general chemistry laboratory. Journal of Chemical Education. 2011, 88 (5), 634–636. https://doi.org/10.1021/ed100833x
Dickinson, J. R.; Griffiths, T. R.; Potts, P. J. Some applications of computer techniques to absorption spectra. Thiocyanate-cobalt (II) interactions in dimethyl sulphoxide-1 Elucidation of the octahedral-tetrahedral equilibria. Journal of Inorganic and Nuclear Chemistry. 1975, 37 (2), 511–520. https://doi.org/10.1016/0022-1902(75)80365-4
Halpern, A.; Reeves, J. H. Experimental Physical Chemistry: a laboratory textbook. Glenview, Illinois, Boston, London: Scott, Foresman and Company, 1988.
Katzin, L. I.; Gebert, E. Spectrophotometric studies of cobalt (II) thiocyanate complexes in organic solvents. Journal of the American Chemical Society. 1950, 72 (12), 5659–5662. https://doi.org/10.1021/ja01168a083
Lundquist, R.; Markle, G. E.; Boltz, D. F. Ultraviolet spectrophotometric determination of cobalt. Analytical Chemistry. 1955, 27 (11), 1731-1733. https://doi.org/10.1021/ac60107a015
Morais, C. D. L.; Silva, S. R.; Vieira, D. S.; Lima, K. M. Integrating a smartphone and molecular modeling for determining the binding constant and stoichiometry ratio of the iron (II)–phenanthroline complex: an activity for analytical and physical chemistry laboratories. Journal of Chemical Education. 2016, 93 (10), 1760–1765. https://doi.org/10.1021/acs.jchemed.6b00112
Pilarczyk, M.; Grzybkowski, W.; Klinszporn, L. Ionization equilibria in solutions of cobalt (II) thiocyanate in N, N-dimethylformamide. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases. 1987, 83 (8), 2261–2269. https://doi.org/10.1039/F19878302261
Reddy, B. R.; Radhika, P.; Kumar, J. R.; Priya, D. N.; Rajgopal, K. Extractive spectrophotometric determination of cobalt (II) in synthetic and pharmaceutical samples using cyanex 923. Analytical Sciences. 2004, 20 (2), 345–349. https://doi.org/10.2116/analsci.20.345
Ren, J.; Lin, T.; Sprague, L. W.; Peng, I.; Wang, L. Q. Exploring chemical equilibrium for alcohol-based cobalt complexation through visualization of color change and UV–vis spectroscopy. Journal of Chemical Education. 2019, 97 (2), 509–516. https://doi.org/10.1021/acs.jchemed.9b00264
Rodríguez, H. B.; Mirenda, M. A simplified undergraduate laboratory experiment to evaluate the effect of the ionic strength on the equilibrium concentration quotient of the bromcresol green dye. Journal of Chemical Education. 2012, 89 (9), 1201–1204. https://doi.org/10.1021/ed200733k
Samayoa-Oviedo, H. Y.; Mehnert, S. A.; Espenship, M. F.; Weigand, M. R.; Laskin, J. Measurement of the speciation diagram of thymol blue using spectrophotometry. Journal of Chemical Education. 2022, 100 (2), 815–821. https://doi.org/10.1021/acs.jchemed.2c00746
Senise, P.; Perrier, M. Spectrophotometric investigation in the near ultraviolet of the cobalt (II) monothiocyanato complex. Journal of the American Chemical Society. 1958, 80 (16), 4194–4196. https://doi.org/10.1021/ja01549a019
Silber, H. B.; Murguia, M. A. Spectrophotometric investigations of the octahedral-tetrahedral equilibria in cobalt (II)-thiocyanate systems in aqueous methanol. Inorganic Chemistry. 1985, 24 (23), 3794–3802. https://doi.org/10.1021/ic00217a020
Singh, A. K.; Kumar, D. I. N. E. S. H.; Katyal, M. O. H. A. N. Spectrophotometric determination of cobalt (II) based on the ion-pair of tetrathiocyanatocobaltate (II) with neotetrazolium chloride. Analytica Chimica Acta. 1985, 172, 303–306. https://doi.org/10.1016/S0003-2670(00)82620-3
Velloso, N. C. F.; Neves, E. A.; Gutz, I. G. Spectrophotometric and potentiometric study of the cobalt (II)-thiocyanate system in aqueous medium. Polyhedron. 1985, 4 (12), 2043–2050. https://doi.org/10.1016/S0277-5387(00)86733-9
Wilson, A. M.; McFarland, O. K. Utilization of Tricaprylmethylammonium Thiocyanate as a Selective Extraction Agent in the Spectrophotometric Determination of Cobalt. Analytical Chemistry. 1963, 35 (3), 302–307. https://doi.org/10.1021/ac60196a009

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