Abstract
The complex formation of cobalt (II) with citrate (cit3–) and molybdate (MoO42–) ions in 0.3 mol·l-1 Na2SO4 solution at 20°C was studied by spectrophotometric method. It has been established that in a citrate-molybdate electrolyte at pH 9.0, cobalt (II) ions form, depending on the ratio of the equilibrium concentrations of ligands: molybdate [Co(MoO4)2]2–, citrate [Co(cit)2]4– and polyligand complexes [Co(cit)m(MoO4)n]+2-(3m+2n). The composition of [Co(cit)(MoO4)]3– polyligand complexes was determined, the equilibrium constant Ke of the reaction of their formation and their stability constant (lgβMLX = 5.86) The dependence of the degree of formation of molybdate, citrate and polyligand complexes of cobalt (II) in citrate-molybdate electrolyte on the logarithm of the ratio of equilibrium concentrations of ligands was calculated.
References
Kublanovsky V.S., Nikitenko V.N. Mechanism of the electrodeposition of palladium coatings from glycinate electrolytes. J. Electroanal. Chem. 2013. 699: 14–20. doi:
https://doi.org/10.1016/j.jelechem.2013.03.021
Kublanovsky V.S., Nikitenko V.N. Electrochemical properties of palladium (II) trans- and cis-diglycinate complexes. Electrochim. Acta. 2011. 56: 2110.
Yapontseva Y.S., Маltseva T.V. Кublanovsky V.S. Corrosion Properties of Electrolytic Coatings Based on СоW, CoRe, and CoWRe Alloys. Mater Sci. 2021. 56: 649–653.
Yapontseva Yu. S., Maltseva T.V., Kublanovsky V.S., Vyshnevskyi O.A. Electrodeposition of CoWRe alloys from polyligand citrate-pyrophosphate electrolyte. J. Alloys Compd. 2019. 803: 1–8.
Vernickaite E., Tsyntsaru N., Sobczak K., Cesiulis H. Electrodeposited tungsten-rich Ni-W, Co-W and Fe-W cathodes for efficient hydrogen evolution in alkaline medium. Electrochim. Acta. 2019. 318: 597–606.
Nikitenko V. М., Yapontseva Yu. S., Kublanovsky V. S. Determination of polyligand complexes of cobalt (II) with citrate and pyrophosphate ions. Ukrainian Chemistry Journal. 2022. 88: 113–122.
Gapon Yu. K., Sakhnenko N. D., Ved' M. V., Nenastina T. A. Patterns of cobalt (II) complexes formation. Visnyk of NTU “KhPI”. 2014. 51: 136–140.
Sillen L.G., Martell A. E. Stability Constants of Metal–Ion Complexes and Supplement. Special Publications No. 17 and 25. – London: The Chemical Society, Vol. 1, 1964; Vol. 2, 1971.
Zhao-Hui, Yuan-Fu Dong, and Hui-Lin Wan. Structural Diversities of Cobalt(II) Coordination Polymers whit Citric Acid. Crystal Growth & Desing. 2005. 5 (3): 1109.
Galloway K. W., Whyte A. M., Wernsdorfer W., Sanchez-Benitez J., Kamenev K. V., Parkin A., Peacock R. D., Murrie M. Cobalt(II) Citrate Cubane Single-Molecule Magnet. Inorg. Chem. 2008. 47: 7438.
Kotsakis N., Raptopoulou C.P., Tangoulis V., Terzis A., Giapintzakis J., Jakusch T., Kiss T., Salifoglou A. Correlations of Synthetic, Spectroscopic, Structural, and Speciation Studies in the Biologically Relevant Cobalt(II)-Citrate System: The Tale of the First Aqueous Dinuclear Cobalt(II)-Citrate Complex. Inorg. Chem. 2003. 42: 22.
Matezapetakis M., Dakanali M., Raptopoulou C.P. et al. Tangoulis V., Terzis A., Moon N., Giapintzakis J., Sulifoglou A. Synthetic, Spectroscopic, and Structural characterization of the first aqueous Cobalt(II)-Citrate complex: toward a potentially bioavailable form of cobalt in biologically relevant fluids. JBIC. 2000. 5: 469.
Wyrzykowski D., Chmurzynski L. Thermodynamics of Citrate complexation with Mn2+, Co2+, Ni2+ and Zn2+ ions J. Therm. Anal. Calorim. 2010. 102: 61.
Yahia Z, Hamada, Nabil Baayakly, Denisha George, and Troy Greer. Speciation of Molybdenum (VI)-Citric Acid Complexes in Aqueous Solutions . Synthesis and Reactivity, in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 2008. 38: 664-668.
Anderegg G., Malik S.C. Komplexone XLVII. The Stability of Palladium (II) Complexes with Aminopolycarbonate Anions. Helv. Chim. Acta. 1976. 59: 4981511.
Beck M., Nagypal I. Chemistry of complex equilibria. Budapest: Akademiai Kiado, 1989.
Drago R.S., Physical methods in chemistry. (Saunders company: Philadelphia, London, Toronto, 1978).
