Abstract
This work is devoted to a detailed study of the complex formation of iron(II) and iron(III) ions with a series of alkyl- and phenyl-substituted salts of 6,7-dihydroxybenzopyrylium (R). Such complexes are of interest due to their potential application as analytical reagents for photometric determination of trace amounts of metals in aqueous systems, particularly in drinking water. The optimal conditions for the reactions in the studied chemical systems have been established: pH range of 3–7 and the analytical signal observed at λ = 550–580 nm. Under these conditions, the maximum color intensity of the complexes is achieved, which indicates their stability and reproducibility.
Using the methods of molar ratios and Bent – French analysis, it was shown that under optimal conditions the complex formation proceeds stepwise with the formation of stable compounds with a metal-to-ligand ratio of 1:3. This confirms the ability of iron cations to form polynuclear and multicoordinated structures with R. To characterize the spectrophotometric properties of the complexes, the molar absorption coefficient was determined, and the logarithm of the stability constant (lgβ) was calculated using the Komar method, which allowed a quantitative evaluation of the stability level of the obtained complexes.
Special attention was given to the study of the metrological characteristics of the proposed technique: the linearity intervals of the calibration curves, as well as the limits of detection and quantification of iron ions, were established. The practical application of the method was demonstrated on samples of tap water. The obtained results showed that the iron content complies with hygienic standards according to DSANPIN 2.2.4–171.10 and statistically agrees with the results obtained by an independent ICP-OES method, which confirms the reliability and reproducibility of the developed approach.
Thus, the conducted research not only expands the understanding of the complex formation of iron with 6,7-dihydroxybenzopyrylium derivatives but also demonstrates the practical applicability of these systems in drinking water quality control and environmental monitoring.
References
Cheng Q., Nengzi L., Bao L., Huang Y., Liu S., Cheng X., Zhang J. Distribution and genetic diversity of microbial populations in the pilot-scale biofilter for simultaneous removal of ammonia, iron and manganese from real groundwater. Chemosphere. 2017. 182: 450–457.
https://doi.org/10.1016/j.chemosphere. 2017.05.075
Almeida J. S., Souza O.C.C.O., Teixeira L.S.G. Determination of Pb, Cu and Fe in ethanol fuel samples by high-resolution continuum source electrothermal atomic absorption spectrometry by exploring a combination of sequential and simultaneous strategies. Microchemical Journal. 2018. 137: 22–26.
https://doi.org/10.1016/j.microc.2017.09. 012
Pohl P., Welna M., Szymczycha-Madeja A., Greda K., Jamroz P., Dzimitrowicz A. Response surface methodology assisted development of a simplified sample preparation procedure for the multielement (Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Sr and Zn) analysis of different coffee brews by means of inductively coupled plasma optical emission spectrometry. Talanta. 2022. 241: 123215.
https://doi.org/10.1016/j.talanta.2022. 123215
Xu L., Yang J., Xie L., Wang H., Yang Y., Huang C., Wu S. Evaluation of plasma condition, concentration effect, position effect, and nickel-doping method on non-matrix-matched Fe isotopic analysis by femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry. Spectrochimica Acta Part B: Atomic Spectroscopy. 2022. 189: 106374.
https://doi.org/10.1016/j.sab.2022.106374
Zhang Y., Zhang J., Chen H. Study on X-ray fluorescence measurement method for Fe content in secondary circuit sampling filter membranes of nuclear power plants. International Journal of Advanced Nuclear Reactor Design and Technology. 2025. 7: 341–350.
https://doi.org/10.1016/j.jandt.2025.08. 001
Sales T.N.S., Bosch-Santos B., Saiki M., Burimova A., Pereira L.F.D., Saxena R.N., Carbonari A.W. Low temperature synthesis of pure and Fe-doped HfSiO4: Determination of Si and Fe fractions by neutron activation analysis. Radiation Physics and Chemistry. 2019. 155: 287–290.
https://doi.org/10.1016/j.radphyschem. 2018.06.040
Snigur D.V., Chebotaryov O.M., Barbalat D.O., Shcherbakova T.M. Synthesis and chemical and analytical characteristics of fluorine-containing derivatives of 6,7-dihydroxybenzopyrylium chloride. Ukr. khym. zhurn. 2018. 84: 50–55. (in Ukrainian)
Chebotaryov O. M., Toporov S. V., Snigur D. V., Barbalat D. O. Derivatives of 6,7- and 7,8-dihydroxybenzopyrylium: synthesis, properties and analytical application (review). Bulletin of the Odessa National University. Chemistry. 2021. 26: 73–88. (in Ukrainian)
Zhukovetska O.M., Guzenko O.M., Mariychuk R.T., Snigur D.V. Complexation of Ge (IV) with 6,7-dihydroxybenzopyryllium derivatives and their analytical application. Journal of Chemistry and Technologies. 2023. 31: 460–467. (in Ukrainian)
https://doi.org/10.15421/jchemtech.v31i3.287489
Chebotarev A.N., Dubovyi V.P., Demchuk A.V., Barbalat D.A., Snigur D.V. Extraction-Spectrophotometric Determination of Cu(II) with 6,7-Dihydroxy-4-Methyl-2-Phenylbenzopyrylium Chloride in Waters of Various Categories. J. Water Chem. Technol. 2019. 41: 170–174.
http://dx.doi.org/10.3103/S1063455X1903 0068
Galangashi M. A., Kojidi S. F. M., Pendashteh A., Souraki B. A., Mirroshandel A. A. Removing iron, manganese and ammonium ions from water using greensand in fluidized bed process. Journal of Water Process Engineering. 2021. 39: 101714.
