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Calorimetric study of the thermodynamics of iron (III) complexation with nicotinic acid in aqueous ethanol

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Abstract

The changes in enthalpy of Fe(III) complex formation with nicotinic acid (ΔrH), the dissolution enthalpies of nicotinic acid in aqueous ethanol (mole fraction of the organic component varied in the range 0 < XEtOH < 0.7 mol fractions) were determined by calorimetry at the temperature 298.15 ± 0.01 K and I = 0.25 mol∙L−1 (NaClO4). The changes in enthalpy of transfer of nicotinic acid in a mixed solvent ΔtrH0(HNic) were calculated. An increase in the value of ΔtrH0(HNic) was observed. The changes in the enthalpy of transfer of the complexation reaction from water to a mixed solvent ΔtrH 0r are calculated. The significant increase in the exothermicity of the reaction is observed when a small amount of ethanol is added to water. With a further increase in the concentration of ethanol in the solution, a decrease in the heat effect is observed up to the transition to the endothermic region at XEtOH of more than 0.5 mol. fr. The experimental data are considered using an approach based on the thermodynamic characteristics of the solvation of each participant in the processes under study.The analysis of the contributions of reactants enthalpy of reaction into formation [FeHNic]3+ showed that the change in enthalpy of the reaction, when changing the solvent composition, is caused by the changes in solvation state of nicotinic acid at XEtOH from 0 to 0.1 mol. fr. and desolvation of the reaction product in more concentrated solutions (XEtOH > 0.1 mol. fr.).

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Acknowledgements

The study was carried out using the resources of the Center for Shared Use of Scientific Equipment of the ISUCT (with the support of the Ministry of Science and Higher Education of Russia, grant No. 075-15-2021-671) with the financial support of the Ministry of Science and Higher Education of the Russian Federation (project FZZW-2020-0009)

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  1. Ivanovo State University of Chemistry and Technology, Ivanovo, Russia

    Natalia N. Kuranova & Valentin A. Sharnin

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  1. Natalia N. Kuranova
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Correspondence to Natalia N. Kuranova.

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Kuranova, N.N., Sharnin, V.A. Calorimetric study of the thermodynamics of iron (III) complexation with nicotinic acid in aqueous ethanol. J Therm Anal Calorim 147, 5519–5524 (2022). https://doi.org/10.1007/s10973-022-11300-z

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  • DOI: https://doi.org/10.1007/s10973-022-11300-z

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