Thermodynamics of reactions of stepwise complex formation of silver(I) ion with pyridine in binary solvents

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL Journal of Chemical Thermodynamics Pub Date : 2023-11-17 DOI:10.1016/j.jct.2023.107210

Irina A. Kuz'mina , Mariia A. Kovanova

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Abstract

In this study, the enthalpies of stepwise complexation reactions between silver(I) ions and pyridine in methanol–acetonitrile mixed solvents (MeOH-AN, with molar fractions of AN varying from 0 to 1) were determined by the calorimetric method at 298.15 K. The analysis of the solvation contributions of the reactants to the alterations in the thermodynamic characteristics associated with the formation of [AgPy]⁺ and [AgPy₂]⁺ complexes as the solvent composition transitions, i.e. from methanol to its mixtures with acetonitrile (MeOH → χ_AN), from methanol to its mixtures with N,N-dimethylformamide (MeOH → χ_DMF) and from acetonitrile to its mixtures with dimethyl sulfoxide (AN → χ_DMSO) was carried out. The research methodology was based on the provisions of the solvation-thermodynamic approach, based on the relationship between changes in the thermodynamic characteristics of the reactions of complex formation and solvation of reagents with a change in the composition of the solvent.

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二元溶剂中银(I)离子与吡啶逐步络合反应的热力学

在298.15 K下，用量热法测定了银离子与吡啶在甲醇-乙腈混合溶剂(MeOH-AN, AN的摩尔分数为0 ~ 1)中逐级络合反应的焓。分析了溶剂组成从甲醇到与乙腈的混合物(MeOH→χAN)，从甲醇到与N,N-二甲基甲酰胺的混合物(MeOH→χDMF)，以及从乙腈到与二甲亚砜的混合物(AN→χDMSO)的转变过程中，反应物的溶剂化作用对[AgPy]+和[AgPy2]+络合物形成的热力学特性变化的贡献。研究方法基于溶剂-热力学方法的规定，基于络合物形成反应的热力学特性变化与试剂溶剂化随溶剂组成变化之间的关系。

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来源期刊

Journal of Chemical Thermodynamics 工程技术-热力学

CiteScore

5.60

自引率

15.40%

发文量

199

审稿时长

79 days

期刊介绍： The Journal of Chemical Thermodynamics exists primarily for dissemination of significant new knowledge in experimental equilibrium thermodynamics and transport properties of chemical systems. The defining attributes of The Journal are the quality and relevance of the papers published. The Journal publishes work relating to gases, liquids, solids, polymers, mixtures, solutions and interfaces. Studies on systems with variability, such as biological or bio-based materials, gas hydrates, among others, will also be considered provided these are well characterized and reproducible where possible. Experimental methods should be described in sufficient detail to allow critical assessment of the accuracy claimed. Authors are encouraged to provide physical or chemical interpretations of the results. Articles can contain modelling sections providing representations of data or molecular insights into the properties or transformations studied. Theoretical papers on chemical thermodynamics using molecular theory or modelling are also considered. The Journal welcomes review articles in the field of chemical thermodynamics but prospective authors should first consult one of the Editors concerning the suitability of the proposed review. Contributions of a routine nature or reporting on uncharacterised materials are not accepted.