Thermodynamic studies on the formation of ion-pair cobalt complexes in acetone–water mixtures

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics Pub Date : 2024-04-15 DOI:10.1016/j.jct.2024.107305

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Abstract

Dicarboxylic acids are stronoger acids than moncraboxylic acids and more soluble in water due to the presence of two carboxylic (–COOH) groups which are industrially important in producing polyester, polyamides, and polyols and as a pioneer to pharmaceutical additives. Succinic acid is one of the most prosperous chemicals that can be generated from renewable resources which can be used in the industries of antiseptics, cosmetics, sutures, drugs, solvents, detergents, herbicides, fungicides, synthetic resins, and inks. The ion–pair formation is very important in diferent applications, used widely for inorganic analysis by liquid chromatography and used for the heavy metal removal from waste water, so studing the ion-pair association constant (K_A) formed between chloropentamminecobalt(III) cation [CpX²⁺] and a different ligands of dicarboxylate anions (AC^2-), have been determined by EMF technique in different compositions of acetone aqueous media (0–44.20 wt% acetone) for succinic acid and for the other dicarboxylic acids (Maleic, Malonic and Malic) in the same solvent composition (40 wt% acetone) with in temperature range (30 – 60 °C). The thermodynamic association properties ( ${Δ G}_{A}^{°}$ , ${Δ H}_{A}^{°}$ and ${Δ S}_{A}^{°}$ ) have been estimated and discussed. Extra thermodynamic correlations like ${Δ H}_{A}^{°}$ - ${Δ S}_{A}^{°}$ and ${Δ G}_{A}^{°}$ - ${Δ G}_{I (o r I I)}^{°}$ (where I and II are mentioned for the first and second dissociation constant of the dicarboxylic acids) in different compositions of acetone aqueous media for succinic acid and in fixed solvent composition for the other dicarboxylic acids were examined in order to give more information about the behavior of solvent molecules and its effect on formation of the ion-pair molecules. In addition, The Gibbs free energy of transfer for the association process ${Δ G}_{A}^{°}$ (t) from water to acetone mixed solvents were calculated for succinic acid in order to indicate the spontaneous nature and the stabilization of the ion-pair by increasing the acetone weight percent in the mixed acetone – aqueous media. The linear correlation between pK_D values and the relative permittivity of acetone aqueous medium is in accordance to Born’s equation.

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丙酮-水混合物中离子对钴络合物形成的热力学研究

二羧酸是一种比单羧酸更强的酸，由于含有两个羧基（-COOH），因此更易溶于水，在生产聚酯、聚酰胺和多元醇方面具有重要的工业用途，也是医药添加剂的先驱。丁二酸是从可再生资源中生成的最重要的化学品之一，可用于防腐剂、化妆品、缝合线、药品、溶剂、洗涤剂、除草剂、杀菌剂、合成树脂和油墨等行业。离子对的形成在不同的应用中非常重要，广泛用于液相色谱法的无机分析，并用于去除废水中的重金属，因此研究了氯五胺钴(III)阳离子[CpX2+]与不同配体的二羧酸阴离子（AC2-）之间形成的离子对关联常数（KA）。20 wt%丙酮）中测定了琥珀酸和其他二羧酸（马来酸、丙二酸和苹果酸）在相同溶剂成分（40 wt%丙酮）和温度范围（30 - 60 °C）下的热力学关联特性（α-）。对热力学关联特性（ΔGA°、ΔHA° 和 ΔSA°）进行了估算和讨论。研究了琥珀酸在不同成分的丙酮水介质中以及其他二羧酸在固定溶剂成分中的ΔHA°- ΔSA°和ΔGA°- ΔGI(或II)°（其中 I 和 II 指二羧酸的第一和第二解离常数）等额外的热力学相关性，以提供更多有关溶剂分子的行为及其对离子对分子形成的影响的信息。此外，还计算了琥珀酸从水到丙酮混合溶剂的结合过程 ΔGA°(t) 的吉布斯自由转移能，以表明离子对的自发性质以及丙酮-水混合介质中丙酮重量百分比的增加对离子对的稳定作用。pKD 值与丙酮水介质的相对介电常数之间的线性关系符合玻恩方程。

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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.