Structure of Chloric Acid Hydrates and Equilibrium Composition of the HClO4–H2O System

IF 1.2 4区化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Structural Chemistry Pub Date : 2024-07-26 DOI:10.1134/s0022476624070059

V. D. Maiorov, I. S. Kislina, E. G. Tarakanova

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Abstract

Composition, structure, energy parameters, and existence regions of hydrate complexes formed in the HClO₄–H₂O system are studied by IR spectroscopy and quantum chemical methods. Three concentration-structural regions are determined. The HClO₄–H₂O solutions diluted to the 1:13.3 molar ratio of components contain \(\text{ClO}^{-}_4\) and \(\text{H}_5\text{O}^{+}_2\) solvate-separated ions, each hydrated by four water molecules. More concentrated solutions (1:13.3-1:5) contain hydrated ion pairs \(\text{ClO}^{-}_4\cdot\text{H}_5\text{O}^{+}_2\) that are contact ion pairs if the [HClO₄]:[H₂O] ratio falls within the region 1:9-1:5. As the acid concentration increases further up to the transition of the HClO₄–H₂O system into the solid phase, pair complexes are formed. The structure of the latter is formed by a cycle of two contact ion pairs \(\text{ClO}^{-}_4\cdot\text{H}_5\text{O}^{+}_2\) connected by two H-bonds. The solid phase consists of interacting polymer chains formed by \(\text{ClO}^{-}_4\cdot\text{H}_5\text{O}^{+}_2\) and \(\text{ClO}^{-}_4\cdot\text{H}_3\text{O}^{+}\) ion pairs.

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氯酸水合物的结构和 HClO4-H2O 系统的平衡成分

摘要利用红外光谱和量子化学方法研究了 HClO4-H2O 体系中形成的水合物复合物的组成、结构、能量参数和存在区域。确定了三个浓度-结构区域。稀释到 1:13.3 摩尔比的 HClO4-H2O 溶液含有（text{ClO}^{-}_4\）和（text{H}_5\text{O}^{+}_2\）溶解分离的离子，每个离子都由四个水分子水合。浓度较高的溶液（1:13.3-1:5）含有水合离子对 \(\text{ClO}^{-}_4\cdot\text{H}_5\text{O}^{+}_2\)，如果[HClO4]:[H2O]的比例在 1:9-1:5 的范围内，这些离子对就是接触离子对。随着酸浓度的进一步增加，直至 HClO4-H2O 体系过渡到固相，就会形成离子对复合物。后者的结构是由两个接触离子对循环形成的（\text{ClO}^{-}_4\cdot\text{H}_5\text{O}^{+}_2\) 由两个 H 键连接。固相由离子对（text{ClO}^{-}_4\cdot\text{H}_5\text{O}^{+}_2\ ）和（text{ClO}^{-}_4\cdot\text{H}_3\text{O}^{+} ）形成的相互作用聚合物链组成。

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来源期刊

Journal of Structural Chemistry 化学-无机化学与核化学

CiteScore

1.60

自引率

12.50%

发文量

142

审稿时长

8.3 months

期刊介绍： Journal is an interdisciplinary publication covering all aspects of structural chemistry, including the theory of molecular structure and chemical bond; the use of physical methods to study the electronic and spatial structure of chemical species; structural features of liquids, solutions, surfaces, supramolecular systems, nano- and solid materials; and the crystal structure of solids.