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Thermodynamics of dissolution of non-electrolytes and electrolytes in non-aqueous solvents

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Abstract

Experimental results on the ΔH soln of noble gases, polar non-electrolyte molecules, porphyrins, their metallocomplexes and organic electrolytes in individual and mixed solvents are discussed. Xe was shown to indicate changes in solvent mixtures and also to exert a noticeable influence on the character of intermolecular interactions in solutions. The thermodynamic characteristics of the solvation of a series of non-polar and polar molecules are given and their dependence on the solvent nature, composition, isotopy and temperature is shown. For the first time the thermodynamic characteristics of porphyrins and metalloporphyrins in different non-aqueous solvents have been found by direct calorimetry. The possibility of axial coordination of porphyrin metallocomplexes is treated and a method is proposed for estimation of the influence of the functional substituents and the metal atom on the electronic effects in them. Compared to simple inorganic electrolyte solutions, the dependence of ΔH soln on various factors reveals a specific character.

Zusammenfassung

Experimentelle Daten zur Lösungswärme ΔH soln von Edelgasen, polaren Nichtelektrolyten, Porphyrinen und ihren Metallkomplexen und organischen Eletrolyten in einfachen und gemischten Lösungsmitteln werden diskutiert.

Es wird gezeigt, dass Xe nicht nur auf Veränderungen in der Zusammensetzung von Lösungsmittelmischungen anspricht, sondern selbst einen merklichen Einfluss auf den Charakter der intermolekularen Wechselwirkungen ausübt. Thermodynamische Charakteristika der Solvatation einer Reihe unpolarer und polarer Moleküle werden aufgeführt und die Abhängigkeit von der Natur, Zusammensetzung (auch isotopisch) und Temperatur des Lösungsmittels wird gezeigt. Erstmalig werden die thermodynamischen Charakteristika von Porphyrinen und Metallporphyrinen in verschiedenen Lösungsmitteln direkt kalorimetrisch bestimmt. Die Möglichkeit einer axialen Koordination an Metall-Porphyrin-Komplexen wird gezeigt und eine Methode zum Abschätzen des dabei wirkenden Einflusses der funktioneilen Substituenten und des Metallatoms auf die elektronischen Effekte vorgeschlagen. Verglichen mit einfachen anorganischen Elektrolyt-Lösungen ist' die Abhängigkeit von ΔH soln von verschiedenen Faktoren sehr substanzspezifisch.

резуме

Обсужден эксперимен тальный материал по ΔH pactb. благородных газо в, полярных неэлектро литов, порфиринов, их металл окомплексов и органи ческих электролитов в отдел ьных и смешанных раствори телях. Установлено, чт о ксенон показывает изменени я в смешанных растворителях и оказ ывает заметное влиян ие на характер межмолекул ярных взаимодействи й в растворах. Приведен ы термодинамические характеристики соль ватации ряда полярны х и неполярных неполярных молекул и показана их зависимость от приро ды растворителя, изотоп ного состава и температуры. Впервые методом прямой калор иметрии определены термодин амические характери стики для порфиринов и мета ллопорфиринов в нево дных растворителях. Опред елена возможность осевой координации в металлокомплексах п орфирина и предложен метод опре деления электронного влияни я заместителей и атом а металла в таких комплексах. По с равнению с простыми неорганическими эле ктролитными раствор ами, зависимость ΔH pactb. в изу ченных системах от различных факторо в показывает специфи ческий характер.

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  1. Institute of Chemistry of Non-Aqueous Solutions of the USSR Academy of Sciences, 153751, Ivanovo, USSR

    G. A. Krestov

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Krestov, G.A. Thermodynamics of dissolution of non-electrolytes and electrolytes in non-aqueous solvents. Journal of Thermal Analysis 33, 29–36 (1988). https://doi.org/10.1007/BF01914581

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