IR Spectroscopic and Quantum-Chemical Investigation of Perchlorate Anion Solvation in Acetonitrile

被引：9

作者：

Erkabaev, A. M. ^{[1
]}

Yaroslavtseva, T. V. ^{[1
]}

Popov, S. E. ^{[2
]}

Bushkova, O. V. ^{[1
]}

机构：

[1] Russian Acad Sci, Inst High Temp Electrochem, Ural Branch, Ekaterinburg 620219, Russia

[2] Yeltsin Ural Fed Univ, Ekaterinburg 620002, Russia

来源：

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A | 2015年 / 89卷 / 01期

关键词：

nonaqueous solution; dipolar aprotic solvent; ion solvation; perchlorate-anion; infrared spectroscopy; quantum-chemical calculations; ION-SOLVENT INTERACTIONS; FTIR; LITHIUM; LICLO4;

D O I：

10.1134/S0036024415010057

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The solvation of anions in solutions of tetrabutylammonium perchlorates in acetonitrile is studied by means of quantum-chemical calculations and Fourier-transform infrared spectroscopy. It is shown that perchlorate-anions form stable solvate complexes with acetonitrile molecules due to ion-dipole interactions between atoms of oxygen in the composition of anion and hydrogen atoms of methyl groups of solvent molecules. It is established that the energy of formation of anionic solvate complexes ClO4-(CH3CN)(n) (n = 1-4) is comparable in value that of cation solvate complexes Li+(CH3CN)(n) (n = 1-4) and is about one third of the latter. This requires us to consider the solvation of perchlorate anions along with the solvation of metal cations in acetonitrile. Spectroscopic signs of perchlorate anion solvation by acetonitrile molecules are analyzed.

引用

页码：76 / 81

页数：6

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