Role of Anions (Tetrafluoroborate, Perchlorate) of Tetrabutylammonium Salts in Determining Solvation Effects Prevailing in Industrially Essential Solvents Probed by Conductance and FT-IR Spectra

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• 作者：Ishani Banik ; Mahendra Nath Roy
• 刊名：Journal of Chemical & Engineering Data
• 出版年：2013
• 出版时间：December 12, 2013
• 年：2013
• 卷：58
• 期：12
• 页码：3378-3386
• 全文大小：440K
• 年卷期：v.58,no.12(December 12, 2013)
• ISSN：1520-5134

文摘

Molecular interactions of tetrabutylammonium salts prevailing in organic solvent media have been analyzed, both qualitatively and quantitatively, using conductometric studies and validating the results with Fourier transform infrared (FT-IR) measurements. From conductometric studies of tetrabutylammonium tetrafluoroborate [Bu₄NBF₄] and tetrabutylammonium perchlorate [Bu₄NClO₄] in nitromethane (NM), N-methyl formamide (NMF), and formamide (FA) at 298.15 K, it is revealed that high molecular interaction is mainly because of ion鈥揹ipole interactions, which is evidenced from the FT-IR measurements. The 1978 Fuoss conductance-concentration equation in terms of the limiting molar conductance (螞_o), the association constant (K_A), and the association diameter (R) was used to interpret the conductance data. Tetrabutylammonium tetraphenylborate [Bu₄NBPh₄] as the 鈥渞eference electrolyte鈥?was used to estimate the ionic contributions to the limiting molar conductance. The degree of interaction is articulated in terms of the association constant (K_A), which illustrates that viscosity of the solvent plays an important role in the ion鈥揹ipole interaction.The ionic interaction obtained is highest in the case of [Bu₄NBF₄] and FA in comparison to the other systems. The consequences have been considered in terms of dipole鈥揹ipole interactions, hydrogen bond formation, structural feature, and configurational theory. The FT-IR spectroscopic studies of the variational intensity of characteristic bands of the solvents have been undertaken, and the solvation phenomenon is evidenced by the change of band intensities owing to the occurrence of the electrolytes.