FTIR vibrational and 13 C NMR spectroscopic study of the effect on ionic transport behavior of NaClO 4 in N , N -dimethylacetamide and its binary mixtures with 2-aminoethanol

Ionics(2023)

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摘要
This study explores the vibrational and nuclear magnetic resonance spectra of free ions as well as those coordinated with sodium ions, which are commonly utilized to study ion-ion and ion-solvent interactions in electrolytic solutions of dipolar aprotic solvents. The spectral investigations suggested the origin of new bands due to solvent shell of sodium ions. The ion-solvent interactions were confirmed by the carbonyl symmetric stretch ring deformation bands in N , N -dimethylacetamide. The probability of new contact ion pairs between sodium and perchlorate ions with N,N-dimethylacetamide (DMA) increases on enhancing the increase in electrolytic concentration of sodium perchlorate in binary solvent mixtures. FTIR vibrational spectra and 13 C-NMR spectra of several electrolytic concentration solutions of sodium perchlorate (NaClO 4 ) were studied in pure DMA and its binary mixture with 2-aminoethanol (AE). The study investigates the vibrational spectra of free ions as well as those coordinated with Na + ions, which are widely used to study ion-ion and ion-solvent interactions in electrolytic solutions of dipolar aprotic solvents. The solutions of the salt at different concentrations were prepared in the molar ratio of NaClO 4 /AE/DMA (4:4:4) from 0.25 to 1.0 m. The vibrational spectroscopic and 13 C-NMR studies suggested the origin of new bands due to solvent shell of Na + ions, which is due to O=C–N deformation behavior. The study revealed that the Na + ions interacted through the coordinate bond to both N-atom of NH 4 + structure as well as oxygen atom of the C=O (carbonyl group) of amide. The interaction between Na + ions and solvent suggests preferential solvated by DMA in the binary solvent mixtures. The ion-solvent interactions were confirmed by the carbonyl symmetric stretch ring deformation bands in DMA. The new contact ion-pairs between Na + and ClO 4 − ions are more probable with increase in the concentration of sodium perchlorate in binary solvent mixtures. Graphical abstract
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关键词
Ion-solvent interaction, Preferential solvation of ions, Vibrational bands, Chemical shift, Bathochromic shift
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